Resin sheet for forming insulating layer of semiconductor package substrate

Abstract

The present invention addresses the problem of providing a resin sheet from which a cured product having a low melt viscosity, a low dielectric loss tangent, a low dielectric constant, good crack resistance, and excellent stain removability can be obtained. The solution of the invention is a resin sheet for forming an insulating layer of a semiconductor package substrate, which comprises a support body and a resin composition layer arranged on the support body. The resin composition layer contains (A) a radically polymerizable group-containing compound having a carbodiimide structure, (B) one or more antioxidants selected from the group consisting of phenolic antioxidants and sulfur antioxidants, (C) a thermosetting resin, and (D) an inorganic filler.

Description

Technical Field

[0001] The present invention relates to a resin sheet for forming an insulating layer of a semiconductor package substrate, a resin sheet obtained using the resin composition, a printed wiring board, and a semiconductor device. Background Art

[0002] As a manufacturing technology for printed wiring boards, a manufacturing method using a stacking method in which insulating layers and conductive layers are alternately stacked is known. In the manufacturing method using the stacking method, the insulating layer is generally formed by curing a resin composition. For example, Patent Document 1 discloses a resin composition comprising an epoxy resin, an active ester compound, an inorganic filler, and an antioxidant. In addition, Patent Document 2 discloses a technology for forming an insulating layer by curing a resin composition comprising a carbodiimide compound.

[0003] Prior art literature Patent Literature Patent Document 1: Japanese Patent Application Laid-Open No. 2023-68335 Patent document 2: International Publication No. 2023 / 027013. Summary of the Invention

[0004] Technical problem to be solved by the invention In recent years, electronic components have been required to be micro-wiring for functional improvement. In order to achieve further miniaturization of wiring, it is necessary to bring a resin composition with a low melt viscosity, a low dielectric loss tangent and a low dielectric constant (relative dielectric constant). In addition, it is also necessary to bring a resin composition with an insulating layer having excellent crack resistance and excellent contamination removal. However, at the current stage, the status quo is to fail to meet all these requirements. Hereinafter, dielectric loss tangent and relative dielectric constant are sometimes referred to as dielectric properties.

[0005] An object of the present invention is to provide a resin sheet that can produce a cured product having low melt viscosity, low dielectric loss tangent and dielectric constant, excellent crack resistance, and excellent stain removability.

[0006] Technical solutions used to solve technical problems In order to solve the problems of the present invention, the present inventors conducted intensive research and found that by using a resin composition comprising (A) a compound containing a free radical polymerizable group having a carbodiimide structure, (B) one or more antioxidants selected from phenolic antioxidants and sulfur-based antioxidants, (C) a thermosetting resin, and (D) an inorganic filler, a cured product with low dielectric loss tangent and dielectric constant, good crack resistance and embedding properties, and excellent contamination removability can be obtained, thereby completing the present invention.

[0007] That is, the present invention includes the following contents. [1] A resin sheet for forming an insulating layer of a semiconductor package substrate, comprising a support and a resin composition layer provided on the support. The resin composition layer comprises: (A) a radical polymerizable group-containing compound having a carbodiimide structure, (B) one or more antioxidants selected from phenolic antioxidants and sulfur antioxidants, (C) thermosetting resin, and (D) Inorganic filling materials. [2] The resin sheet for forming an insulating layer of a semiconductor package substrate according to [1], wherein the content of the component (A) is 0.1% by mass or more and 25% by mass or less, based on 100% by mass of the resin component of the resin composition layer. [3] The resin sheet for forming an insulating layer of a semiconductor package substrate according to [1] or [2], wherein the content of the component (B) is 0.1% by mass or more and 10% by mass or less, based on 100% by mass of the resin component of the resin composition layer. [4] The resin sheet for forming an insulating layer of a semiconductor package substrate according to any one of [1] to [3], wherein the content of the component (C) is 50% by mass or more and 98% by mass or less, based on 100% by mass of the resin component of the resin composition layer. [5] The resin sheet for forming an insulating layer of a semiconductor package substrate according to any one of [1] to [4], wherein the content of the component (D) is 45% by mass or more and 85% by mass or less, when the non-volatile matter of the resin composition layer is 100% by mass. [6] The resin sheet for forming an insulating layer of a semiconductor package substrate according to any one of [1] to [5], wherein the melt viscosity of the resin composition layer is 3000 poise or less. [7] A semiconductor chip package substrate comprising an insulating layer formed from a cured product of a resin composition layer of a resin sheet for forming an insulating layer of a semiconductor package substrate according to any one of [1] to [6]. [8] A semiconductor device comprising the semiconductor chip package substrate described in [7].

[0008] Effects of the Invention According to the present invention, it is possible to provide a resin sheet capable of producing a cured product having low melt viscosity, low dielectric loss tangent and dielectric constant, excellent crack resistance, and excellent stain removability. DETAILED DESCRIPTION

[0009] Hereinafter, the present invention will be described in detail with reference to its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be modified as desired without departing from the scope of the claims and their equivalents.

[0010] [Resin sheet for forming an insulating layer of a semiconductor package substrate] The resin sheet for forming an insulating layer of a semiconductor package substrate of the present invention comprises a support and a resin composition layer disposed on the support. The resin composition layer comprises (A) a compound having a carbodiimide structure and containing a free radical polymerizable group, (B) one or more antioxidants selected from phenolic antioxidants and sulfur-based antioxidants, (C) a thermosetting resin, and (D) an inorganic filler. Using such a resin sheet, a cured product having low melt viscosity, low dielectric loss tangent and dielectric constant, excellent crack resistance, and superior contamination removability can be obtained.

[0011] The resin sheet for forming an insulating layer on a semiconductor chip package substrate of the present invention can be used as an insulating layer for a semiconductor package substrate. Examples of semiconductor package substrates include FC-CSP, MIS-BGA packages, ETS-BGA packages, fan-out WLP (wafer level package), fan-in WLP, fan-out PLP (panel level package), and fan-in PLP. Hereinafter, the "resin sheet for forming an insulating layer on a semiconductor package substrate" may be simply referred to as the "resin sheet."

[0012] <Support> The resin sheet has a support, and the support is bonded to one surface of the resin composition layer. Examples of the support include films made of plastic materials, metal foils, and release paper, with films made of plastic materials and metal foils being preferred.

[0013] When a film formed of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter also abbreviated as "PET") and polyethylene naphthalate (hereinafter also abbreviated as "PEN"), acrylics such as polycarbonate (hereinafter also abbreviated as "PC") and polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, and polyimide. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0014] When a metal foil is used as a support, examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. The copper foil may be a foil made of copper alone or an alloy of copper and other metals (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

[0015] The surface of the support that contacts the resin composition layer may be subjected to matte treatment, corona discharge treatment, or antistatic treatment.

[0016] In addition, as the support, a support with a release layer having a release layer on the surface bonded to the resin composition layer can be used. As a release agent for the release layer of the support with a release layer, for example, one or more release agents selected from alkyd resins, polyolefin resins, polyurethane resins and silicone resins can be mentioned. The support with a release layer can use commercially available products, for example, "SK-1", "AL-5", "AL-7" made by Lintec Co., Ltd., "LUMIRROR T60" made by Toray Industries, Ltd., "Purex" made by Teijin Limited, "Unipeel" made by Unitika Co., Ltd., etc., which are PET films having a release layer with an alkyd resin release agent as the main component, can be mentioned.

[0017] The thickness of the support is not particularly limited, but is preferably 1 μm or more, more preferably 5 μm or more, further preferably 10 μm or more, preferably 75 μm or less, more preferably 60 μm or less, and further preferably 50 μm or less. When a support with a release layer is used, the overall thickness of the support with the release layer is preferably within the above range.

[0018] <Resin composition layer> The resin sheet has a resin composition layer and is provided on a support. The insulating layer can be formed by thermally curing the resin composition layer. Usually, the insulating layer comprises a cured product of the resin composition layer, preferably a cured product comprising only the resin composition layer. The resin composition layer comprises (A) a compound containing a free radical polymerizable group having a carbodiimide structure, (B) one or more antioxidants selected from phenolic antioxidants and sulfur-based antioxidants, (C) a thermosetting resin, and (D) an inorganic filler. The resin composition layer may further comprise (E) a polymer component, (F) a curing accelerator, (G) other additives, and (H) a solvent as needed.

[0019] In the present invention, unless otherwise expressly stated, the content of each component in the resin composition layer is the value when the non-volatile component in the resin composition layer is set to 100% by mass. The non-volatile component refers to all non-volatile components in the components constituting the resin composition layer except for the solvent (H) described below. In addition, in the present invention, the resin component in the resin composition layer refers to the components in the non-volatile components of the resin composition layer excluding the inorganic filler.

[0020] -(A) Compounds containing a radically polymerizable group and having a carbodiimide structure- The resin composition layer contains (A) a compound having a carbodiimide structure and containing a free radical polymerizable group as component (A). By incorporating component (A) into the resin composition layer, while maintaining a low dielectric loss tangent and a low dielectric constant, the solubility in alkaline solutions is increased, thereby improving stain removability.

[0021] (A) The compound containing a free radical polymerizable group having a carbodiimide structure refers to a compound having one or more carbodiimide structures (-N=C=N-) in one molecule and containing one or more free radical polymerizable groups. Component (A) may also have one or more carbamate bonds (-O-CO-NH-) in one molecule. The carbodiimide structure, the free radical polymerizable group, and the carbamate bond may each have two or more in one molecule. In the case where the (C) thermosetting resin described below includes an epoxy resin, component (A) sometimes has a function of reacting with the epoxy resin to cure it. Component (A) may be used alone or in combination of two or more.

[0022] A free radical polymerizable group refers to a group having a free radical polymerizable ethylenically unsaturated bond. Examples of the free radical polymerizable group 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, methacryloyl, and maleimide (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl). The free radical polymerizable group is preferably present at the end of component (A).

[0023] The component (A) preferably contains a structural unit represented by the following formula (A-1) in addition to the radical polymerizable group. [Chemical Formula 1] In formula (A-1), Y represents a divalent hydrocarbon group which may have a substituent.

[0024] In formula (A-1), Y represents a divalent hydrocarbon group optionally having a substituent. The number of carbon atoms in the divalent hydrocarbon group in Y is usually 1 or more, preferably 2 or more, and usually 30 or less. The divalent hydrocarbon group may 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, and includes any of linear, branched, and cyclic hydrocarbon groups.

[0025] Preferred examples of the divalent hydrocarbon group in Y include an alkylene group, a cycloalkylene group, an arylene group, and a group obtained by combining these groups.

[0026] The number of carbon atoms in the alkylene group in Y is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 6, further preferably 1 to 4, further preferably 1 to 3. This number of carbon atoms does not include the number of carbon atoms in the substituents. Preferred examples of the alkylene group include methylene, ethylene, propylene, and butylene.

[0027] The number of carbon atoms in the cycloalkylene group in 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 in the substituent. Preferred examples of the cycloalkylene group include cyclopropylene, cyclobutylene, cyclopentylene, and cyclohexylene.

[0028] The arylene group in Y represents a group obtained by removing two hydrogen atoms from an aromatic ring of an aromatic hydrocarbon. The number of carbon atoms in the arylene group is preferably 6 to 24, more preferably 6 to 18, further preferably 6 to 14, and further preferably 6 to 10. This number of carbon atoms does not include the number of carbon atoms in the substituent. Preferred examples of the arylene group include phenylene, naphthylene, and anthrylene.

[0029] The substituent in Y is not particularly limited, and examples thereof include a halogen atom, an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy group, an alkyl-oxy-carbonyl group, an alkenyl-oxy-carbonyl group, an aryl-oxy-carbonyl group, an alkyl-carbonyl-oxy group, an alkenyl-carbonyl-oxy group, and an aryl-carbonyl-oxy group. Among them, the divalent hydrocarbon group in Y preferably has no substituent.

[0030] More preferably, Y represents a divalent saturated hydrocarbon group having 2 to 30 carbon atoms which may have a substituent, or a divalent unsaturated hydrocarbon group having 2 to 30 carbon atoms which may have a substituent. Even more preferably, Y represents a divalent saturated hydrocarbon group having 2 to 30 carbon atoms which may have a substituent and has a ring structure (e.g., a ring structure selected from a cycloalkane ring, a benzene ring, and a naphthalene ring), or a divalent unsaturated hydrocarbon group having 2 to 30 carbon atoms which may have a substituent and has a ring structure (e.g., a ring structure selected from a cycloalkane ring, a benzene ring, and a naphthalene ring).

[0031] Y in the formula (A-1) preferably represents a divalent group represented by the following formula (A-2). [Chemical Formula 2] In formula (A-2), Y a 、Y b and Y c Each independently represents a single bond, or C(R y )2; R yEach independently represents a hydrogen atom or a methyl group; Ring Y 1 and Ring Y 2 Each independently represents a cycloalkane ring having 4 to 10 carbon atoms and optionally having a substituent, a benzene ring optionally having a substituent, or a naphthalene ring optionally having a substituent; n y Indicates 0 or 1; * indicates the binding site.

[0032] In formula (A-2), Y a 、Y b and Y c Each independently represents a single bond, or C(R y )2. Better is Y a and Y c is a single bond and Y b Represents C(R y )2. R y Each independently represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

[0033] In formula (A-2), ring Y 1 and Ring Y 2 Each independently represents a cycloalkane ring having 4 to 10 carbon atoms which may have a substituent, a benzene ring which may have a substituent, or a naphthalene ring which may have a substituent. Ring Y is preferably 1 and Ring Y 2 Each independently represents a cycloalkane ring having 4 to 10 carbon atoms which may have a substituent. Examples of the cycloalkane ring having 4 to 10 carbon atoms include monocyclic saturated hydrocarbon rings such as a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, and a cyclodecane ring; bicyclic saturated hydrocarbon rings such as a bicyclo[2.2.1]heptane ring (norbornane ring), a bicyclo[4.4.0]decane ring (decalin ring), a bicyclo[5.3.0]decane ring, a bicyclo[4.3.0]nonane ring (hexahydroindan ring), a bicyclo[3.3.0]octane ring, and a bicyclo[3.3.1]nonane ring; and tricyclic saturated hydrocarbon rings such as a tricyclo[5.2.1.0 2,6 ] decane ring (tetrahydrodicyclopentadiene ring), tricyclic [3.3.1.1 3,7 ] decane ring (adamantane ring) and other tricyclic saturated hydrocarbon rings. More preferably, ring Y 1 and Ring Y 2 Each independently represents a cyclohexane ring optionally having a substituent. As substituents in the cycloalkane ring, benzene ring and naphthalene ring, there are no particular limitations, and examples thereof include halogen atoms, alkyl groups, alkenyl groups, aryl groups, aryl-alkyl groups (alkyl groups substituted with aryl groups), alkyl-aryl groups (aryl groups substituted with alkyl groups), 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. Among them, ring Y 1and Ring Y 2 An unsubstituted cyclohexane ring is particularly preferred.

[0034] Specific examples of Y include divalent groups represented by formulae (Y1) to (Y14), and particularly preferred is a divalent group represented by formula (Y1). In formulae (Y1) to (Y14), * represents a bonding site. [Chemical Formula 3]

[0035] In a preferred example, relative to 100 mass % of the mass of all molecules of component (A), the proportion of the structural unit represented by formula (A-1) contained in component (A) is preferably 50 mass % or more, more preferably 60 mass % or more, further preferably 70 mass % or more, particularly preferably 80 mass % or more, and can be 90 mass % or more.

[0036] The component (A) is preferably a compound represented by the formula (A-3). [Chemical Formula 4] In formula (A-3), R each independently represents a hydrogen atom or a methyl group; X 1 Each independently represents a carbonyl group, a methylene group, a phenylene group, or a phenylene-methylene group; X 2 Each independently represents a divalent saturated hydrocarbon group having 2 to 4 carbon atoms; Z each independently represents a divalent saturated hydrocarbon group having 2 to 300 carbon atoms, which may be substituted, or a divalent unsaturated hydrocarbon group having 2 to 300 carbon atoms, which may be substituted; a each independently represents an integer of 0 or 1 or greater; b each independently represents 1 or greater; c each independently represents 1 or greater; d each represents 0 or 1 or greater; and Y each independently represents the above-mentioned groups. Units a, b, c, and d may be the same or different in each unit.

[0037] In formula (A-3), R each independently represents a hydrogen atom or a methyl group.

[0038] In formula (A-3), X 1 Each independently represents a carbonyl group, a methylene group, a phenylene group, or a phenylene-methylene group (the bonding direction is not particularly limited, but the phenylene side is preferably bonded to the C in "RC"). 1 Each independently represents a methylene group or a carbonyl group. Phenylene-methylene groups include 1,2-phenylene-methylene groups, 1,3-phenylene-methylene groups, and 1,4-phenylene-methylene groups.

[0039] In formula (A-3), X 2Each independently represents a divalent saturated hydrocarbon group having 2 to 4 carbon atoms. The divalent saturated hydrocarbon group may be linear, branched, or cyclic. Specific examples of the divalent saturated hydrocarbon group having 2 to 4 carbon atoms include linear 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 ethylidene, propylidene, isopropylidene, and ethylmethylmethylene. In one embodiment, X 2 Each independently represents preferably a divalent saturated hydrocarbon group having 2 or 3 carbon atoms, more preferably an ethylene group (-CH2-CH2-).

[0040] In formula (A-3), Z each independently represents a divalent saturated hydrocarbon group having 2 to 300 carbon atoms, which may have a substituent, or a divalent unsaturated hydrocarbon group having 2 to 300 carbon atoms, which may have a substituent. Preferably, Z each independently represents 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, Z each independently represents a divalent hydrocarbon group having 300 or less carbon atoms, which has a structural unit selected from the following formulas (Z1) to (Z8). Even more preferably, Z each independently represents a divalent hydrocarbon group having 300 or less carbon atoms, which is formed from a structural unit selected from the following formulas (Z1) to (Z8). [Chemical Formula 5]

[0041] Z each independently represents more preferably a divalent hydrocarbon group having 300 or less carbon atoms having a structural unit represented by formula (Z1), and further preferably represents a divalent hydrocarbon group having 300 or less carbon atoms formed from structural units selected from formulae (Z1) to (Z8) and having at least a structural unit represented by formula (Z1). Among them, Z is particularly preferably a divalent hydrocarbon group having 300 or less carbon atoms represented by the following formula (Z-1). [Chemical Formula 6] In formula (Z-1), n z represents an integer greater than or equal to 1, and * represents a binding site.

[0042] In formula (A-3), a each independently represents 0 or an integer of 1 or greater, preferably 0 or an integer of 1 to 10, more preferably 0 or 1.

[0043] In formula (A-3), b represents the average degree of polymerization of the carbodiimide group. Each b independently represents 1 or more, preferably an integer of 1 or more, more preferably an integer of 1-100, further preferably an integer of 1-10 or an integer of 1-10.

[0044] In formula (A-3), c represents the average degree of polymerization of the optionally substituted divalent saturated hydrocarbon group having 2 to 300 carbon atoms represented by Z. Each c independently represents 1 or more, preferably an integer of 1 or more, more preferably 1 to 100, further preferably an integer of 1 to 100, 1 to 10, an integer of 1 to 10, or 1.

[0045] In formula (A-3), d represents the average degree of polymerization of the group represented by Z and the polycarbodiimide. d each independently represents 0 or 1 or more, preferably 0, or an integer of 1 to 100, more preferably 0, or an integer of 1 to 100, further preferably 0, or an integer of 1 to 10.

[0046] Component (A) may contain an isocyanate group (-N=C=O) in the molecule due to its preparation method. The isocyanate group content (also referred to as "NCO content") in component (A) is preferably 5 mass% or less, more preferably 4 mass% or less, further preferably 3 mass% or less, further preferably 2 mass% or less, particularly preferably 1 mass% or less or 0.5 mass% or less.

[0047] As specific examples of component (A), compounds represented by the following (S1) to (S5) can be cited. However, component (A) is not limited to these specific examples. In the formula, b' is the same as b in formula (A-3), d' is the same as d in formula (A-3), and e' is the same as c in formula (A-3). It should be noted that in formula (S3), as the e' unit, only 1,2-addition structural units are represented, but 1,4-addition structural units (cis and trans) are also included. [Chemical Formula 7]

[0048] (A) component can be prepared by currently known methods. As a known method, for example, carbodiimidization reaction can be carried out by mixing and stirring diisocyanate compounds such as dicyclohexylmethane -4,4'- diisocyanate and carbodiimidization catalysts such as 3-methyl -1-phenyl-2-phospholene -1- oxide to obtain isocyanate-terminated polycarbodiimide. Then, the obtained isocyanate-terminated polycarbodiimide, a compound with free radical polymerizable groups such as (meth) acryloyl, and other polymerizable compounds such as two-terminal hydroxy polybutadiene used as needed are reacted. If it is a person skilled in the art, reaction temperature, reaction time, etc. can be appropriately set.

[0049] The weight average molecular weight of the component (A) is preferably at least 500, more preferably at least 600, further preferably at least 700, further preferably at least 800, further preferably at least 900, further preferably at least 1000, and is preferably at most 10000, more preferably at most 8000, further preferably at most 7000, further preferably at most 6000. The weight average molecular weight of the component (A) can be measured by gel permeation chromatography (GPC) (polystyrene conversion).

[0050] When the non-volatile component in the resin composition layer is set to 100 mass%, the content of component (A) is preferably 0.1 mass% or more, more preferably 0.3 mass% or more, further preferably 0.5 mass% or more, preferably 10 mass% or less, more preferably 8 mass% or less, further preferably 5 mass% or less.

[0051] When the resin component in the resin composition layer is set to 100% by mass, the content of component (A) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, preferably 25% by mass or less, more preferably 20% by mass or less, further preferably 15% by mass or less.

[0052] - (B) one or more antioxidants selected from phenolic antioxidants and sulfur antioxidants - The resin composition layer contains (B) one or more antioxidants selected from phenolic antioxidants and sulfur antioxidants as the (B) component. The (B) component does not include substances belonging to the above-mentioned (A) component. If the resin composition layer is made to contain the (B) component, the crosslinking degree during solidification is reduced, so the stress of the solidified material is relaxed. As a result, the generation of cracks in the solidified material can be suppressed. In addition, by making the resin composition layer contain the (B) component, the melt viscosity of the resin composition layer can be reduced, and as a result, the embedding property can be improved, and the rise of the dielectric loss tangent is also suppressed. One (B) component can be used alone, or two or more can be used in combination.

[0053] The phenolic antioxidant is an antioxidant having a phenolic hydroxyl group in the molecule, and is preferably a hindered phenolic antioxidant. The phenolic antioxidant preferably has a group represented by the following formula (B-1). [Chemical Formula 8] In formula (B-1), R 1 and R 2 Each independently represents a hydrogen atom or a hydrocarbon group.

[0054] R 1The hydrocarbon group shown is a monovalent hydrocarbon group. The number of carbon atoms in the hydrocarbon group is usually 1 or more, preferably 2 or more, more preferably 3 or more, and preferably 12 or less, more preferably 8 or less, and further preferably 6 or less.

[0055] R 1 The hydrocarbon group shown may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof. In addition, the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. Furthermore, the aliphatic hydrocarbon group may be a linear or branched chain hydrocarbon group, a cyclic hydrocarbon group (i.e., an alicyclic hydrocarbon group), or a combination of a chain hydrocarbon group and a cyclic hydrocarbon group. Among them, an aliphatic hydrocarbon group is preferred, a saturated aliphatic hydrocarbon group is more preferred, and a branched or cyclic aliphatic hydrocarbon group is further preferred.

[0056] As R 1 Preferred specific examples of the hydrocarbon group represented by , include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, and heptyl, and cycloalkyl groups such as cyclopentyl and cyclohexyl. When the hindered phenol compound contains two or more groups represented by formula (B-1) in one molecule, R 1 It can be the same or different.

[0057] In formula (B-1), R 2 represents a hydrogen atom or a hydrocarbon group. 2 The range can be compared with R 1 In addition, R 1 With R 2 They may be the same or different. However, in the group represented by formula (B-1), R 1 and R 2 At least one of is a hydrocarbon group. Furthermore, it is preferred that R 1 and R 2 Both of these are hydrocarbon groups.

[0058] The phenolic antioxidant may contain only one group represented by formula (B-1) in one molecule, or may contain two or more groups. When one molecule of the phenolic antioxidant contains two or more groups represented by formula (B-1), the groups represented by formula (B-1) may be the same or different.

[0059] The phenolic antioxidant preferably contains an aliphatic hydrocarbon group in combination with a group represented by formula (B-1). Examples of the aliphatic hydrocarbon group include alkyl groups such as methyl and ethyl, and alkylene groups such as methylene and ethylene. Furthermore, the group represented by formula (B-1) is preferably combined with the aliphatic hydrocarbon group.

[0060] Examples of the phenolic antioxidant include 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 4,4',4"-(1-methylpropyl-3-ylidene)tris(6-tert-butyl-m-cresol), 6,6'-di-tert-butyl-4,4'-butylidenedi-m-cresol, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}- 2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), 2,2-thio-diethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, N,N'-bis-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionylhexamethylenediamine, etc.

[0061] Commercially available phenolic antioxidants may be used. Examples of commercially available products include "AO-20," "AO-30," "AO-40," "AO-50," "AO-60," "AO-60G," "AO-80," and "AO-330" manufactured by ADEKA Corporation, and "HP-300" manufactured by Kawaguchi Chemical Industry Co., Ltd.

[0062] As the sulfur-based antioxidant, an antioxidant having a sulfur atom in the molecule can be used, and one molecule may contain only one sulfur atom or two or more sulfur atoms.

[0063] The sulfur-based antioxidant preferably contains, in addition to a sulfur atom, an ester bond (-OC(=O)-) and an aliphatic hydrocarbon group. Examples of the aliphatic hydrocarbon group include an alkyl group. The alkyl group is preferably a long-chain alkyl group, and the number of carbon atoms in the alkyl group is preferably 5 or more, more preferably 8 or more, further preferably 10 or more, and preferably 30 or less, more preferably 20 or less, and further preferably 15 or less.

[0064] The sulfur-based antioxidant is preferably any of a thiol-based antioxidant and a thioether-based antioxidant, and is more preferably a thioether-based antioxidant from the viewpoint of controlling the reactivity in the system.

[0065] Examples of the sulfur-based antioxidant include 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], ditridecyl-3,3'-thiodipropionate, thiododecyl-3,3'-thiodipropionate, and thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0066] Commercially available sulfur-based antioxidants may be used, such as "AO-412S," "AO-503," and "AO-26" manufactured by ADEKA Corporation, and "Irganox PS800," "Irganox 1726," and "Irganox 1035" manufactured by BASF Japan.

[0067] When the non-volatile component in the resin composition layer is set to 100 mass%, the content of component (B) is preferably 0.01 mass% or more, more preferably 0.03 mass% or more, further preferably 0.05 mass% or more, preferably 3 mass% or less, more preferably 2 mass% or less, further preferably 1 mass% or less, or 0.8 mass% or less.

[0068] When the resin component in the resin composition layer is set to 100% by mass, the content of component (B) is preferably 0.1% by mass or more, more preferably 0.15% by mass or more, further preferably 0.2% by mass or more, 0.5% by mass or more, 1% by mass or more, 1.5% by mass or more, preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less.

[0069] When the content of the (A) component when the non-volatile component in the resin composition layer is 100% by mass is a, and the content of the (B) component when the non-volatile component in the resin composition layer is 100% by mass is b, a / b is preferably 100 or less, more preferably 80 or less, further preferably 70 or less, 50 or less, 30 or less, 10 or less, or 5 or less, preferably 0.3 or more, more preferably 0.5 or more, and further preferably 1 or more, 1.5 or more, or 2 or more, from the viewpoint of reducing the melt viscosity and the dielectric loss tangent.

[0070] -(C) Thermosetting resin- The resin composition layer contains a thermosetting resin (C) as component (C). The thermosetting resin (C) as component (C) does not include components (A) to (B). The type of thermosetting resin (C) is not particularly limited as long as it can be cured by heat. The thermosetting resin (C) may be used alone or in combination of two or more.

[0071] Examples of the thermosetting resin (C) include epoxy resins, radical polymerizable resins, phenolic resins, cyanate resins, active ester resins, carbodiimide resins (excluding those included in component (A)), acid anhydride resins, amine resins, benzoxazine resins, and thiol resins. The thermosetting resins may be used alone or in combination of two or more.

[0072] From the viewpoint of significantly obtaining the effects of the present invention, (C) the thermosetting resin is preferably a combination of an epoxy resin and a resin that can react with the epoxy resin to solidify the resin composition layer. Hereinafter, the resin that can react with the epoxy resin to solidify the resin composition layer is sometimes referred to as a "curing agent". As a curing agent, for example, phenolic resins, cyanate resins, active ester resins, carbodiimide resins, acid anhydride resins, amine resins, benzoxazine resins, thiol resins, etc. can be cited. Among them, as a curing agent, phenolic resins and active ester resins are preferred. One curing agent can be used alone or two or more can be used in combination. As an embodiment, the thermosetting resin includes an epoxy resin and a phenolic resin.

[0073] Epoxy resin is a thermosetting resin having an epoxy group. Examples of epoxy resins include tetramethyl bisphenol epoxy resin (biphenyl epoxy resin), biphenyl epoxy resin, naphthalene epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AF epoxy resin, dicyclopentadiene epoxy resin, trisphenol epoxy resin, naphthol novolac epoxy resin, phenol novolac epoxy resin, tert-butyl catechol epoxy resin, naphthol epoxy resin, anthracene epoxy resin, glycidylamine epoxy resin. Epoxy resins, glycidyl ester epoxy resins, cresol novolac epoxy resins, phenol aralkyl epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexane epoxy resins, cyclohexanedimethanol epoxy resins, naphthyl ether epoxy resins, trimethylol epoxy resins, tetraphenylethane epoxy resins, isocyanurate epoxy resins, phenol phthalimidine epoxy resins, etc. The epoxy resins may be used alone or in combination of two or more.

[0074] The (C) thermosetting resin preferably includes an epoxy resin having two or more epoxy groups in one molecule. The proportion of the epoxy resin having two or more epoxy groups in one molecule relative to 100 mass% of the non-volatile component of the epoxy resin is preferably 50 mass% or more, more preferably 60 mass% or more, particularly preferably 70 mass% or more.

[0075] Epoxy resins include those that are liquid at 20°C (hereinafter referred to as "liquid epoxy resins") and those that are solid at 20°C (hereinafter referred to as "solid epoxy resins"). The resin composition layer may contain only the liquid epoxy resin, only the solid epoxy resin, or a combination of the liquid epoxy resin and the solid epoxy resin.

[0076] The liquid epoxy resin is preferably one having two or more epoxy groups in one molecule.

[0077] As liquid epoxy resins, preferred are bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexanedimethanol type epoxy resins, and epoxy resins having a butadiene structure; more preferred are glycidyl amine type epoxy resins, bisphenol A type epoxy resins, and bisphenol F type epoxy resins; and even more preferred are naphthalene type epoxy resins, bisphenol A type epoxy resins, and bisphenol F type epoxy resins.

[0078] Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation, "828US", "828EL", "jER828EL", "825", and "EPIKOTE" manufactured by Mitsubishi Chemical Corporation, and "HP4032D", "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation. 828EL" (bisphenol A type epoxy resin), "jER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER152" (novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "630", "630LSD" and "604" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "ED-523T" (GLYCIROL type epoxy resin) manufactured by ADEKA Corporation, "EP-3950L" and "EP-3980S" (glycidylamine type epoxy resin) manufactured by ADEKA Corporation, "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA Corporation, "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel Chemical Materials Co., Ltd., Nagase Examples include "EX-721" (glycidyl ester epoxy resin) manufactured by ChemteX Corporation, "CELLOXIDE 2021P" (alicyclic epoxy resin with an ester skeleton) manufactured by Daicel Corporation, "PB-3600" (epoxy resin with a butadiene structure) manufactured by Nippon Soda Co., Ltd., "JP-100" and "JP-200" (epoxy resin with a butadiene structure (epoxidized polybutadiene resin)), and "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane epoxy resin) manufactured by Nippon Steel Chemicals Co., Ltd. These resins may be used alone or in combination.

[0079] The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups in one molecule, more preferably an aromatic solid epoxy resin having three or more epoxy groups in one molecule.

[0080] As solid epoxy resins, preferred are tetramethylbisphenol-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, naphthol novolac-type epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, naphthyl ether-type epoxy resins, anthracene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol AF-type epoxy resins, phenol aralkyl-type epoxy resins, tetraphenylethane-type epoxy resins, and phenol benzopyrrolidone-type epoxy resins, and better still are biphenyl-type epoxy resins.

[0081] Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC Corporation, "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC Corporation, "N-690" (cresol novolac-type epoxy resin) manufactured by DIC Corporation, "N-695" (cresol novolac-type epoxy resin) manufactured by DIC Corporation, "HP-7200", "HP-7200HH", "HP-7200H", and "HP-7200L" (dicyclopentadiene-type epoxy resin) manufactured by DIC Corporation, and "HP-7200HH" and "HP-7200H" manufactured by DIC Corporation. "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthyl ether type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Steel Chemical Materials Co., Ltd.'s "ESN475V", "ESN4100V" (naphthalene type epoxy resin), Nippon Steel Chemical Materials Co., Ltd.'s "ESN485" (naphthol type epoxy resin), Nippon Steel Chemical Materials Co., Ltd.'s "ESN375" (dihydroxynaphthalene type epoxy resin), Mitsubishi Chemical Corporation's "YX4000H", "YX4000", "YX4000HK", "YL7890" (biphenyl type epoxy resin), Mitsubishi Chemical Corporation's "YL6121" (biphenyl type epoxy resin), Mitsubishi Chemical Corporation's "YX8800" (anthracene type epoxy resin), Mitsubishi Examples of the epoxy resins include "YX7700" (phenol aralkyl type epoxy resin) manufactured by Osaka Gas Chemical Co., Ltd., "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YX7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1010" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation, and "WHR991S" (phenol benzopyrrolidone type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. These resins may be used alone or in combination of two or more.

[0082] When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the mass ratio thereof (liquid epoxy resin:solid epoxy resin) is preferably from 1:0.01 to 1:20, more preferably from 1:0.05 to 1:10, particularly preferably from 1:0.1 to 1:7.

[0083] The epoxy equivalent of the epoxy resin is preferably 50 g / eq. to 5000 g / eq., more preferably 60 g / eq. to 3000 g / eq., further preferably 80 g / eq. to 2000 g / eq., and particularly preferably 110 g / eq. to 1000 g / eq. The epoxy equivalent represents the mass of the resin per equivalent of epoxy groups. This epoxy equivalent can be measured in accordance with JIS K7236.

[0084] The weight average molecular weight (Mw) of the epoxy resin is preferably from 100 to 5000, more preferably from 250 to 3000, further preferably from 400 to 1500. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0085] When the non-volatile component in the resin composition layer is set to 100 mass%, the content of the epoxy resin as the (C) thermosetting resin is preferably 1 mass% or more, more preferably 3 mass% or more, further preferably 5 mass% or more, preferably 30 mass% or less, more preferably 25 mass% or less, further preferably 20 mass% or less.

[0086] When the resin component in the resin composition layer is set to 100 mass%, the content of the epoxy resin as the (C) thermosetting resin is preferably 20 mass% or more, more preferably 25 mass% or more, further preferably 30 mass% or more, preferably 50 mass% or less, more preferably 45 mass% or less, and particularly preferably 40 mass% or less.

[0087] The type of radical polymerizable resin as component (C) is not particularly limited as long as it has one or more, preferably two or more, radical polymerizable unsaturated groups in one molecule. Examples of radical polymerizable resins include resins having one or more radical polymerizable unsaturated groups selected from maleimide, vinyl, allyl, styryl, vinylphenyl, acryloyl, methacryloyl, fumaryl, and maleoyl groups. From the perspective of significantly achieving the effects of the present invention, the radical polymerizable resin is preferably a maleimide resin, a (meth)acrylic resin, or a styrene resin.

[0088] The type of maleimide resin is not particularly limited as long as it has one or more, preferably two or more, maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl) in one molecule. Examples of maleimide resins include (1) "BMI-3000J", "BMI-5000", "BMI-1400", "BMI-1500", "BMI-1700", and "BMI-689" (all manufactured by Designer Molecules Co., Ltd.). Inc.), "SLK6895-T90" (manufactured by Shin-Etsu Chemical Co., Ltd.), etc., containing a maleimide resin having an aliphatic skeleton (preferably an aliphatic skeleton having 36 carbon atoms derived from dimerized diamine), (2) a maleimide resin containing an indane skeleton as described in the Japan Invention Association's Public Technical Bulletin No. 2020-500211, (3) a maleimide resin containing an aromatic ring skeleton directly bonded to the nitrogen atom of the maleimide group, such as "MIR-3000-70MT" (manufactured by Nippon Kayaku Co., Ltd.), "BMI-4000" (manufactured by Yamato Chemicals Co., Ltd.), and "BMI-80" (manufactured by KI Chemicals Co., Ltd.).

[0089] As a (meth)acrylic resin, as long as it has one or more, preferably two or more (meth)acryloyl groups in one molecule, its type is not particularly limited, and it can be a monomer or an oligomer. Here, the term "(meth)acryloyl" refers to the general term for acryloyl and methacryloyl. As methacrylic resins, in addition to (meth)acrylate monomers, for example, "A-DOG" (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), "DCP-A" (manufactured by Kyoeisha Chemical Co., Ltd.), "NPDGA", "FM-400", "R-687", "THE-330", "PET-30", "SA9000" (manufactured by SABIC Innovative Plastics (SABIC) Co., Ltd.), "DPHA" (all manufactured by Nippon Kayaku Co., Ltd.) and other (meth)acrylic resins can also be cited.

[0090] Styrene resins are compounds having one or more, preferably two or more, vinyl groups directly bonded to aromatic carbon atoms. Examples of styrene resins include low molecular weight (molecular weight less than 1000) styrene 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 resins such as vinylbenzyl-modified polyphenylene ether resins and styrene-divinylbenzene copolymers. Examples of commercially available styrene resins include "ODV-XET (X03)", "ODV-XET (X04)", and "ODV-XET (X05)" (styrene-divinylbenzene copolymers) manufactured by Nippon Steel Chemical Materials Co., Ltd., and "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether resins) manufactured by Mitsubishi Gas Chemical Co., Ltd.

[0091] When the non-volatile component in the resin composition layer is set to 100 mass%, the content of the free radical polymerizable resin as the (C) thermosetting resin is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, further preferably 1 mass% or more, preferably 10 mass% or less, more preferably 5 mass% or less, further preferably 3 mass% or less.

[0092] When the resin component in the resin composition layer is set to 100 mass%, the content of the free radical polymerizable resin as the (C) thermosetting resin is preferably 1 mass% or more, more preferably 2 mass% or more, further preferably 3 mass% or more, preferably 15 mass% or less, more preferably 12 mass% or less, further preferably 10 mass% or less.

[0093] As phenolic resin, a compound having one or more, preferably two or more, hydroxyl groups bound to aromatic rings such as benzene rings and naphthalene rings in one molecule can be used. When combined with an epoxy resin, the phenolic resin can react with the epoxy resin to solidify the resin composition layer, so it is sometimes referred to as a "phenolic curing agent". From the viewpoint of significantly obtaining the effect of the present invention, the phenolic resin is preferably a phenolic resin with a phenolic structure. In addition, from the viewpoint of close adhesion, a nitrogen-containing phenolic resin is preferably used, and a phenolic resin containing a triazine skeleton is more preferably used. Among them, from the viewpoint of significantly obtaining the effect of the present invention, a linear phenolic resin containing a triazine skeleton is preferably used. Specific examples of phenolic resins include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Chemicals Co., Ltd.; "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd.; "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", and "SN-395" manufactured by Nippon Steel Chemicals Co., Ltd.; and "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", "TD-2090-60M", and "KA-1163" manufactured by DIC Corporation.

[0094] As active ester resins, it is generally preferred to use compounds having ester groups with more than two highly reactive groups in one molecule, such as phenolic esters, thiophenolic esters, N-hydroxylamine esters, and esters of heterocyclic hydroxyl compounds. Active ester resins can react with epoxy resins to solidify the resin composition layer when combined with epoxy resins, so they are sometimes referred to as "active ester curing agents". The active ester resins are preferably compounds obtained by the condensation reaction of carboxylic acid compounds and / or thiocarboxylic acid compounds with hydroxyl compounds and / or thiol compounds. In particular, from the viewpoint of improving the high-temperature reflow soldering expansion tolerance, active ester resins obtained from carboxylic acid compounds and hydroxyl compounds are preferably active ester resins obtained from carboxylic acid compounds and phenolic compounds and / or naphthol compounds, and more preferably active ester resins obtained from carboxylic acid compounds and phenolic compounds and / or naphthol compounds. As carboxylic acid compounds, for example, benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc. can be cited. Examples of the phenolic compound or naphthol compound 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-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyrogallol, dicyclopentadiene-type diphenolic compounds, and novolac resins. Here, the term "dicyclopentadiene-type diphenolic compound" refers to a diphenolic compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

[0095] Specifically, preferred active ester resins include dicyclopentadiene-type active ester resins, naphthalene-type active ester resins containing a naphthalene structure, active ester resins containing acetylated products of novolac resins, and active ester resins containing benzoylated products of novolac resins. Among these, at least one selected from dicyclopentadiene-type active ester resins and naphthalene-type active ester resins is more preferred. Preferred dicyclopentadiene-type active ester resins include active ester resins containing a dicyclopentadiene-type diphenol structure.

[0096] Examples of commercially available active ester resins include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000L-65TM", "HPC-8000-65T", "EXB-8000H", and "EXB-8000L-65TM" (manufactured by DIC Corporation) as active ester curing agents containing a dicyclopentadiene-type diphenol structure, and "EXB-9416-70BK", "EXB-8100L-65T", "HPC-8150-62T", "EXB-8150L-65T", "EXB-8100L-65T", and "EXB -8" (manufactured by DIC Corporation), "EXB9401" (manufactured by DIC Corporation) as a phosphorus-containing active ester curing agent, "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent containing an acetylated product of a linear phenolic resin, "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) and "EXB-8500-65T" (manufactured by DIC Corporation) as active ester curing agents containing a benzoylated product of a linear phenolic resin, and "PC1300-02-65T" and "PC1300-02-65MA" (manufactured by Air Water Co., Ltd.) as active ester curing agents containing a styrene group and a naphthalene structure.

[0097] As the cyanate resin, a compound having one or more, preferably two or more, cyanate groups in one molecule can be used. When combined with an epoxy resin, the cyanate resin can react with the epoxy resin to cure the resin composition layer, and is therefore sometimes referred to as a "cyanate curing agent." Examples of the cyanate resin include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenylcyanate), 4,4'-ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylene))benzene, bis(4-cyanatephenyl)sulfide, and bis(4-cyanatephenyl)ether; polyfunctional cyanate resins derived from phenol novolac resins and cresol novolac resins; and prepolymers in which a portion of these cyanate resins is triazinated. Specific examples of cyanate resins include "PT30" and "PT60" manufactured by Arxada (both are novolac-type multifunctional cyanate resins), "BA230" and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate is triazine-treated to form a trimer), etc.

[0098] As the carbodiimide resin (excluding the substance included in component (A)), a compound having one or more, preferably two or more, carbodiimide structures per molecule and having no radically polymerizable groups can be used. When combined with an epoxy resin, a carbodiimide resin can react with the epoxy resin to cure the resin composition layer, and is therefore sometimes referred to as a "carbodiimide-based curing agent."

[0099] Specific examples of the carbodiimide resin include: aliphatic biscarbodiimides such as tetramethylene-bis(tert-butylcarbodiimide) and cyclohexanebis(methylene-tert-butylcarbodiimide); aromatic biscarbodiimides such as phenylene-bis(xylylcarbodiimide); aliphatic polycarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), and poly(isophoronecarbodiimide); poly(phenylenecarbodiimide), poly Aromatic polycarbodiimides such as (naphthylenecarbodiimide), poly(tolylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylenediphenylenecarbodiimide), and poly[methylenebis(methylphenylene)carbodiimide] are also included.

[0100] Examples of commercially available carbodiimide resins include "CARBODILITE V-02B", "CARBODILITE V-03", "CARBODILITE V-04K", "CARBODILITE V-07", and "CARBODILITE V-09" manufactured by Nisshinbo Chemical Co., Ltd., and "Stabaxol P", "Stabaxol P100", "Stabaxol P400", and "Hycasyl 510" manufactured by LANXESS.

[0101] As the acid anhydride resin, a compound having one or more, preferably two or more, acid anhydride groups in one molecule can be used. When combined with an epoxy resin, the acid anhydride resin can react with the epoxy resin to cure the resin composition layer, so it is sometimes called an "acid anhydride curing agent". Specific examples of the acid anhydride resin 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-furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, Polymer-type acid anhydrides such as benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), and styrene-maleic acid resin obtained by copolymerizing styrene and maleic acid. Commercially available products of the acid anhydride resin include, for example, "HNA-100", "MH-700", "MTA-15", "DDSA", and "OSA" manufactured by Shin Nippon Rika Co., Ltd., "YH-306" and "YH-307" manufactured by Mitsubishi Chemical Corporation, "HN-2200" and "HN-5500" manufactured by Risenoko Co., Ltd., and "EF-30", "EF-40", "EF-60", and "EF-80" manufactured by Cray Valley Co., Ltd.

[0102] As the amine resin, a compound having one or more, preferably two or more, amino groups per molecule can be used. When combined with an epoxy resin, the amine resin can react with the epoxy resin to cure the resin composition layer, and is therefore sometimes referred to as an "amine curing agent." Examples of the amine resin include aliphatic amines, polyether amines, alicyclic amines, and aromatic amines, with aromatic amines being preferred. The amine resin is preferably a primary amine or a secondary amine, more preferably a primary amine. Specific examples of the amine resin include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, m-phenylenediamine, m-xylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxy phenyl)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. Examples of commercially available amine resins include "SEIKACURE-S" manufactured by Seika Corporation, "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", and "KAYAHARD AS" manufactured by Nippon Kayaku Co., Ltd., "EPICURE W" manufactured by Mitsubishi Chemical Corporation, and "DTDA" manufactured by Sumitomo Seika Chemicals Co., Ltd.

[0103] Benzoxazine resins, when combined with epoxy resins, react with the epoxy resin to cure the resin composition layer, and are therefore sometimes referred to as "benzoxazine-based curing agents." Specific examples of benzoxazine resins include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Corporation, "HFB2006M" manufactured by Showa Highpolymer Co., Ltd., and "Pd" and "Fa" manufactured by Shikoku Chemicals Co., Ltd.

[0104] When combined with an epoxy resin, a thiol resin can react with the epoxy resin to cure the resin composition layer, and is therefore sometimes referred to as a "thiol curing agent." Examples of thiol resins include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), and tris(3-mercaptopropyl)isocyanurate.

[0105] The active group equivalent weight of the curing agent is preferably 50 g / eq. to 3000 g / eq., more preferably 100 g / eq. to 1000 g / eq., further preferably 100 g / eq. to 500 g / eq., particularly preferably 100 g / eq. to 300 g / eq. The active group equivalent weight is the mass of the curing agent per equivalent of active groups.

[0106] The weight average molecular weight (Mw) of the curing agent is preferably from 100 to 5000, more preferably from 250 to 3000, further preferably from 400 to 1500. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0107] When the number of epoxy groups of the epoxy resin is 1, the number of active groups of the curing agent is preferably 0.01 or more, more preferably 0.05 or more, further preferably 0.1 or more, preferably 5 or less, more preferably 3 or less, and particularly preferably 2 or less. The "number of epoxy groups of the epoxy resin" represents the value obtained by adding up all the values ​​obtained by dividing the mass of the non-volatile components of the epoxy resin present in the resin composition layer by the epoxy equivalent. In addition, the "number of active groups of the curing agent" represents the value obtained by adding up all the values ​​obtained by dividing the mass of the non-volatile components of the curing agent present in the resin composition layer by the active group equivalent.

[0108] When the non-volatile component in the resin composition layer is set to 100 mass%, the content of the curing agent as the (C) thermosetting resin is preferably 1 mass% or more, more preferably 3 mass% or more, further preferably 5 mass% or more, preferably 30 mass% or less, more preferably 25 mass% or less, further preferably 23 mass% or less.

[0109] When the resin component in the resin composition layer is set to 100 mass%, the content of the curing agent as the (C) thermosetting resin is preferably 30 mass% or more, more preferably 35 mass% or more, further preferably 40 mass% or more, preferably 60 mass% or less, more preferably 55 mass% or less, further preferably 50 mass% or less.

[0110] When the non-volatile component in the resin composition layer is set to 100 mass%, the content of the (C) thermosetting resin is preferably 2 mass% or more, more preferably 4 mass% or more, further preferably 6 mass% or more, 8 mass% or more, or 10 mass% or more, and preferably 65 mass% or less, more preferably 50 mass% or less, further preferably 45 mass% or less, or 40 mass% or less.

[0111] When the resin component in the resin composition layer is set to 100 mass%, the content of the (C) thermosetting resin is preferably 50 mass% or more, more preferably 60 mass% or more, further preferably 70 mass% or more, preferably 98 mass% or less, more preferably 93 mass% or less, further preferably 90 mass% or less.

[0112] When the non-volatile component in the resin composition layer is set to 100% by mass, the total content of component (A), component (B) and component (C) is preferably 15% by mass or more, more preferably 20% by mass or more, further preferably 25% by mass or more, preferably 55% by mass or less, more preferably 50% by mass or less, further preferably 45% by mass or less, 40% by mass or less, or 35% by mass or less.

[0113] - (D) Inorganic fillers - The resin composition layer contains an inorganic filler (D) as the component (D). Using a resin composition layer containing the component (D) can produce a cured product with a low dielectric loss tangent. The inorganic filler (D) may be used alone or in combination of two or more in any ratio.

[0114] (D) The inorganic filler is contained in the resin composition layer in the form of particles. As the material of the inorganic filler (D), an inorganic compound is used. As the material of the inorganic filler (D), for example, silica, aluminum oxide, 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, calcium zirconate, zirconium phosphate and zirconium tungstate phosphate, etc., can be mentioned. Among them, silica is particularly preferred. As silica, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. can be mentioned. In addition, spherical silica is preferred as silica.

[0115] Examples of commercially available inorganic fillers (D) include "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemicals Co., Ltd.; "YC100C," "YA050C," "YA050C-MJE," "YA010C," "SC2500SQ," "SO-C4," "SO-C2," and "SO-C1" manufactured by Yaduma Co., Ltd.; "UFP-30," "DAW-03," and "FB-105FD" manufactured by DENKA Corporation; "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.

[0116] The average particle size of the inorganic filler (D) is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, further preferably 3 μm or less, even more preferably 2 μm or less, and particularly preferably 1.5 μm or less. The lower limit of the average particle size of the inorganic filler (D) is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, further more preferably 0.1 μm or more, and particularly preferably 0.2 μm or more.

[0117] (D) The average particle size of the inorganic filler can be measured by a laser diffraction scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be made on a volume basis by using a laser diffraction scattering particle size distribution measuring device, and the median particle size can be measured as the average particle size. The determination sample can be obtained by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing the sample for 10 minutes by ultrasonic wave. For the determination sample, a laser diffraction particle size distribution measuring device is used, and the light source wavelength is blue and red. The particle size distribution of the volume basis of the inorganic filler is measured in a flow cell manner, and the average particle size is calculated as the median particle size according to the obtained particle size distribution. As a laser diffraction particle size distribution measuring device, for example, "LA-960" made by Horiba Manufacturing Co., Ltd. can be cited.

[0118] (D) The specific surface area of ​​the inorganic filler is not particularly limited, but is preferably 0.1 m 2 / g or more, more preferably 0.5m 2 / g or more, more preferably 1m 2 / g or more, particularly preferably 3m 2 The upper limit of the specific surface area of ​​the inorganic filler (D) is not particularly limited, but is preferably 100 m 2 / g or less, preferably 70m 2 / g or less, more preferably 50m 2 / g or less, and even better is 30m 2 / g or less, particularly preferably 10m 2 The specific surface area of ​​the inorganic filler can be obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring apparatus (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) according to the BET method and calculating the specific surface area by the BET multipoint method.

[0119] From the viewpoint of improving moisture resistance and dispersibility, the (D) inorganic filler is preferably treated with a surface treatment agent. Examples of the surface treatment agent include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate coupling agents. The surface treatment agent may be used alone or in any combination of two or more.

[0120] Examples of commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBE903” (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “SZ-31” (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM103” (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM-4803” (long-chain epoxy-type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., and “KBM-7103” (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.

[0121] From the viewpoint that the dispersibility of inorganic filler improves, the degree of the surface treatment carried out by surface treatment agent is preferably within the prescribed range. Specifically, inorganic filler 100% by mass is preferably surface treated by a surface treatment agent of 0.2% by mass to 5% by mass, more preferably surface treated by a surface treatment agent of 0.2% by mass to 3% by mass, and further more preferably surface treated by a surface treatment agent of 0.3% by mass to 2% by mass.

[0122] The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of ​​the inorganic filler is preferably 0.02 mg / m 2 More than 0.1 mg / m 2 More than 0.2 mg / m2 On the other hand, from the viewpoint of increasing the melt viscosity of the resin composition layer and preventing the increase in the melt viscosity in the sheet form, it is preferably 1.0 mg / m 2 Below, more preferably 0.8mg / m 2 Below, more preferably 0.5 mg / m 2 the following.

[0123] (D) The amount of carbon per unit surface area of ​​the inorganic filler can be measured after the surface-treated inorganic filler is cleaned with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK is added as a solvent to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid component, the amount of carbon per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

[0124] When the non-volatile component in the resin combination layer is made into 100 mass %, the content of (D) inorganic filler is preferably more than 45 mass %, more preferably more than 50 mass %, further more preferably more than 55 mass %, more than 60 mass %, more than 65 mass %. The upper limit is preferably below 85 mass %, more preferably below 80 mass %, further more preferably below 75 mass %.

[0125] -(E)Polymer components- The resin composition layer may contain a polymer component (E) as the component (E). The polymer component (E) does not include components (A) to (D). By including the component (E) in the resin composition layer, stress in the resin composition layer is relaxed, resulting in a cured product with improved crack resistance. The components (E) may be used alone or in combination of two or more.

[0126] As the component (E), a component having a high weight average molecular weight can be used. Examples of such components include polyimide resins, phenoxy resins, polyimide resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyamide-imide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, and polyester resins.

[0127] The weight average molecular weight (Mw) of the component (E) is preferably greater than 5,000, more preferably at least 8,000, further preferably at least 10,000, particularly preferably at least 20,000, and is preferably at most 100,000, more preferably at most 70,000, further preferably at most 60,000, particularly preferably at most 50,000.

[0128] The polyimide resin may be a resin having an imide structure, and generally includes a resin obtained by an imidization reaction of a diamine compound and an acid anhydride.

[0129] The diamine compound used for preparing the polyimide resin is not particularly limited, and examples thereof include aliphatic diamine compounds and aromatic diamine compounds.

[0130] Examples of the aliphatic diamine compound include linear aliphatic diamine compounds such as 1,2-ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-hexanediamine, 1,5-diaminopentane, and 1,10-diaminodecane; branched aliphatic diamine compounds such as 1,2-diamino-2-methylpropane, 2,3-diamino-2,3-butane, and 2-methyl-1,5-diaminopentane; alicyclic diamine compounds such as 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, and 4,4'-methylenebis(cyclohexylamine); and dimer acid-type diamines (hereinafter also referred to as "dimer diamines"). Dimer acid-type diamines are diamine compounds in which the two terminal carboxyl groups (-COOH) of dimer acid are replaced with aminomethyl groups (-CH2-NH2) or amino groups (-NH2). Dimer acid is a known compound obtained by dimerizing unsaturated fatty acids (preferably unsaturated fatty acids having 11 to 22 carbon atoms, particularly preferably unsaturated fatty acids having 18 carbon atoms), and its industrial production process is largely standardized in the industry.

[0131] Examples of the aromatic diamine compound include phenylenediamine compounds, naphthalenediamine compounds, and diphenylamine compounds.

[0132] Phenylenediamine compounds are compounds consisting of a benzene ring with two amino groups, wherein the benzene ring may optionally have one to three substituents. The substituents are not particularly limited. Specific examples of phenylenediamine compounds include 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 3,5-diaminobiphenyl, and 2,4,5,6-tetrafluoro-1,3-phenylenediamine.

[0133] A naphthalene diamine compound is a compound consisting of a naphthalene ring with two amino groups. The naphthalene ring may optionally have one to three substituents. The substituents are not particularly limited. Specific examples of naphthalene diamine compounds include 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,6-diaminonaphthalene, and 2,3-diaminonaphthalene.

[0134] A diphenylamine compound refers to a compound containing two aniline structures within the molecule, wherein the two benzene rings in the two aniline structures may each optionally have 1 to 3 substituents. The substituents are not particularly limited. The two aniline structures in the diphenylamine compound may be directly bonded and / or bonded via one or two linker structures having 1 to 100 skeletal atoms selected from carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms. Diphenylamine compounds also include compounds in which the two aniline structures are bonded via two bonds.

[0135] Specific examples of the "linker structure" in the diphenylamine compound include -NHCO-, -CONH-, -OCO-, -COO-, -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2-, -CH(CH3)-, -C(CH3)2-, -C(CF3)2-, -CH=CH-, -O-, -S-, -C O-, -SO2-, -NH-, -Ph-, -Ph-Ph-, -C(CH3)2-Ph-C(CH3)2-, -O-Ph-O-, -O-Ph-Ph-O-, -O-Ph-SO2-Ph-O-, -O-Ph-C(CH3)2-Ph-O-, -C(CH3)2-Ph-C(CH3)2-, groups represented by the following formulas (I) and (II), and groups formed by combinations thereof. In this specification, "Ph" represents 1,4-phenylene, 1,3-phenylene, and 1,2-phenylene. [Chemical Formula 9]

[0136] In one embodiment, specific examples of the diphenylamine compound include 4,4'-diamino-2,2'-bis(trifluoromethyl)-1,1'-biphenyl, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 4-aminophenyl 4-aminobenzoate, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis(4-aminophenyl)propane, 4,4'-(hexafluoroisopropylidene)diphenylamine, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenyl)

[0014] Examples of the following substances include hexafluoropropane, α,α-bis[4-(4-aminophenoxy)phenyl]-1,3-diisopropylbenzene, α,α-bis[4-(4-aminophenoxy)phenyl]-1,4-diisopropylbenzene, 4,4'-(9-fluorenylidene)diphenylamine, 2,2-bis(3-methyl-4-aminophenyl)propane, 2,2-bis(3-methyl-4-aminophenyl)benzene, 4,4'-diamino-3,3'-dimethyl-1,1'-biphenyl, 4,4'-diamino-2,2'-dimethyl-1,1'-biphenyl, 9,9'-bis(3-methyl-4-aminophenyl)fluorene, and 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindane.

[0137] As the diamine compound, a commercially available compound may be used, or a compound synthesized by a known method may be used. The diamine compound may be used alone or in combination of two or more.

[0138] The acid anhydride used to prepare the polyimide resin is not particularly limited, but in a preferred embodiment, it is aromatic tetracarboxylic dianhydride. Examples of aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, naphthalenetetracarboxylic dianhydride, anthracenetetracarboxylic dianhydride, and diphthalic dianhydride, with diphthalic dianhydride being preferred.

[0139] Pyromellitic dianhydride is a dianhydride of benzene having four carboxyl groups, wherein the benzene ring may optionally have 1 to 3 substituents. Here, the substituents are preferably selected from halogen atoms, cyano groups and -X 330 -R 330 (The same as the definition of the following formula (E-1)) Specific examples of pyromellitic dianhydride include trimellitic dianhydride and 1,2,3,4-pyromellitic dianhydride.

[0140] Naphthalenetetracarboxylic dianhydride refers to a naphthalene dianhydride having four carboxyl groups, wherein the naphthalene ring may optionally have 1 to 3 substituents. Here, the substituents are preferably selected from halogen atoms, cyano groups and -X 330 -R 330(The same as the definition of the following formula (E-1)) Specific examples of naphthalenetetracarboxylic dianhydride include 1,4,5,8-naphthalenetetracarboxylic dianhydride and 2,3,6,7-naphthalenetetracarboxylic dianhydride.

[0141] Anthracenetetracarboxylic dianhydride refers to an anthracene dianhydride having four carboxyl groups, wherein the anthracene ring may optionally have 1 to 3 substituents. Here, the substituents are preferably selected from halogen atoms, cyano groups and -X 330 -R 330 (The same as the definition of the following formula (E-1)) The substituents are: anthracenetetracarboxylic dianhydride, specifically, 2,3,6,7-anthracenetetracarboxylic dianhydride and the like.

[0142] Diphthalic anhydride refers to a compound containing two phthalic anhydrides in the molecule, and further, the two benzene rings in the two phthalic anhydrides may each have 1 to 3 substituents. Here, as the substituent, it is preferably selected from halogen atoms, cyano groups and -X 330 -R 330 The two phthalic anhydrides in diphthalic dianhydride may be directly bonded or bonded via a linker structure having 1 to 100 skeletal atoms selected from carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms.

[0143] As diphthalic dianhydride, the compound represented by Formula (E-1) is mentioned, for example. [Chemical Formula 10] Where R 11 and R 12 Each independently represents a halogen atom, a cyano group, a nitro group or -X 13 -R 13 , X 13 Each independently represents a single bond, -NR 13 '-, -O-, -S-, -CO-, -SO2-, -NR 13 'CO-、-CONR 13 '-, -OCO- or -COO-, R 13 Each independently represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, R 13 'respectively independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, Y represents a single bond or a linker structure having 1 to 100 skeletal atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms, n1 and m1 each independently represent an integer of 0 to 3.

[0144] Y preferably has a linker structure having 1 to 100 backbone atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms.

[0145] The "linker structure" in Y has 1 to 100 backbone atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms. The "linker structure" is preferably -[A-Ph] a -A-[Ph-A] b -represented by a divalent group; wherein A each independently represents a single bond, -(substituted or unsubstituted alkylene)-, -O-, -S-, -CO-, -SO2-, -CONH-, -NHCO-, -COO- or -OCO-, and a and b each independently represent an integer from 0 to 2, preferably 0 or 1.

[0146] Specific examples of the "linker structure" in Y include -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH(CH3)-, -C(CH3)2-, -O-, -CO-, -SO2-, -Ph-, -O-Ph-O-, -O-Ph-SO2-Ph-O-, -O-Ph-C(CH3)2-Ph-O-, etc., and preferably -O-Ph-C(CH3)2-Ph-O-.

[0147] Specific examples of diphthalic dianhydrides include 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenyl ethertetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, and 2,3,3'-diphenyltetracarboxylic dianhydride. ,4'-benzophenone tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl sulfone tetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl)sulfone dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylene-4,4'-diphthalic dianhydride, 2,2-propylene-4,4'-diphthalic Acid dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-propylene-4,4'-diphthalic dianhydride, 1,4-butylene-4,4'-diphthalic dianhydride, 1,5-pentylene-4,4'-diphthalic dianhydride, 1,3-bis(3,4-dicarboxyphenyl)phthalic dianhydride, 1,4-bis(3,4-dicarboxyphenyl)phthalic dianhydride, 1, 3-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic dianhydride (BPADA), 4,4'-oxydiphthalic dianhydride, etc.

[0148] As the acid anhydride, a commercially available compound may be used, or a compound synthesized by a known method or a method based thereon may be used. The acid anhydride may be used alone or in combination of two or more.

[0149] Polyimide resins can be prepared by conventional methods. Examples of conventional methods include heating a mixture of a diamine compound, an acid anhydride, and a solvent to react. The amount of the diamine compound used is typically 0.5 to 1.5 molar equivalents, preferably 0.9 to 1.1 molar equivalents, relative to the acid anhydride.

[0150] A commercially available polyimide resin may be used, and examples of the commercially available polyimide resin include "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by Shin Nippon Chemical Co., Ltd.

[0151] Examples of the phenoxy resin include phenoxy resins having one or more skeletons selected from the group consisting of bisphenol A skeletons, bisphenol F skeletons, bisphenol S skeletons, bisphenol acetophenone skeletons, phenolic skeletons, biphenyl skeletons, fluorene skeletons, dicyclopentadiene skeletons, norbornene skeletons, naphthalene skeletons, anthracene skeletons, adamantane skeletons, terpene skeletons, and trimethylcyclohexane skeletons. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. Specific examples of phenoxy resins include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both are phenoxy resins containing a bisphenol A skeleton), "YX8100" manufactured by Mitsubishi Chemical Corporation (a phenoxy resin containing a bisphenol S skeleton), "YX6954" manufactured by Mitsubishi Chemical Corporation (a phenoxy resin containing a bisphenol acetophenone skeleton), "FX280" and "FX293" manufactured by Nippon Steel & Sumitomo Metal Chemicals Corporation, "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482" and "YL7891BH30" manufactured by Mitsubishi Chemical Corporation, etc.

[0152] Examples of the polyvinyl acetal resin include polyvinyl formal resin and polyvinyl butyral resin, preferably polyvinyl butyral resin. Specific examples of the polyvinyl acetal resin include S-LEC BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, and BM series manufactured by Sekisui Chemical Co., Ltd.

[0153] Examples of the polyolefin resin include low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymers, ethylene-ethyl acrylate copolymers, ethylene-methyl acrylate copolymers and other ethylene-based copolymers; and polyolefin polymers such as polypropylene and ethylene-propylene block copolymers.

[0154] Examples of the polybutadiene resin include resins containing a hydrogenated polybutadiene skeleton, hydroxyl group-containing polybutadiene resins, phenolic hydroxyl group-containing polybutadiene resins, carboxyl group-containing polybutadiene resins, acid anhydride group-containing polybutadiene resins, epoxy group-containing polybutadiene resins, isocyanate group-containing polybutadiene resins, urethane group-containing polybutadiene resins, and polyphenylene ether-polybutadiene resins.

[0155] Specific examples of polyamide-imide resins include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of polyamide-imide resins include modified polyamide-imides such as "KS9100" and "KS9300" (polyamide-imides containing a polysiloxane skeleton) manufactured by Risenoko Co., Ltd.

[0156] Specific examples of the polyethersulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

[0157] Specific examples of the polysulfone resin include polysulfone "P1700" and "P3500" manufactured by Solvay High Performance Polymers Co., Ltd.

[0158] Specific examples of the polyphenylene ether resin include "NORYL SA90" manufactured by SABIC Innovative Plastics, and the like. Specific examples of the polyetherimide resin include "ULTEM" manufactured by GE Plastics.

[0159] Examples of polycarbonate resins include hydroxyl group-containing carbonate resins, phenolic hydroxyl group-containing carbonate resins, carboxyl group-containing carbonate resins, acid anhydride group-containing carbonate resins, isocyanate group-containing carbonate resins, and urethane group-containing carbonate resins. Specific examples of polycarbonate resins include "FPC0220" manufactured by Mitsubishi Gas Chemical Co., Ltd., "T6002" and "T6001" (polycarbonate diols) manufactured by Asahi Kasei Corporation, and "C-1090," "C-2090," and "C-3090" (polycarbonate diols) manufactured by Kuraray Co., Ltd. Specific examples of polyetheretherketone resins include "SUMIPLOY K" manufactured by Sumitomo Chemical Co., Ltd.

[0160] Examples of the polyester resin include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, and polycyclohexanedimethylene terephthalate resin.

[0161] The (E) thermoplastic resin may be an organic filler that is insoluble in a solvent described below and present in the resin composition layer in the form of particles. Examples of the organic filler include rubber particles, polyamide microparticles, silicone particles, and core-shell particles, with rubber particles being preferred.

[0162] Examples of the rubber component contained in the rubber particles include olefinic 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-butylene terpolymer; and thermoplastic elastomers such as acrylic thermoplastic elastomers such as polypropyl(meth)acrylate, polybutyl(meth)acrylate, polycyclohexyl(meth)acrylate, and polyoctyl(meth)acrylate. Olefinic thermoplastic elastomers are preferred, and styrene-butadiene copolymers are more preferred. Silicone rubbers such as polyorganosiloxane rubbers may also be mixed with the rubber component. Furthermore, the glass transition temperature of the rubber component contained in the rubber particles is, for example, 0°C or less, preferably -10°C or less, more preferably -20°C or less, and even more preferably -30°C or less.

[0163] As the rubber particles, commercially available products may be used, and examples thereof include "EXL2655" manufactured by Dow Chemical Japan Ltd. and "AC3401N" and "AC3816N" manufactured by AICA Industries, Ltd.

[0164] Core-shell particles refer to particulate organic fillers comprising a core particle of the rubber component cited above and a shell portion covering the core particle. In addition, core-shell particles are preferably core-shell graft copolymer particles comprising a core particle of the rubber component cited above and a shell portion obtained by graft copolymerization of a monomer component copolymerizable with the rubber component contained in the rubber particle. The core-shell type particles mentioned here do not only refer to those in which the core particle and the shell portion are clearly distinguishable, but also include those in which the boundary between the core particle and the shell portion is unclear, and the core particle may not be completely covered by the shell portion.

[0165] The rubber component preferably contains more than 40 mass % in the core-shell type graft copolymer particles, more preferably contains more than 50 mass %, and further more preferably contains more than 60 mass %. The upper limit of the content of the rubber component in the core-shell type graft copolymer particles is not particularly limited, and from the viewpoint of fully coating the core particles with the shell portion, for example, preferably below 95 mass %, 90 mass %.

[0166] Examples of the monomer component forming the shell portion of the core-shell graft copolymer particles include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, and glycidyl (meth)acrylate; (meth)acrylic acid; N-substituted maleimides such as N-methylmaleimide and N-phenylmaleimide; maleimide; α,β-unsaturated carboxylic acids such as maleic acid and itaconic acid; aromatic vinyl compounds such as styrene, 4-vinyltoluene, and α-methylstyrene; and (meth)acrylonitrile. Preferred are (meth)acrylates, and more preferred is methyl (meth)acrylate.

[0167] Examples of commercially available core-shell graft copolymer particles include “CHT” manufactured by Samsung SDI Co., Ltd., “B602” manufactured by Techno UMG Co., Ltd., “PARALOID XL2602”, “PARALOID EXL2603”, “PARALOID EXL2655”, “PARALOID EXL2311”, “PARALOID XL2313”, “PARALOID EXL2315”, “PARALOID KM330”, “PARALOID KM336P”, and “PARALOID KCZ201” manufactured by The Dow Chemical Company, Ltd., “METABLEN C-223A”, “METABLEN E-901”, “METABLEN S-2001”, “METABLEN W-450A”, and “METABLEN SRK-200” manufactured by Mitsubishi Rayon Co., Ltd., and “Kane Ace M-511” and “Kane Ace M-600", "Kane Ace M-400", "Kane Ace M-580", "Kane Ace MR-01", etc. These particles may be used alone or in combination of two or more.

[0168] The average particle size (average primary particle size) of core-shell type graft copolymer particles is not particularly limited, preferably more than 20nm, more preferably more than 50nm, further more preferably more than 80nm, especially better more than 100nm, preferably below 5000nm, more preferably below 2000nm, further more preferably below 1000nm, especially better below 500nm.The average particle size (average primary particle size) of core-shell type graft copolymer particles can be measured using ζ-potential particle size distribution measuring device etc.

[0169] When the non-volatile component of the resin composition layer is set to 100 mass%, the content of the (E) component is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, further preferably 1 mass% or more, preferably 5 mass% or less, more preferably 3 mass% or less, further preferably 2 mass% or less.

[0170] When the resin component of the resin composition layer is set to 100% by mass, the content of the (E) component is preferably 1% by mass or more, more preferably 1.5% by mass or more, further preferably 2% by mass or more, preferably 10% by mass or less, more preferably 8% by mass or less, further preferably 5% by mass or less.

[0171] -(F) Curing accelerator- The resin composition layer may contain a curing accelerator (F) as the component (F). The curing accelerator (F) as the component (F) does not include the substances included in the above-mentioned components (A) to (E). The curing accelerator (F) functions as a curing catalyst that accelerates the curing of the epoxy resin in the component (C).

[0172] As the curing accelerator (F), a compound that accelerates the curing of epoxy resins can be used. Examples of such curing accelerators (F) 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. The curing accelerators (F) can be used alone or in combination of two or more.

[0173] Phosphorus curing accelerators include, for example, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitic acid salt, tetrabutylphosphonium hexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butyldimethylphosphonium tetraphenylborate and other aliphatic phosphonium salts; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, para-methyl Aromatic phosphonium salts such as phenyltriphenylphosphonium tetra-p-tolyl borate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolyl borate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone addition reactants such as triphenylphosphine-p-benzoquinone addition reactants; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butylphosphine aliphatic phosphines such as 2-butyl-2-butenyl phosphine, di-tert-butyl-3-methyl-2-butenyl phosphine, tricyclohexyl phosphine; dibutylphenyl phosphine, di-tert-butylphenyl phosphine, methyldiphenyl phosphine, ethyldiphenyl phosphine, butyldiphenyl phosphine, diphenylcyclohexyl phosphine, 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-dimethylphenyl)phosphine Aromatic phosphines such as 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 are also included.

[0174] Examples of the urea curing accelerator 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, Aromatic dimethylureas such as 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].

[0175] Examples of the guanidine curing accelerator 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.

[0176] Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1' )]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline and other imidazole compounds, and adducts of imidazole compounds with epoxy resins. Commercially available imidazole curing accelerators include, for example, "1B2PZ", "2E4MZ", "2MZA-PW", "2MZ-OK", "2MA-OK", "2MA-OK-PW", "2PHZ", "2PHZ-PW", "Cl1Z", "Cl1Z-CN", "Cl1Z-CNS", and "C11Z-A" manufactured by Shikoku Chemicals Co., Ltd., and "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0177] Examples of metallic 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 organocobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate; organocopper complexes such as copper (II) acetylacetonate; organozinc complexes such as zinc (II) acetylacetonate; organoiron complexes such as iron (III) acetylacetonate; organonickel complexes such as nickel (II) acetylacetonate; and organomanganese complexes such as manganese (II) acetylacetonate. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0178] Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo[5.4.0]undecene. Amine curing accelerators that are commercially available may be used, and examples thereof include "MY-25" manufactured by Ajinomoto Fine Technology Co., Ltd.

[0179] When the non-volatile component in the resin composition layer is set to 100 mass%, the content of the (F) curing accelerator is preferably 0.001 mass% or more, more preferably 0.005 mass% or more, further preferably 0.01 mass% or more, 0.05 mass% or more, preferably 1.5 mass% or less, more preferably 1 mass% or less, further preferably 0.5 mass% or less.

[0180] When the resin component in the resin composition layer is set to 100% by mass, the content of the (F) curing accelerator is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, further preferably 0.3% by mass or more, preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 1% by mass or less.

[0181] -(G) Other additives- The resin composition layer may contain (G) other additives as an optional non-volatile component. Examples of (G) other additives include: elastomers (excluding those belonging to component (E)); polymerization initiators; organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as Benton (bentonite) and montmorillonite; defoamers such as silicone-based defoamers, acrylic-based defoamers, fluorine-based defoamers, and vinyl resin-based defoamers; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion enhancers such as urea silane; triazole-based adhesion imparting agents, tetrazole-based Adhesion-imparting agents such as adhesion-imparting agents and triazine-based adhesion-imparting agents; antioxidants such as hindered phenol-based antioxidants; fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; dispersants such as phosphate-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic anhydride-based stabilizers; photopolymerization initiation aids such as tertiary amines; photosensitizers such as pyrazolines, anthracenes, coumarins, xanthones, and thioxanthones; antioxidants (excluding those included in component (B)). (G) Other additives may be used alone or in combination of two or more.

[0182] -(H)Solvent- The resin composition layer may be combined with the non-volatile components (A) to (G) components mentioned above and further contain (H) solvent as an arbitrary volatile component. As the (H) solvent, an organic solvent is generally used. Examples of the organic solvent include: ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and carbitol acetate. Ether ester solvents such as methyl acetate, γ-butyrolactone, and methyl methoxypropionate; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (H) Solvents may be used alone or in combination.

[0183] The amount of the solvent (H) is not particularly limited and may be, for example, 60% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, relative to 100% by mass of all components of the resin composition layer, or 0% by mass.

[0184] From the perspective of thinning the printed wiring board and providing a cured product having excellent insulation properties even when the cured product of the resin composition layer is a film, the thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, and further preferably 55 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited and can generally be 5 μm or more, 10 μm or more, etc.

[0185] <Protective film> The resin sheet may, as needed, include a protective film selected based on the support as an additional layer. The protective film is provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface opposite the support). By laminating the protective film on the resin sheet, it is possible to prevent the surface of the resin composition layer from being adhered to by dirt or otherwise damaged.

[0186] Examples of the protective film include films made of plastic materials, metal foils, and release papers, and films made of plastic materials and metal foils are preferred.

[0187] When a film formed of a plastic material is used as the protective film, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes referred to as "PET") and polyethylene naphthalate (hereinafter sometimes referred to as "PEN"), acrylics such as polycarbonate (hereinafter sometimes referred to as "PC") and polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, and polyimide. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0188] When a metal foil is used as the protective film, examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. The copper foil may be a foil made of copper alone or an alloy of copper and other metals (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

[0189] The surface of the protective film that contacts the resin composition layer may be subjected to matte treatment, corona discharge treatment, or antistatic treatment.

[0190] In addition, as the protective film, a protective film with a release layer having a release layer on the surface bonded to the resin composition layer can be used. As a release agent for the release layer of the protective film with a release layer, for example, one or more release agents selected from alkyd resins, polyolefin resins, polyurethane resins and silicone resins can be mentioned. Commercially available products can be used as the protective film with a release layer, for example, "SK-1", "AL-5", and "AL-7" manufactured by Lintec Co., Ltd., which are PET films having a release layer with an alkyd resin release agent as a main component, "LUMIRROR T60", "LUMIRROR R80", and "LUMIRROR" manufactured by Toray Industries, Ltd., "Purex" manufactured by Teijin Limited, and "Unipeel" manufactured by Unitika Co., Ltd. can be mentioned.

[0191] The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. When the protective film has a multilayer structure such as a protective film with a release layer, the thickness of the entire protective film is preferably within the above range.

[0192] <Method for producing resin sheet> The resin sheet can be produced, for example, by preparing a resin varnish by dissolving the components contained in the resin composition layer in a solvent, applying the resin varnish on a support using a die coater or the like, and drying the varnish to form the resin composition layer.

[0193] Examples of the solvent include the same solvents as those described as components of the resin composition layer. The solvents may be used alone or in combination of two or more.

[0194] Drying can be carried out by heating, blowing hot air, or the like. Drying conditions are not particularly limited, but drying is performed under conditions such that the solvent content in the resin composition layer is generally 10% by mass or less, preferably 5% by mass or less. Depending on the boiling point of the solvent in the resin composition, for example, when using a resin composition containing 30% to 60% by mass of a solvent, the resin composition layer can be formed by drying at 50° C. to 150° C. for 3 to 10 minutes.

[0195] The resin sheet can be stored in a roll. If the resin sheet has a protective film, it can usually be used by peeling off the protective film.

[0196] <Physical Properties of Resin Sheets> The resin composition layer combination in the resin sheet of the present invention includes components (A) to (D), so the cured product of the resin composition layer shows the characteristic of low dielectric loss tangent. Therefore, an insulating layer with low dielectric loss tangent is provided. The dielectric loss tangent of the cured product obtained by thermal curing at 190° C. for 90 minutes is preferably 0.0050 or less, more preferably 0.0045 or less, further preferably 0.004 or less, and particularly preferably 0.003 or less. The lower limit is not particularly limited and may be, for example, 0.0010 or more. The dielectric loss tangent can be measured by the method described in the examples described later.

[0197] The resin composition layer combination in the resin sheet of the present invention includes components (A) to (D), so the cured product of the resin composition layer exhibits the characteristic of a low relative dielectric constant. Thus, an insulating layer with a low relative dielectric constant is provided. The relative dielectric constant of the cured product is preferably 3.5 or less, more preferably 3.4 or less, and further preferably 3.3 or less. The lower limit is not particularly limited and may be, for example, 0.1 or more. The relative dielectric constant can be measured by the method described in the embodiments described below.

[0198] The resin composition layer in the resin sheet shows the characteristic of low melt viscosity (minimum melt viscosity). Therefore, an insulating layer with excellent embedding properties is provided. The melt viscosity can be measured using a dynamic viscoelasticity measuring device, for example, under the measurement conditions of a heating rate of 5°C / min, a measurement temperature interval of 2.5°C, and a vibration frequency of 1Hz when the temperature range is 60°C to 200°C. The melt viscosity when measured in the temperature range of 60°C to 200°C is preferably 4000 poise or less, 3500 poise or less, and more preferably 3000 poise or less. There is no particular restriction on the lower limit, and it may be 10 poise or more. The melt viscosity can be measured according to the method described in the examples described later.

[0199] The cured product of the resin composition layer exhibits the property of easily removing stains generated when the through-hole is formed (excellent stain removability). That is, it provides an insulating layer that exhibits good stain removability. Because of the excellent stain removability, the maximum stain length measured from the wall side of the through-hole bottom is preferably less than 5 μm, more preferably less than 3 μm, and further preferably less than 3 μm. The lower limit is not particularly limited and may be 0.01 μm or more. The stain removability can be measured according to the method described in the examples described below.

[0200] The cured product of the resin composition layer shows a characteristic that can suppress the generation of cracks after decontamination treatment (roughening treatment). Thus, an insulating layer with excellent crack resistance is provided. Specifically, after making a circuit substrate and performing decontamination treatment, when observing 100 copper pads of the circuit substrate, the number of cracks is preferably less than 20, and more preferably less than 10. The evaluation of crack resistance can be evaluated according to the method described in the embodiments described below.

[0201] [Semiconductor package substrate and manufacturing method thereof] The semiconductor chip package of the present invention comprises a circuit substrate and a semiconductor chip mounted on the circuit substrate. The circuit substrate comprises an insulating layer formed from a cured product of the resin composition layer in the resin sheet of the present invention. The semiconductor chip package can be manufactured by bonding the semiconductor chip to the circuit substrate. The circuit substrate will be described later.

[0202] As long as the terminal electrodes of the semiconductor chip are connected to the circuit wiring of the circuit substrate by conductors, the joining conditions are not particularly limited, and the known conditions used in the flip-chip mounting of the semiconductor chip can be adopted. In addition, the semiconductor chip and the circuit substrate can be joined by an insulating adhesive.

[0203] A preferred embodiment is to press-bond the semiconductor chip to the circuit board. As press-bonding conditions, for example, the pressing temperature can be set in the range of 120°C to 240°C, preferably in the range of 130°C to 200°C, and more preferably in the range of 140°C to 180°C, and the pressing time can be set in the range of 1 second to 60 seconds, preferably in the range of 5 seconds to 30 seconds.

[0204] In another preferred embodiment, the semiconductor chip is bonded to the circuit board by reflow soldering. The reflow soldering conditions may be, for example, within a range of 120°C to 300°C.

[0205] After the semiconductor chip is bonded to the circuit substrate, for example, the semiconductor chip may be filled with a mold underfill material to obtain a semiconductor chip package. The method of filling with a mold underfill material can be carried out by a known method.

[0206] The circuit board includes an insulating layer formed from a cured product of the resin composition layer in the resin sheet of the present invention. The circuit board can be produced, for example, by a production method comprising the following steps (I) and (II): (I) a step of laminating a resin sheet on the inner substrate in such a manner that the resin composition layer of the resin sheet is bonded to the inner substrate; (II) A step of curing the resin composition layer to form an insulating layer.

[0207] The "inner substrate" used in step (I) refers to a component of a substrate that becomes a circuit substrate, and examples thereof include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. In addition, the substrate may have a conductor layer on one or both sides thereof, and the conductor layer may be patterned. An inner substrate having a conductor layer (circuit) formed on one or both sides of a substrate is sometimes referred to as an "inner circuit substrate". In addition, intermediate products that require further formation of an insulating layer and / or a conductor layer when manufacturing a circuit substrate are also included in the above-mentioned "inner substrate". In the case where the circuit substrate is a circuit board with built-in components, an inner substrate with built-in components can be used.

[0208] The lamination of the inner substrate and the resin sheet can be carried out by, for example, heat-pressing the resin sheet to the inner substrate from the support body side. As a component for heat-pressing the resin sheet to the inner substrate (hereinafter also referred to as "heat-pressing component"), for example, a heated metal plate (SUS end plate, etc.) or a metal roller (SUS roller, etc.) can be cited. It should be noted that it is better not to press the heat-pressing component directly on the resin sheet, but to press it with an elastic material such as heat-resistant rubber so that the resin sheet fully conforms to the surface unevenness of the inner substrate.

[0209] The inner layer substrate and the resin sheet can be laminated by vacuum lamination. In vacuum lamination, the heating and pressing temperature is preferably in the range of 60°C to 160°C, more preferably 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 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 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions of 26.7 hPa or less.

[0210] Lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressure laminator manufactured by Meiki Mfg. Co., Ltd., a vacuum applicator manufactured by Nikko Materials Co., Ltd., and a batch vacuum pressure laminator.

[0211] After lamination, the laminated resin sheets can be smoothed by, for example, pressing a heat-pressing member from the support side under normal pressure (atmospheric pressure). The pressing conditions for the smoothing treatment can be the same as those for the heat-pressing conditions for lamination described above. The smoothing treatment can be performed using a commercially available laminator. It should be noted that lamination and smoothing can be performed continuously using the above-mentioned commercially available vacuum laminator.

[0212] The support may be removed between step (I) and step (II), or may be removed after step (II).

[0213] In step (II), the resin composition layer is cured to form an insulating layer formed from a cured product of the resin composition layer. The curing of the resin composition layer is usually performed by thermal curing. The specific curing conditions of the resin composition layer can use the conditions commonly used when forming an insulating layer of a printed wiring board.

[0214] For example, the thermal curing conditions of the resin composition layer also 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.

[0215] Before heat-curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, before heat-curing the resin composition layer, the resin composition layer may be preheated at a temperature of 50°C to 150°C, preferably 60°C to 140°C, and more preferably 70°C to 130°C for 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes.

[0216] When manufacturing a circuit substrate, the process of (III) opening a hole in the insulating layer, the process of (IV) roughening the insulating layer, and the process of (V) forming a conductor layer can be further implemented. These processes (III) to (V) can be implemented according to various methods known to those skilled in the art for the manufacture of circuit substrates. It should be noted that when the support body is removed after process (II), the removal of the support body can be implemented between process (II) and process (III), between process (III) and process (IV), or between process (IV) and process (V). In addition, the formation of the insulating layer and the conductor layer of processes (I) to (V) can be repeatedly implemented as needed to form a multilayer wiring board.

[0217] Step (III) is a step of drilling holes in the insulating layer, thereby forming holes such as through holes and vias in the insulating layer. Step (III) can be carried out using, for example, a drill, 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 wiring board.

[0218] Step (IV) is a step of roughening the insulating layer. Typically, contamination removal is also performed in step (IV). The steps and conditions for the roughening treatment are not particularly limited and can be those commonly used to form the insulating layer of a printed wiring board. For example, the insulating layer can be roughened by sequentially performing a swelling treatment using a swelling solution, a roughening treatment using an oxidizing agent, and a neutralization treatment using a neutralizing solution.

[0219] As the swelling liquid used for the roughening treatment, for example, an alkaline solution, a surfactant solution, etc. can be mentioned, and an alkaline solution is preferred. As the alkaline solution, a sodium hydroxide solution or a potassium hydroxide solution is more preferred. As commercially available swelling liquids, for example, "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan Co., Ltd. can be mentioned. The swelling treatment using the swelling liquid can be carried out, for example, by immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of controlling the swelling of the resin of the insulating layer to an appropriate level, it is preferred to immerse the insulating layer in a swelling liquid at 40°C to 80°C for 5 minutes to 15 minutes.

[0220] As the oxidizing agent used in the roughening treatment, an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide can be cited. The roughening treatment using an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. As commercially available oxidizing agents, alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan Co., Ltd. can be cited.

[0221] The neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution. Commercially available products include, for example, "Reduction Solution Securiganth P" manufactured by Atotech Japan Co., Ltd. Treatment with the neutralizing solution can be performed by immersing the surface roughened with an oxidizing agent in the neutralizing solution at a temperature of 30°C to 80°C for 5 to 30 minutes. From the perspective of operability, immersing the surface roughened with an oxidizing agent in the neutralizing solution at a temperature of 40°C to 70°C for 5 to 20 minutes is preferred.

[0222] In one embodiment, the arithmetic mean roughness (Ra) of the insulating layer surface after roughening treatment is preferably less than 500nm, more preferably less than 400nm, and further preferably less than 300nm. There is no particular limitation on the lower limit, for example, it can be set to more than 1nm, more than 2nm, etc. In addition, the root mean square roughness (Rq) of the insulating layer surface after roughening treatment is preferably less than 500nm, more preferably less than 400nm, and further preferably less than 300nm. There is no particular limitation on the lower limit, for example, it can be set to more than 1nm, more than 2nm, etc. The arithmetic mean roughness (Ra) and root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter.

[0223] Step (V) is a step of forming a conductor layer, in which a conductor layer 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 may be a single metal layer or an alloy layer. As the alloy layer, for example, a layer formed by an alloy of two or more metals selected from the above metals (e.g., nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy) can be cited. Among them, from the viewpoints of versatility, cost, ease of pattern formation, etc. of the formation of the conductor layer, preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy or copper-titanium alloy, more preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy, more preferably a single metal layer of copper.

[0224] The conductor layer may have a single-layer structure or a multilayer structure in which two or more single metal layers or alloy layers composed of different types of metals or alloys are stacked. In the case of a multilayer 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 a nickel-chromium alloy.

[0225] The thickness of the conductor layer varies depending on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0226] 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 a semi-additive process or a fully additive process to form a conductor layer having a desired wiring pattern. From the perspective of manufacturing simplicity, a semi-additive process is preferred. An example of forming a conductor layer using a semi-additive process is shown below.

[0227] First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer, exposing a portion of the plating seed layer in accordance with the desired wiring pattern. After a metal layer is formed on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. The unnecessary plating seed layer is then removed by etching or other methods, thereby forming a conductor layer having the desired wiring pattern.

[0228] In another embodiment, the conductor layer can be formed using metal foil. When a metal foil is used to form the conductor layer, process (V) is preferably implemented between process (I) and process (II). For example, after process (I), the support is removed and a metal foil is laminated on the surface of the exposed resin composition layer. The lamination of the resin composition layer and the metal foil can be implemented by a vacuum lamination method. The lamination conditions can be the same as those described for process (I). Then, process (II) is implemented to form an insulating layer. Then, the metal foil on the insulating layer can be used to form a conductor layer with a desired wiring pattern by conventionally known techniques such as a subtractive method and a modified semi-additive method.

[0229] Metal foil can be produced by known methods such as electrolysis and rolling. Commercially available metal foils include HLP foil and JXUT-III foil manufactured by JX Metals Co., Ltd., and 3EC-III foil and TP-III foil manufactured by Mitsui Mining & Smelting Co., Ltd.

[0230] [Semiconductor devices] Examples of semiconductor devices to which the semiconductor chip package of the present invention is to be mounted include various semiconductor devices for use in electrical products (e.g., computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, and televisions) and vehicles (e.g., motorcycles, automobiles, trains, ships, and aircraft). Example

[0231] The present invention is described in detail below by way of examples. The present invention is not limited to these examples. It should be noted that, hereinafter, "parts" and "%" indicating quantities refer to "parts by mass" and "mass %" respectively, unless otherwise specified. Unless otherwise specified, the temperature condition is room temperature (23°C), and unless otherwise specified, the pressure condition is atmospheric pressure (1 atm).

[0232] <Synthesis Example 1: Synthesis of a Radically Polymerizable Group-Containing Compound Having a Carbodiimide Structure> 100 parts by mass of dicyclohexylmethane-4,4'-diisocyanate (HMDI) and 0.5 parts by mass of 3-methyl-1-phenyl-2-phosphole-1-oxide as a carbodiimidization 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 flow to perform a carbodiimidization reaction to obtain an isocyanate-terminated polycarbodiimide. The obtained isocyanate-terminated polycarbodiimide was measured by IR spectroscopy and a wavelength of 2150 cm was confirmed. -1 The terminal NCO content was 8.19% by mass, and the average polymerization degree of the carbodiimide groups determined by the above-mentioned measurement method was 3.5.

[0233] Next, 8.8 parts by mass of ethylene glycol monoacrylate was added to the isocyanate-terminated polycarbodiimide at 150°C under a nitrogen stream, and the mixture was heated to 180°C and stirred for 2 hours to react. IR spectroscopy was performed to confirm the presence of a wavelength of 2200 to 2300 cm -1 After the absorption peak of the isocyanate group disappears, the reaction product is taken out from the reaction container and cooled to room temperature to obtain a light yellow transparent solid polycarbodiimide compound (a compound containing a free radical polymerizable group having a carbodiimide structure, the main component of which is the compound of the above formula (S1), and b' represents the average polymerization degree of the carbodiimide group). [Chemical Formula 11]

[0234] <Synthesis Example 2: Synthesis of a Radically Polymerizable Group-Containing Compound Having a Carbodiimide Structure> In Synthesis Example 1, 8.8 parts of ethylene glycol monoacrylate was replaced with 8.8 parts of ethylene glycol monoallyl ether. The same procedures as in Synthesis Example 1 were followed except for the above matters to obtain a solid polycarbodiimide compound (a compound having a carbodiimide structure and containing a radically polymerizable group, the main component of which is the compound of formula (S2), b' being the same as above). [Chemical Formula 12]

[0235] <Synthesis Example 3: Synthesis of a Radically Polymerizable Group-Containing Compound Having a Carbodiimide Structure> To the isocyanate-terminated polycarbodiimide obtained by the same method as in Synthesis Example 1, 8.8 parts by mass of ethylene glycol monoacrylate and 4 parts by mass of polybutadiene at both ends ("G-1000" manufactured by Nippon Soda Co., Ltd., number average molecular weight 1400, 85% or more of 1,2-addition structural units, 15% or less of trans-1,4-addition structural units) were added, and the mixture was heated to 180°C and stirred for 2 hours to react. IR spectroscopy was performed to confirm that the wavelength was 2200 to 2300 cm -1 After the absorption peak of the isocyanate group disappears, the reaction product is taken out from the reaction vessel and cooled to room temperature to obtain a light yellow transparent solid polycarbodiimide compound (a compound containing a free radical polymerizable group having a carbodiimide structure, the main component of which is the compound of the above formula (S3), b' is the same as above. d' represents the average degree of polymerization of the combined units of polybutadiene and polycarbodiimide. e' represents the average degree of polymerization of the butadiene unit corresponding to the above number average molecular weight. As the e' unit, only 1,2-addition structural units are represented, but 1,4-addition structural units (cis, trans) are also included). [Chemical Formula 13]

[0236] <Synthesis Example 4: Synthesis of Maleimide A> A MEK solution (non-volatile content 62% by mass) of a maleimide compound synthesized by the method described in Synthesis Example 1 of Japan Invention Association Publication No. 2020-500211 was prepared. The maleimide compound has a structure represented by the following formula (1) (Mw / Mn = 1.81, t" = 1.47 (mainly 1, 2, or 3)). [Chemical Formula 14]

[0237] <Synthesis Example 5: Synthesis of Polyimide B> A 500mL separable flask equipped with a reflux condenser, a nitrogen inlet tube, and a stirrer was prepared. 20.3g of 4,4'-oxydiphthalic anhydride (ODPA), 200g of γ-butyrolactone, 20g of toluene, and 29.6g of 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindane were added to the flask and stirred at 45°C for 2 hours under a nitrogen stream to allow the reaction to proceed. The reaction solution was then heated and maintained at approximately 160°C while azeotropically removing the condensed water along with the toluene under a nitrogen stream. Confirmation was made that the specified amount of water had accumulated in the water-quantifying receiver and that no water outflow was observed. After this confirmation, the reaction solution was heated again and stirred at 200°C for 1 hour. The mixture was then cooled to obtain a polyimide solution (non-volatile content 20% by mass) containing a polyimide resin having a 1,1,3-trimethylindane skeleton. The resulting polyimide resin had a repeating unit represented by the following formula (X1) and a repeating unit represented by the following formula (X2). The weight-average molecular weight of the polyimide resin was 12,000. [Chemical Formula 15]

[0238] <Manufacturing of resin varnish> Each component was weighed according to the mass parts described in the following table, and further 10 parts of MEK and 10 parts of cyclohexanone were mixed and uniformly dispersed using a high-speed rotary mixer to obtain a resin varnish. [Table 1] (Table 1)

[0239] The details of each component described in the table are as follows. (A) Compounds containing a radically polymerizable group and having a carbodiimide structure Synthesis Example 1: Compound containing a free radical polymerizable group and having a carbodiimide structure synthesized in Synthesis Example 1 Synthesis Example 2: Compound containing a free radical polymerizable group and having a carbodiimide structure synthesized in Synthesis Example 2 Synthesis Example 3: Compound containing a free radical polymerizable group and having a carbodiimide structure synthesized in Synthesis Example 3 (B) Antioxidants AO-330: Phenolic antioxidant, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, manufactured by ADEKA Corporation AO-20: Phenolic antioxidant, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by ADEKA Corporation HP-300: Phenolic antioxidant, N,N'-bis-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionylhexamethylenediamine, manufactured by Kawaguchi Chemical Industry Co., Ltd. AO-503: Thioether antioxidant, ditridecyl-3,3'-thiodipropionate, manufactured by ADEKA Corporation (C) Thermosetting resin HP-4032-SS: Naphthalene-based epoxy resin, epoxy equivalent weight 144 g / eq., manufactured by DIC Corporation NC-3000-L: Biphenyl epoxy resin, epoxy equivalent weight 269g / eq., manufactured by Nippon Kayaku Co., Ltd. ZX1059: A 1:1 mixture of bisphenol A epoxy resin and bisphenol F epoxy resin, epoxy equivalent weight 169 g / eq., manufactured by Nippon Steel Chemicals Co., Ltd. HPC-8150-62T: Active ester resin with a naphthalene structure, epoxy equivalent weight 223 g / eq., toluene solution containing 65% nonvolatile matter, manufactured by DIC Corporation HPC-8000L-65MT: Active ester resin containing a dicyclopentadiene-type diphenol structure, epoxy equivalent weight 229 g / eq., MEK / toluene mixed solution with a solid content of 65% by mass, manufactured by DIC Corporation LA-3018-50P: a phenolic resin containing a triazine skeleton, a 1-methoxy-2-propanol solution containing 50% by mass of non-volatile matter, manufactured by DIC Corporation BA230S75: Bisphenol A dicyanate prepolymer, functional group equivalent weight 232 g / eq., MEK solution with a non-volatile content of 75% by mass, manufactured by Arxada V03: Carbodiimide resin, functional group equivalent weight 216 g / eq., toluene solution containing 50% by mass of non-volatile matter, manufactured by Nisshinbo Chemical Co., Ltd. Stabaxol P100: Carbodiimide resin, functional group equivalent weight 272 g / eq., manufactured by LANXESS Maleimide A: the compound synthesized in Synthesis Example 4 SA9000: Methacryloyl-modified polyphenylene ether, manufactured by SABIC Innovative Plastics ODV-XET-X04: polystyrene resin, toluene solution containing 50% by mass of non-volatile matter, manufactured by Nippon Steel Chemicals Co., Ltd. (D) Inorganic filling materials SO-C2: Spherical silica surface-treated with an amine alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), average particle size 0.5 μm, specific surface area 5.8 m 2 / g, made by Yadoma Co., Ltd. UFP-30: Spherical silica surface-treated with an amine alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), with an average particle size of 0.3 μm and a specific surface area of ​​5.8 m 2 / g, made by DENKA Co., Ltd. (E) High molecular weight components YX7553BH30: phenoxy resin, 1:1 solution of MEK and cyclohexanone with a non-volatile content of 30% by mass, weight average molecular weight of 35,000, manufactured by Mitsubishi Chemical Corporation Polyimide B: the compound synthesized in Synthesis Example 5 AC3816N: STAPHYLOID, manufactured by AICA Industries, Ltd. (F) Curing accelerator ·PERHEXYL D: Made by NOF Co., Ltd. 1B2PZ: Made by Shikoku Chemical Industry Co., Ltd. Co(III): Metal catalyst, manufactured by Tokyo Chemical Industry Co., Ltd. (G) Other additives JP-360: Phosphorus antioxidant, manufactured by Johoku Chemical Co., Ltd. ANTAGE 3C: an amine antioxidant, manufactured by Kawaguchi Chemical Industries, Ltd.

[0240] <Preparation of a Resin Sheet Having a Resin Composition Layer Thickness of 40 μm> A polyethylene terephthalate film ("AL5" manufactured by Lintec Corporation, 38 μm thick) with a release layer was prepared as a support. The resin varnishes obtained in the Examples and Comparative Examples were evenly applied to the release layer of the support so that the thickness of the resin composition layer after drying was 40 μm. The resin composition was then dried at 80°C to 100°C (90°C on average) for 2 minutes to obtain a resin sheet comprising the support and the resin composition layer.

[0241] <Measurement of Dielectric Constant / Dielectric Dissipation Tangent (Dielectric Properties)> (1) Preparation of solidified material The resin sheets obtained in Examples and Comparative Examples were cured for 90 minutes in an oven at 190° C. The support was peeled off from the resin sheet taken out of the oven to obtain a cured product of the resin composition layer.

[0242] (2) Determination of dielectric constant and dielectric loss tangent The cured product was cut into pieces 80 mm long and 2 mm wide. The dielectric constant and dielectric loss tangent (Dk value and Df value) were measured using an Agilent Technologies "HP8362B" resonant cavity perturbation method at a measurement frequency of 5.8 GHz and measurement temperatures of 23°C and 90°C. The measurements were performed on two test pieces, and the average value was calculated.

[0243] <Measurement of melt viscosity> A portion of the resin composition layer was peeled from the resin sheet, and the melt viscosity was measured using a dynamic viscoelasticity measuring apparatus ("Rheosol-G3000" manufactured by UBM Co., Ltd.). Using parallel plates with a diameter of 18 mm, the temperature of 1 g of the resin composition layer was raised from a starting temperature of 60°C to 200°C at a heating rate of 5°C / min. The dynamic viscoelastic modulus was measured under the following measurement conditions: a measurement interval temperature of 2.5°C, an oscillation frequency of 1 Hz, and a strain of 5 degrees. The minimum melt viscosity (poise) was calculated.

[0244] <Evaluation of stain removability> (1) Base treatment of inner substrate As the inner layer substrate, a glass cloth-based epoxy resin double-sided copper-clad laminate with copper foil on its surface was prepared (copper foil thickness 18 μm, substrate thickness 0.8 mm, Panasonic Corporation "R1515A"). The copper foil on the surface of this inner layer substrate was etched with a microetchant (MEC Corporation "CZ8101") at a copper etching depth of 1 μm to perform a roughening treatment. The substrate was then dried at 190°C for 30 minutes.

[0245] (2) Lamination and curing of resin sheets The resin sheets obtained in the Examples and Comparative Examples were laminated onto both surfaces of the inner-layer substrate using a batch vacuum press laminator (Nikko Materials Co., Ltd., two-stage stack laminator "CVP700"), so that the resin composition layer was bonded to the inner-layer substrate. Lamination was performed by reducing the pressure for 30 seconds to 13 hPa or less, followed by pressing at a temperature of 100°C and a pressure of 0.74 MPa for 30 seconds.

[0246] The laminated resin sheet was then smoothed by hot pressing at 100°C and 0.5 MPa for 60 seconds under atmospheric pressure, and then heated in a 130°C oven for 30 minutes and then in a 170°C oven for 30 minutes.

[0247] (3) Formation of through-holes The insulating layer was processed using a CO2 laser processing machine (LK-2K212 / 2C) manufactured by Via Machine Co., Ltd. at a frequency of 2000 Hz, a pulse width of 3 μs, an output power of 0.95 W, and a shot count of 3. Through-holes with a top diameter of 50 μm and a bottom diameter of 40 μm were formed on the insulating layer surface. The support was then peeled off.

[0248] (4) Roughening treatment The inner layer substrate was immersed in Swelling Dip Securiganth P (manufactured by Atotech Japan Co., Ltd.) as a swelling solution at 60°C for 10 minutes. Next, it was immersed in Concentrate Compact P (a 60 g / L KMnO4, 40 g / L NaOH aqueous solution) (manufactured by Atotech Japan Co., Ltd.) as a roughening solution at 80°C for 20 minutes. Finally, it was immersed in Reduction Solution Securiganth P (manufactured by Atotech Japan Co., Ltd.) as a neutralizing solution at 40°C for 5 minutes. The resulting substrate was designated Evaluation Substrate A.

[0249] (5) Evaluation of residue (contamination) at the bottom of through-holes The periphery of the through-hole bottom was observed using a scanning electron microscope (SEM), and the maximum contamination length from the wall surface of the through-hole bottom was measured based on the obtained image and evaluated according to the following criteria. ◎: Maximum contamination length is less than 3μm ○: Maximum contamination length is 3 μm or more and less than 5 μm ×: The maximum stain length is 5 μm or more.

[0250] <Evaluation of cracks after desmearing treatment (roughening treatment)> On both sides of a core material ("E705GR" manufactured by Nikko-Norco, Ltd., 400 μm thick) having circular copper pads (copper thickness 35 μm) with a diameter of 350 μm formed in a grid pattern at intervals of 400 μm to achieve a residual copper rate of 60%, the resin sheets obtained in the examples and comparative examples were laminated to both sides of the inner layer substrate using a batch vacuum press laminator (Nikko-Materials Co., Ltd., two-stage stacking laminator "CVP700") so that the resin composition layer was bonded to the inner layer substrate. The lamination was carried out as follows: after reducing the pressure for 30 seconds to 13 hPa or less, the pressure was pressed at a temperature of 100°C and a pressure of 0.74 MPa for 30 seconds. The sheet was placed in an oven at 130°C and heated for 30 minutes, and then moved to an oven at 170°C and heated for 30 minutes. The support layer was then peeled off, and the resulting circuit board was immersed in Swelling DipSecuriganth P (manufactured by Atotech Japan Co., Ltd.) as a swelling solution at 60°C for 10 minutes. Next, it was immersed in Concentrate Compact P (an aqueous solution of 60 g / L KMnO4 and 40 g / L NaOH) (manufactured by Atotech Japan Co., Ltd.) as a roughening solution at 80°C for 30 minutes. Finally, it was immersed in Reduction SolutionSecuiganth P (manufactured by Atotech Japan Co., Ltd.) as a neutralizing solution at 40°C for 5 minutes. 100 copper pads of the roughened circuit board were observed to confirm the presence of cracks in the resin composition layer and evaluated according to the following evaluation criteria. ○: There are 10 or fewer cracks △: There are more than 10 and less than 20 cracks ×: The number of cracks was greater than 20.

[0251] [Table 2] (Table 2)

Claims

1. A resin sheet for forming an insulating layer of a semiconductor package substrate, wherein: A support and a resin composition layer provided on the support, The resin composition layer comprises: (A) a radical polymerizable group-containing compound having a carbodiimide structure, (B) one or more antioxidants selected from phenolic antioxidants and sulfur antioxidants, (C) thermosetting resin, and (D) Inorganic filling materials.

2. The resin sheet for forming an insulating layer of a semiconductor package substrate according to claim 1, wherein When the resin component of the resin composition layer is 100 mass %, the content of the component (A) is 0.1 mass % or more and 25 mass % or less.

3. The resin sheet for forming an insulating layer of a semiconductor package substrate according to claim 1, wherein When the resin component of the resin composition layer is 100 mass %, the content of the component (B) is 0.1 mass % or more and 10 mass % or less.

4. The resin sheet for forming an insulating layer of a semiconductor package substrate according to claim 1, wherein When the resin component of the resin composition layer is 100 mass %, the content of the component (C) is 50 mass % or more and 98 mass % or less.

5. The resin sheet for forming an insulating layer of a semiconductor package substrate according to claim 1, wherein When the nonvolatile matter of the resin composition layer is 100 mass %, content of the component (D) is 45 mass % or more and 85 mass % or less.

6. The resin sheet for forming an insulating layer of a semiconductor package substrate according to claim 1, wherein The melt viscosity of the resin composition layer is 3000 poise or less.

7. A semiconductor chip packaging substrate, wherein: The insulating layer is formed of a cured product of the resin composition layer of the resin sheet for forming an insulating layer of a semiconductor package substrate according to any one of claims 1 to 6.

8. A semiconductor device, wherein: A semiconductor chip package substrate comprising the semiconductor chip package substrate according to claim 7.

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