WO2024253037A1 - Feuille métallique équipée d'une résine - Google Patents

Feuille métallique équipée d'une résine Download PDF

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Publication number
WO2024253037A1
WO2024253037A1 PCT/JP2024/020017 JP2024020017W WO2024253037A1 WO 2024253037 A1 WO2024253037 A1 WO 2024253037A1 JP 2024020017 W JP2024020017 W JP 2024020017W WO 2024253037 A1 WO2024253037 A1 WO 2024253037A1
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Prior art keywords
resin
metal foil
resin layer
coated metal
polymer
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Ceased
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PCT/JP2024/020017
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English (en)
Japanese (ja)
Inventor
蔵 藤岡
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AGC Inc
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Asahi Glass Co Ltd
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Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to KR1020257031918A priority Critical patent/KR20260020377A/ko
Priority to CN202480037286.2A priority patent/CN121335803A/zh
Priority to JP2025526089A priority patent/JPWO2024253037A1/ja
Publication of WO2024253037A1 publication Critical patent/WO2024253037A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/30—Particles characterised by physical dimension
    • B32B2264/302—Average diameter in the range from 100 nm to 1000 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/40—Pretreated particles
    • B32B2264/402—Pretreated particles with organic substances
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a resin-coated metal foil.
  • the present invention relates to a resin-coated metal foil that has a resin layer containing a tetrafluoroethylene-based polymer and has low transmission loss even in the high frequency range and excellent electrical properties.
  • Patent Document 1 discloses a thermosetting resin composition containing a specific polyphenylene ether compound and an elastomer, and the content of tetrafluoroethylene-based polymer particles is within a specific range.
  • Patent Document 2 discloses a resin composition containing a modified polyphenylene ether having an unsaturated double bond at its terminal, a crosslinking agent, a polymerization inhibitor, composite particles having a fluororesin core, and a solvent.
  • Resin-coated copper foils (CCLs) containing a layer made of the resin composition disclosed in Patent Documents 1 and 2 tend to have high transmission loss in the high frequency range, and may be difficult to fully exhibit physical properties based on tetrafluoroethylene polymers or polyphenylene ethers.
  • multi-layer printed circuit boards including a resin layer containing a tetrafluoroethylene-based polymer and a prepreg layer are being considered. In this case, the issues are to ensure interlayer adhesion between the layers and to suppress warping due to heating while expressing physical properties based on the resin characteristics of each layer.
  • the present inventors have found that, when a resin layer containing a specific polyphenylene ether and an elastomer is further present in addition to a metal foil and a resin layer containing a tetrafluoroethylene-based polymer, even if the resin layer containing a tetrafluoroethylene-based polymer is made thicker than the metal foil, warping due to heating can be suppressed and transmission loss in the high frequency range can be improved.Then, they have found that this can be effectively applied to the manufacture of a printed circuit board, and have arrived at the present invention.
  • the present inventors also found that, when a specific inorganic filler is contained in both the resin layer containing a tetrafluoroethylene-based polymer and the layer derived from an aromatic resin, even if the resin layer containing a tetrafluoroethylene-based polymer is made thicker than the metal foil, the warping caused by heating can be suppressed and the transmission loss in the high frequency range can be improved. They also found that this can be effectively applied to the manufacture of a printed circuit board, and thus the present invention was completed.
  • the object of the present invention is to provide a resin-coated metal foil which has excellent electrical properties with little transmission loss even in the high frequency range, in which the physical properties of a tetrafluoroethylene-based polymer and an aromatic resin are fully expressed, and which has suppressed warping and excellent interlayer adhesion.
  • the aromatic resin is a modified polyphenylene ether resin having a polymerizable carbon-carbon double bond, and the second resin layer contains a styrene-based elastomer, or
  • the first resin layer and the second resin layer each contain an inorganic filler having an average particle size of less than 15 ⁇ m and having been surface-treated with a silane coupling agent; Resin-coated metal foil.
  • the silane coupling agent is an acrylic silane coupling agent or a vinyl silane coupling agent.
  • a resin-coated metal foil which has excellent electrical properties with small transmission loss even in the high frequency range, in which the physical properties of the tetrafluoroethylene-based polymer and aromatic resin are fully expressed, and which has suppressed warping and excellent interlayer adhesion. From the resin-coated metal foil of the present invention, a printed circuit board having small transmission loss even in the high frequency range and excellent electrical properties can be produced.
  • the average particle size (D50) is the volume-based cumulative 50% diameter of a particle or filler determined by a laser diffraction/scattering method. That is, the particle size distribution is measured by a laser diffraction/scattering method, a cumulative curve is calculated with the total volume of a group of particles or fillers set to 100%, and the average particle size (D50) is the particle size at the point on the cumulative curve where the cumulative volume is 50%.
  • the D50 of the particles or filler is determined by dispersing the particles or filler in water and analyzing it by a laser diffraction/scattering method using a laser diffraction/scattering type particle size distribution measuring device (LA-920 measuring device, manufactured by Horiba, Ltd.).
  • Melting temperature is the temperature corresponding to the maximum of the melting peak of a polymer as measured by differential scanning calorimetry (DSC).
  • Glass transition temperature (Tg)” is a value measured by analyzing a polymer using dynamic mechanical analysis (DMA) method.
  • the "viscosity” is determined by measuring the composition using a Brookfield viscometer at 25° C. and a rotation speed of 30 rpm.
  • a "unit" in a polymer means an atomic group based on a monomer formed by polymerization of the monomer.
  • the unit may be a unit formed directly by a polymerization reaction, or may be a unit in which a part of the unit is converted into a different structure by processing the polymer.
  • a unit based on monomer a is also referred to simply as a "monomer a unit.”
  • the resin-coated metal foil of the present invention (hereinafter also referred to as “the resin-coated metal foil”) is a resin-coated metal foil having, in this order, a metal foil, a first resin layer containing a tetrafluoroethylene-based polymer (hereinafter also referred to as "F polymer”), and a second resin layer derived from an aromatic resin, in which the ratio of the thickness of the first resin layer to the thickness of the metal foil is greater than 0.33, and at least the aromatic resin is a modified polyphenylene ether resin having a polymerizable carbon-carbon double bond, and the second resin layer contains a styrene-based elastomer, or at least the first resin layer and the second resin layer each contain an inorganic filler that has been surface-treated with a silane coupling agent and has an average particle size of less than 15 ⁇ m.
  • F polymer tetrafluoroethylene-based polymer
  • a preferred embodiment of the present resin-coated metal foil is a resin-coated metal foil (hereinafter also referred to as "the present resin-coated metal foil 1") having a metal foil, a first resin layer containing an F polymer, and a second resin layer derived from a polyphenylene ether resin, in that order, in which the ratio of the thickness of the first resin layer to the thickness of the metal foil is greater than 0.33, the polyphenylene ether resin is a modified polyphenylene ether resin having a polymerizable carbon-carbon double bond, and the second resin layer contains a styrene-based elastomer.
  • This resin-coated metal foil 1 has excellent mechanical properties, heat resistance, and electrical properties (low linear expansion coefficient, low dielectric constant, and low dielectric tangent) based on the first resin layer containing an F polymer and the second resin layer derived from a polyphenylene ether resin, and also has small transmission loss even in the high frequency range, suppressed warping, and excellent interlayer adhesion.
  • the first resin layer containing an F polymer has a high linear expansion coefficient, making it difficult to simultaneously suppress warping due to heating and maintain dimensional stability, and to ensure heat resistance and electrical properties while also ensuring interlayer adhesion, and is therefore subject to restrictions on the thickness of each layer. This tendency is particularly pronounced when attempting to make the first resin layer containing an F polymer thicker relative to the thickness of the metal foil.
  • the second resin layer is derived from a modified polyphenylene ether resin having a polymerizable carbon-carbon double bond and contains a styrene-based elastomer.
  • the polyphenylene ether resin which can also be considered as a cross-linked polyphenylene ether resin, hardens and interacts with the styrene-based elastomer through stacking, and it is assumed that a matrix structure that loosely incorporates the polyphenylene ether resin is likely to be formed.
  • the flexibility of the styrene-based elastomer in the second resin layer is fully expressed, and the buffering effect against the linear expansion of the first resin layer containing the F polymer is improved.
  • the first resin layer containing the F polymer is made thicker than the thickness of the copper foil, specifically when the ratio of the thickness of the first resin layer to the thickness of the metal foil is more than 0.33, it is believed that warping due to heating is suppressed and the interlayer adhesion of the resin-coated metal foil is improved.
  • the inventors have discovered that because the first resin layer, which is sufficiently thick relative to the thickness of the metal foil and contains an F polymer, is in contact with the metal foil, it is possible to improve electrical properties and reduce transmission loss in the high frequency range. They have also discovered that this effect is more pronounced when the first resin layer contains a specific F polymer, which will be described later.
  • a preferred embodiment of the resin-coated metal foil of the present invention is a resin-coated metal foil (hereinafter also referred to as "the resin-coated metal foil 2 of the present invention") having, in this order, a metal foil, a first resin layer containing an F polymer, and a second resin layer derived from an aromatic resin, in which the ratio of the thickness of the first resin layer to the thickness of the metal foil is greater than 0.33, and the first resin layer and the second resin layer each contain an inorganic filler that has been surface-treated with a silane coupling agent and has an average particle size of less than 15 ⁇ m.
  • This resin-coated metal foil 2 has excellent mechanical properties, heat resistance, and electrical properties (low linear expansion coefficient, low dielectric constant, and low dielectric tangent) based on the first resin layer containing an F polymer and the second resin layer derived from an aromatic resin, and also has small transmission loss even in the high frequency range, suppressed warping, and excellent interlayer adhesion.
  • the first resin layer containing an F polymer has a high linear expansion coefficient, making it difficult to simultaneously suppress warping due to heating to maintain dimensional stability, and to ensure heat resistance and electrical properties while also ensuring interlayer adhesion, and is therefore subject to restrictions on the thickness of each layer. This tendency is particularly pronounced when attempting to make the first resin layer containing an F polymer thicker relative to the thickness of the metal foil.
  • both the first resin layer containing the F polymer and the second resin layer derived from an aromatic resin are surface-treated with a silane coupling agent and contain a fine-grained inorganic filler with improved affinity to the resin. It is believed that the fine-grained inorganic filler is uniformly distributed in the first resin layer containing the F polymer, thereby controlling the linear expansion of the first resin layer, and that the inorganic filler present near the interface of the first resin layer improves the affinity with the second resin layer. It is believed that the distribution of the fine-grained inorganic filler in the second resin layer improves the affinity between the two resin layers and enhances the buffering effect of the second resin layer against the linear expansion of the first resin layer.
  • the first resin layer containing the F polymer is made thicker than the thickness of the copper foil, for example, even if the ratio of the thickness of the first resin layer to the thickness of the metal foil exceeds 0.33, it is believed that the warping of the resin-coated metal foil due to heating is suppressed and the interlayer adhesion of the resin-coated metal foil is improved.
  • the inventors have discovered that because the first resin layer containing an F polymer, which is sufficiently thick relative to the thickness of the metal foil, is in contact with the metal foil, it is possible to improve electrical properties and reduce transmission loss in the high frequency range. They have also discovered that when the first resin layer contains a specific F polymer described below, the aromatic resin constituting the second resin layer is a modified polyphenylene ether resin and further contains a styrene-based elastomer, this effect is significantly manifested.
  • the metal foil constituting the resin-coated metal foil includes metal foils of copper, nickel, aluminum, titanium, and alloys thereof. Of these, copper is preferred. Examples of the copper foil include rolled copper foil and electrolytic copper foil.
  • the surface of the metal foil may be formed with an anti-rust layer such as a chromate layer, a heat-resistant layer, etc. Furthermore, at least a part of the surface of the metal foil may be treated with a silane coupling agent.
  • the ten-point average roughness of the surface of the metal foil is preferably 0.01 to 4 ⁇ m, in which case the interlayer adhesion with the first resin layer is good, and it is easy to obtain a resin-coated metal foil with excellent transmission properties.
  • the thickness of the metal foil is preferably 5 ⁇ m or more and 40 ⁇ m or less, and more preferably 5 ⁇ m or more and 25 ⁇ m or less.
  • the F polymer constituting the first resin layer of the resin-coated metal foil is a polymer containing units (hereinafter also referred to as "TFE units") based on tetrafluoroethylene (hereinafter also referred to as "TFE units").
  • TFE units polymer containing units
  • the F polymer may be either heat-fusible or non-heat-fusible, but it is preferable that at least one type of F polymer is heat-fusible.
  • the heat-fusible polymer means a polymer that has a temperature at which the melt flow rate is 1 to 1000 g/10 min under a load of 49 N.
  • the melting temperature of the heat-fusible F polymer is preferably 200° C. or higher, more preferably 260° C. or higher.
  • the melting temperature of the F polymer is preferably 325° C. or lower, more preferably 320° C. or lower.
  • the glass transition temperature of the F polymer is preferably from 60 to 120°C.
  • the fluorine content of the F polymer is preferably from 70 to 76% by mass.
  • the surface tension of the F polymer is preferably 16 to 26 mN/m.
  • the surface tension of the F polymer can be measured by placing a droplet of a mixture for wetting tension testing (manufactured by Wako Pure Chemical Industries, Ltd.) specified in JIS K 6768 on a flat plate made of the F polymer.
  • F polymer includes polytetrafluoroethylene (PTFE), polymer containing TFE unit and unit based on ethylene (ETFE), polymer containing TFE unit and unit based on propylene, polymer containing TFE unit and unit based on perfluoro(alkyl vinyl ether) (PAVE) (PAVE unit) (PFA), polymer containing TFE unit and unit based on hexafluoropropylene (FEP).
  • PTFE polytetrafluoroethylene
  • ETFE ethylene
  • PAVE perfluoro(alkyl vinyl ether)
  • FEP hexafluoropropylene
  • F polymer is preferably PFA or FEP, more preferably PFA.
  • PAVE is preferably CF 2 ⁇ CFOCF 3 , CF 2 ⁇ CFOCF 2 CF 3 or CF 2 ⁇ CFOCF 2 CF 2 CF 3 (hereinafter also referred to as “PPVE”), and more preferably PPVE.
  • At least one of the F polymers preferably has an oxygen-containing polar group, more preferably has a hydroxyl- or carbonyl-containing group, and even more preferably has a carbonyl-containing group.
  • the interlayer adhesion between the metal foil, the first resin layer, and the second resin layer in the resin-coated metal foil is likely to be improved.
  • the resin-coated metal foil is likely to have excellent physical properties such as heat resistance and electrical properties (low linear expansion coefficient, low dielectric constant, and low dielectric tangent), and the transmission loss in the high frequency range is likely to be small.
  • the hydroxyl-containing group is preferably a group containing an alcoholic hydroxyl group, more preferably --CF 2 CH 2 OH or --C(CF 3 ) 2 OH.
  • the carbonyl group-containing group is preferably a carboxyl group, an alkoxycarbonyl group, an amide group, an isocyanate group, a carbamate group (-OC(O)NH 2 ), an acid anhydride residue (-C(O)OC(O)-), an imide residue (-C(O)NHC(O)-, etc.), a formyl group, a halogenoformyl group, a urethane group (-NHC(O)O-), a carbamoyl group (-C(O)-NH 2 ), a ureido group (-NH-C(O)-NH 2 ), an oxamoyl group (-NH-C(O)-C(O)-NH 2 ) or a carbonate group (-OC(O)
  • the number of oxygen-containing polar groups in the F polymer is preferably 10 to 5000, more preferably 100 to 3000, per 1 ⁇ 10 6 carbon atoms in the main chain.
  • the number of oxygen-containing polar groups in the F polymer can be quantified by the composition of the polymer or the method described in WO 2020/145133.
  • the oxygen-containing polar group may be contained in a unit based on a monomer in the F polymer, or may be contained in a terminal group of the main chain of the F polymer, with the former being preferred.
  • Examples of the latter include F polymers having an oxygen-containing polar group as a terminal group derived from a polymerization initiator, a chain transfer agent, etc., and F polymers obtained by subjecting F polymers to plasma treatment or ionizing radiation treatment.
  • the heat-fusible F polymer a polymer (1) containing TFE units and PAVE units, with 2.0 to 5.0 mol% of PAVE units relative to the total units, and without oxygen-containing polar groups, or a polymer (2) containing TFE units and PAVE units and with oxygen-containing polar groups, is preferred.
  • a polymer (1) containing TFE units and PAVE units, with 2.0 to 5.0 mol% of PAVE units relative to the total units, and without oxygen-containing polar groups, or a polymer (2) containing TFE units and PAVE units and with oxygen-containing polar groups is preferred.
  • spherulites with a relatively small radius are easily formed. Therefore, the first resin layer in this resin-coated metal foil has high surface smoothness, and the interlayer adhesion between the metal foil and the second resin layer is easily improved.
  • Polymer (1) is composed of only TFE unit and PAVE unit, and more preferably contains PAVE unit more than 2.5 mol% and 5.0 mol% or less with respect to all units.
  • polymer (1) does not have oxygen-containing polar group means that the number of oxygen-containing polar groups that polymer has is less than 100 per 1 x 106 carbon atoms that constitute the polymer main chain.
  • the number of the oxygen-containing polar groups is more preferably less than 50.
  • the lower limit of the number of the oxygen-containing polar groups is 0.
  • the polymer (1) may be produced by using a polymerization initiator or a chain transfer agent that does not generate an oxygen-containing polar group as a terminal group of the polymer chain, or by fluorinating an F polymer having an oxygen-containing polar group (such as an F polymer having an oxygen-containing polar group derived from a polymerization initiator at the terminal group of the polymer main chain).
  • fluorination method include a method using fluorine gas (see JP 2019-194314 A, etc.).
  • the polymer (2) is preferably a thermally meltable F polymer having a carbonyl group-containing group, including TFE units and PAVE units, more preferably a polymer including TFE units, PAVE units, and units based on a monomer having a carbonyl group-containing group, and including these units in the order of 90 to 99 mol%, 0.99 to 9.97 mol%, and 0.01 to 3 mol% relative to the total units.
  • F polymers include the polymers described in WO 2018/16644.
  • the monomer having a carbonyl group-containing group is preferably itaconic anhydride, citraconic anhydride, or 5-norbornene-2,3-dicarboxylic anhydride (hereinafter also referred to as "NAH"), and more preferably NAH.
  • the F polymer constituting the first resin layer is preferably composed of a molten sintered body of a mixture of particles of polytetrafluoroethylene (PTFE) and particles of a heat-fusible F polymer having an oxygen-containing polar group.
  • PTFE polytetrafluoroethylene
  • the content of the PTFE particles in the mixture of the PTFE particles and the particles of the heat-fusible F polymer having an oxygen-containing polar group is preferably 50 to 90 mass%, more preferably 75 to 90 mass%.
  • the present resin-coated metal foil may further contain an aromatic polymer.
  • the affinity with the modified polyphenylene ether resin or styrene-based elastomer described below constituting the second resin layer is likely to be improved, and the interlayer adhesion is likely to be further improved.
  • the aromatic polymer include polyester resins such as liquid crystalline aromatic polyesters, polyimide resins, polyamideimide resins, epoxy resins, maleimide resins, urethane resins, polyphenylene ether resins, polyphenylene oxide resins, and polyphenylene sulfide resins.
  • the aromatic polymer is preferably a polyimide or a precursor thereof, and more preferably at least one polyimide or a precursor thereof selected from the group consisting of aromatic polyimides, aromatic polyamic acids, aromatic polyamideimides, and precursors of aromatic polyamideimides.
  • the content thereof relative to the F polymer is preferably 1 to 25% by mass.
  • the first resin layer in the present resin-coated metal foil 1 may further contain an inorganic filler.
  • inorganic fillers include the present inorganic filler described below.
  • the inorganic filler may be used alone or in combination of two or more kinds. Among the above, from the viewpoint of keeping the dielectric constant and linear expansion coefficient of the first resin layer low and further suppressing warping of the resin-coated metal foil, silica, alumina, titanium oxide, boron nitride, talc, etc. are preferred, and silica is more preferred.
  • the specific surface area of the inorganic filler as measured by the BET method is preferably in the range of 1 to 50 m 2 /g.
  • the average particle size (D50) of the inorganic filler is preferably 0.1 to 20 ⁇ m.
  • the inorganic filler may have various shapes such as a sphere, a cube, an octahedron, a plate, a scale, a bar, a rod, a column, a cone, a frustum, a polyhedron, a hollow shape, and the like.
  • the inorganic filler may be surface-treated with a silicone compound such as a silane coupling agent.
  • the amount of the inorganic filler is preferably 30% by mass or more, more preferably 40% by mass or more, based on the total amount of the F polymer and the inorganic filler.
  • the content of the inorganic filler is preferably 80% by mass or less, more preferably 60% by mass or less, based on the total amount of the F polymer and the inorganic filler.
  • the first resin layer in this resin-coated metal foil 2 contains an inorganic filler that has been surface-treated with a silane coupling agent and has an average particle size of less than 15 ⁇ m. Such inorganic fillers will be described later.
  • the first resin layer in the resin-coated metal foil 2 may further contain an aromatic resin.
  • the affinity with the aromatic resin constituting the second resin layer, which will be described later, is likely to be improved, and the interlayer adhesion is likely to be further improved.
  • the aromatic resin include polyester resins such as liquid crystal aromatic polyesters, polyimide resins, polyamideimide resins, epoxy resins, maleimide resins, urethane resins, polyphenylene ether resins, polyphenylene oxide resins, and polyphenylene sulfide resins.
  • the aromatic resin is preferably polyimide or a precursor thereof, and more preferably at least one polyimide or a precursor thereof selected from the group consisting of aromatic polyimides, aromatic polyamic acids, aromatic polyamideimides, and precursors of aromatic polyamideimides.
  • the content thereof relative to the F polymer is preferably 1 to 25% by mass.
  • the thickness of the first resin layer in this resin-coated metal foil is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and even more preferably 15 ⁇ m or more.
  • the thickness of the first resin layer is preferably 100 ⁇ m or less, and more preferably 50 ⁇ m or less.
  • the ratio of the thickness of the first resin layer to the thickness of the metal foil in this resin-coated metal foil is more than 0.33, preferably 0.5 or more, and more preferably 0.7 or more and 2.0 or less.
  • the ratio of the thickness of the first resin layer to the thickness of the metal foil is more preferably 1, and more preferably 1.7 or less.
  • the content of the F polymer in the first resin layer of the resin-coated metal foil is preferably 25% by mass or more, more preferably 40% by mass or more.
  • the content may be 100% by mass or less, and is preferably 90% by mass or less, more preferably 75% by mass or less.
  • the content of the F polymer in the first resin layer of the resin-coated metal foil 1 is preferably 50% by mass or more, more preferably 60% by mass or more.
  • the content may be 100% by mass or less.
  • the first resin layer does not contain an elastomer.
  • the surface of the first resin layer (the surface opposite to the metal foil) preferably contains an oxygen-containing polar group.
  • the oxygen-containing polar group is present on the surface of the layer, the adhesiveness is increased, and the interlayer adhesiveness with the second resin layer can be improved.
  • the oxygen-containing polar group is preferably a hydroxyl group-containing group or a carbonyl group-containing group.
  • Methods for making the oxygen-containing polar group present on the surface of the first resin layer in the present resin-coated metal foil include a method using an F polymer having an oxygen-containing polar group, or a method in which the surface of the first resin layer is subjected to a surface treatment such as corona discharge treatment, plasma treatment, UV ozone treatment, excimer treatment, chemical etching, or silane coupling treatment to introduce the oxygen-containing polar group.
  • a surface treatment such as corona discharge treatment, plasma treatment, UV ozone treatment, excimer treatment, chemical etching, or silane coupling treatment to introduce the oxygen-containing polar group.
  • the second resin layer of the resin-coated metal foil is an aromatic resin-derived resin.
  • the aromatic resin constituting the second resin layer include polyester resins such as liquid crystalline aromatic polyesters, polyimide resins, polyamideimide resins, epoxy resins, maleimide resins, urethane resins, polyphenylene ether resins, polyphenylene oxide resins, and polyphenylene sulfide resins.
  • the aromatic resin is preferably a polyphenylene ether resin, and more preferably a modified polyphenylene ether resin having a polymerizable carbon-carbon double bond (hereinafter also referred to as a "modified PPE resin").
  • the second resin layer of the resin-coated metal foil 1 is a resin layer derived from a polyphenylene ether resin, and the resin derived from such a polyphenylene ether is a modified PPE resin.
  • a polyphenylene ether resin that has been terminally modified with a group having a polymerizable carbon-carbon double bond is preferred.
  • a modified polyphenylene ether resin that has, as a repeating unit, a polyphenylene ether chain that may have a substituent selected from halogen atoms, alkyl groups, and aryl groups on at least some of the carbon atoms that make up the aromatic ring, and has a group having a polymerizable carbon-carbon double bond bonded to the end of the polyphenylene ether chain is preferred.
  • the above-mentioned groups having a polymerizable carbon-carbon double bond include alkenyl groups such as vinyl, propenyl, butenyl, pentenyl, hexenyl, heptanyl, octenyl, decenyl, dodecenyl, octadecenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl; vinylbenzyl groups (ethenylbenzyl groups) such as p-ethenylbenzyl and m-ethenylbenzyl, vinylphenyl groups, acrylate groups, and methacrylate groups.
  • vinylbenzyl groups, vinylphenyl groups, acrylate groups, and methacrylate groups are preferred, and acrylate groups and methacrylate groups are more preferred.
  • the number average molecular weight of the modified PPE resin is preferably 1000 or more and 5000 or less, and more preferably 1000 or more and 4000 or less, from the viewpoint of easily improving the formability and heat resistance of the second resin layer and easily improving the dielectric properties of the resin-coated metal foil.
  • the number average molecular weight is a standard polystyrene equivalent value measured by gel permeation chromatography (GPC).
  • the second resin layer in the resin-coated metal foil 1 contains a styrene-based elastomer along with the modified PPE resin.
  • the second resin layer acts as a buffer against the linear expansion of the first resin layer, due to the presumed mechanism described above, suppressing warping of the resin-coated metal foil and providing excellent interlayer adhesion.
  • the electrical properties of the resin-coated metal foil are excellent, and transmission loss in the high frequency range is reduced.
  • the second resin layer in the resin-coated metal foil 1 is formed from a prepreg layer containing modified PPE resin as the matrix resin, it is preferable that the styrene-based elastomer constitutes the matrix resin together with the modified PPE resin. Furthermore, when the matrix resin in the prepreg is modified PPE resin and styrene-based elastomer, the content of the matrix resin in the prepreg is preferably 50% by mass or more and 90% by mass or less. Within this range, warping due to heating is suppressed, and it is easy to obtain the resin-coated metal foil with excellent interlayer adhesion. It is preferable that the second resin layer does not contain F polymer, from the viewpoint of further improving the interlayer adhesion and suppression of warping of the resin-coated metal foil.
  • Styrenic elastomers include block copolymers having polymer blocks containing structural units derived from styrene compounds, and polymer blocks containing structural units derived from conjugated diene compounds, or hydrogenated products thereof.
  • Specific examples of styrene elastomers include styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, styrene-ethylene-styrene block copolymers, styrene-propylene-styrene block copolymers, styrene-ethylene/propylene-styrene block copolymers, styrene-ethylene/butylene-styrene block copolymers, styrene-hydrogenated butadiene-styrene block copolymers, styrene-hydrogenated isoprene-
  • the content of the styrene-based elastomer relative to the modified PPE resin in the second resin layer of the resin-coated metal foil 1 is preferably in the range of 1 to 40% by mass, and more preferably 5 to 25% by mass.
  • the resin-coated metal foil is excellent in suppressing warping, has excellent interlayer adhesion with the first resin layer, and has excellent electrical properties such as a low dielectric tangent.
  • the styrene-based elastomer when it has a polymerizable carbon-carbon double bond, it can form a crosslinked structure by reacting with the modified PPE resin constituting the second resin layer, which is more preferable from the viewpoint of making it easier to exhibit the above-mentioned action and effect.
  • the styrene-based elastomer having a polymerizable carbon-carbon double bond may be the above-mentioned styrene-based elastomer further containing a unit based on divinylbenzene in its molecular chain.
  • the divinylbenzene may be any positional isomer of o-divinylbenzene, m-divinylbenzene, or p-divinylbenzene, or a mixture thereof.
  • the second resin layer in the resin-coated metal foil 2 is preferably formed from a prepreg layer having a polyphenylene ether resin, preferably a modified PPE resin, as the matrix resin.
  • the second resin layer is preferably formed from a prepreg having a modified PPE resin as the matrix resin, in which the modified PPE resin is impregnated or applied to a fiber substrate in a semi-cured state.
  • examples of the fiber substrate include fiber substrates made of woven or nonwoven fabrics mainly composed of inorganic fibers such as glass fiber, carbon fiber, silicon carbide fiber, silicon nitride fiber, alumina fiber, silicon carbide fiber, and boron fiber; and organic fibers such as cellulose fiber, aromatic polyamide fiber, polyaramid fiber, polyparaphenylene benzoxazole fiber, polyphenylene sulfide fiber, polyester fiber, polyimide fiber, acrylic fiber, and fluororesin fiber.
  • inorganic fibers such as glass fiber, carbon fiber, silicon carbide fiber, silicon nitride fiber, alumina fiber, silicon carbide fiber, and boron fiber
  • organic fibers such as cellulose fiber, aromatic polyamide fiber, polyaramid fiber, polyparaphenylene benzoxazole fiber, polyphenylene sulfide fiber, polyester fiber, polyimide fiber, acrylic fiber, and fluororesin fiber.
  • the prepreg forming the second resin layer in the resin-coated metal foil 2 can be produced by a method known in the art, such as an impregnation method, a coating method using various coaters, or a spray method.
  • the intrinsic viscosity of the modified PPE resin is preferably 0.03 dl/g or more and 0.12 dl/g or less, and more preferably 0.04 dl/g or more and 0.11 dl/g or less.
  • the intrinsic viscosity is the intrinsic viscosity measured in methylene chloride at 25° C. using a viscometer such as the AVS500 Visco System manufactured by Schott.
  • a commercially available product may be used as the prepreg for forming the second resin layer.
  • the second resin layer in the resin-coated metal foil 2 contains an inorganic filler that has been surface-treated with a silane coupling agent and has an average particle size of less than 15 ⁇ m. Such inorganic fillers will be described later.
  • the second resin layer in the resin-coated metal foil 2 preferably contains a styrene-based elastomer in addition to an aromatic resin, preferably a modified PPE resin.
  • a modified PPE resin preferably a modified PPE resin.
  • the modified PPE resin which can also be considered as a cross-linked polyphenylene ether resin, hardens to form a matrix structure loosely incorporating the styrene-based elastomer.
  • the flexibility of the styrene-based elastomer is fully expressed in the second resin layer, and it has a buffering effect against the linear expansion of the first resin layer containing the F polymer. Therefore, the warping of the resin-coated metal foil can be further suppressed, and the interlayer adhesion is excellent.
  • the electrical properties (dielectric constant and low dielectric tangent) of the resin-coated metal foil are excellent, and the transmission loss in the high frequency range is small.
  • the second resin layer in the resin-coated metal foil 2 is formed from a prepreg layer having a modified PPE resin as the matrix resin
  • the styrene-based elastomer constitutes the matrix resin together with the modified PPE resin.
  • the matrix resin in the prepreg is a modified PPE resin and a styrene-based elastomer
  • the content of the matrix resin in the prepreg is preferably 50% by mass or more and 90% by mass or less. When the content is within this range, warping due to heating is suppressed, and it is easy to obtain a resin-coated metal foil having excellent interlayer adhesion.
  • styrene-based elastomers include elastomers similar to the styrene-based elastomers mentioned above.
  • the content of the styrene-based elastomer relative to the aromatic resin is preferably in the range of 1 to 40% by mass, and more preferably 5 to 25% by mass.
  • the resin-coated metal foil is excellent in suppressing warping, has excellent interlayer adhesion with the first resin layer, and has excellent electrical properties such as a low dielectric tangent.
  • the styrene-based elastomer has a polymerizable carbon-carbon double bond
  • the aromatic resin constituting the second resin layer is a modified PPE resin
  • it can form a crosslinked structure by reacting with the modified PPE resin, which is more preferable from the viewpoint of making it easier to exhibit the above-mentioned action and effect.
  • Specific examples of the styrene-based elastomer having a polymerizable carbon-carbon double bond include the same elastomers as the above-mentioned styrene-based elastomer having a polymerizable carbon-carbon double bond.
  • the thickness of the second resin layer in the present resin-coated copper foil is preferably in the range of 10 to 1000 ⁇ m, more preferably in the range of 50 to 500 ⁇ m.
  • the ratio of the thickness of the second resin layer to the thickness of the first resin layer in the resin-coated copper foil is preferably 2 or more.
  • the thickness ratio is preferably 100 or less, more preferably 10 or less.
  • Both the first resin layer and the second resin layer constituting the present resin-coated metal foil 2 contain an inorganic filler having an average particle diameter of less than 15 ⁇ m that has been surface-treated with a silane coupling agent (hereinafter also referred to as "the present inorganic filler").
  • Examples of materials for the inorganic filler include silica such as quartz powder, crystalline silica, fused silica, and spherical fused silica; silicon compounds such as wollastonite, talc, mica, silicon nitride, silicon carbide, calcium silicate, and mica; nitrogen compounds such as boron nitride and aluminum nitride; aluminum oxide, zinc oxide, titanium oxide, cerium oxide, beryllium oxide, magnesium oxide, nickel oxide, vanadium oxide, zirconium oxide, tin oxide, antimony oxide, indium oxide, tin-doped indium oxide (ITO), and copper oxide.
  • silica such as quartz powder, crystalline silica, fused silica, and spherical fused silica
  • silicon compounds such as wollastonite, talc, mica, silicon nitride, silicon carbide, calcium silicate, and mica
  • nitrogen compounds such as boron nitride and aluminum nitride
  • metal oxides such as iron oxide and silver oxide
  • metal salts such as calcium carbonate, potassium titanate, aluminum hydroxide, magnesium hydroxide, aluminum borate and barium sulfate
  • carbon fibers such as carbon black, acetylene black, ketjen black, graphite, graphene and carbon nanotubes
  • minerals such as montmorillonite, boehmite, kaolin, smectite, zonolite, vermiculite and sericite
  • metals such as silver and copper; glass beads, glass flakes and glass balloons.
  • the inorganic filler may be used alone or in combination of two or more kinds. Among them, from the viewpoint of keeping the dielectric constant and linear expansion coefficient of the first resin layer low, exhibiting the buffering effect of the second resin layer, and further suppressing warping of the resin-coated metal foil, silica, alumina, titanium oxide, boron nitride, talc, etc. are preferred, and silica is more preferred. In other words, it is preferred that the material of the inorganic filler contained in each of the first resin layer and the second resin layer is silica from the viewpoint of further exhibiting the above-mentioned action and effect.
  • the specific surface area of the present inorganic filler as measured by the BET method is preferably in the range of 1 to 50 m 2 /g.
  • the inorganic filler may have various shapes such as a spherical, cubic, octahedral, plate-like, scaly, rod-like, columnar, cone-like, frustum-like, polyhedral, hollow, etc., but is preferably spherical, and more preferably approximately spherical.
  • the silane coupling agent preferably has a trialkoxysilyl group, such as a trimethoxysilyl group or a triethoxysilyl group.
  • the silane coupling agent may be a compound in which a functional group such as a triazine group, an isocyanate group, an isocyanuric acid group, a benzotriazole group, an amino group, an acid anhydride group, a mercapto group, an azasilacyclopentane group, an imidazole group, an epoxy group, a vinyl group, a (meth)acrylic group, or a (meth)acryloyloxy group is bonded to a trialkoxysilyl group via a linking group.
  • a functional group such as a triazine group, an isocyanate group, an isocyanuric acid group, a benzotriazole group, an amino group, an acid anhydride group, a mercapto group, an azasilacycl
  • linking groups include groups having a divalent organic group (such as an alkylene group or an alkylene group having an etheric oxygen atom between carbon atoms) as the main chain.
  • the linking group may further include an imino bond, an amide bond, a urea bond, a urethane bond, and a carbodiimide bond.
  • the silane coupling agent may have a plurality of different types of the above-mentioned functional groups, or may have a plurality of the same type of functional groups.
  • silane coupling agent examples include 3-isocyanatepropyltriethoxysilane, 3-ureidopropyltriethoxysilane, tris(trimethoxysilylpropyl)isocyanurate, tris(triethylsilylpropyl)isocyanurate, 1-(3-(trimethoxysilyl)propyl)-3,5-di-2-propenyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-tris(3-(trimethoxysilyl)propyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, N-[5-(trimethoxysilyl)-2-azane] -1-oxopentyl]caprolactam, N-[5-(triethoxysilyl)-2-aza-1-oxopentyl]caprolactam, N
  • the silane coupling agent is preferably an acrylic silane coupling agent or a vinyl silane coupling agent, and is preferably a silane coupling agent in which a (meth)acrylic group, a (meth)acryloyloxy group or a vinyl group is bonded to a trialkoxysilyl group via a linking group, and for example, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-acryloyloxypropyltrimethoxysilane, or vinyltrimethoxysilane is preferred.
  • a method for surface treating an inorganic filler with a silane coupling agent includes mixing a solution containing the silane coupling agent with the inorganic filler.
  • the mixture of the solution containing the silane coupling agent and the inorganic filler may be heated, preferably under heating reflux conditions, to promote the reaction of the silane coupling agent.
  • the solvent is removed from the solution after the mixing process, and the solution is further dried as necessary to obtain the inorganic filler.
  • the average particle size (D50) of the present inorganic filler is less than 15 ⁇ m, preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and particularly preferably 2.5 ⁇ m or less.
  • the average particle size of the present inorganic filler is preferably 0.1 ⁇ m or more.
  • the ratio of the average particle diameter of the inorganic filler contained in the first resin layer to the average particle diameter of the inorganic filler contained in the second resin layer is preferably 0.02 to 5.
  • the average particle diameter of the inorganic filler contained in the first resin layer is 0.2 to 2 ⁇ m and the average particle diameter of the inorganic filler contained in the second resin layer is 0.2 to 10 ⁇ m, from the viewpoints of controlling the linear expansion of the first resin layer as described above, making it easier for the second resin layer to exhibit a buffering effect against the linear expansion of the first resin layer, suppressing warping of the resin-coated metal foil due to heating and providing excellent interlayer adhesion, providing excellent heat resistance, mechanical properties, electrical properties, etc. based on the physical properties of the F polymer and aromatic resin, and further reducing transmission loss in the high frequency range.
  • the inorganic filler may be a commercially available product (such as a silica filler under the trade name SC2300-SVJ manufactured by Admatechs Co., Ltd.).
  • the content of the inorganic filler relative to the F polymer in the first resin layer of the resin-coated copper foil 2 and the content of the inorganic filler relative to the aromatic resin in the second resin layer are preferably 50% by mass or more, more preferably 60% by mass or more.
  • the above contents may be 100% by mass or less, or may be less than 100% by mass.
  • it is preferable that the content of the inorganic filler relative to the F polymer in the first resin layer is smaller than the content of the inorganic filler relative to the aromatic resin in the second resin layer.
  • the metal foil, the first resin layer, and the second resin layer are laminated in this order. It is preferable that the metal foil and the first resin layer, and the first resin layer and the second resin layer are laminated in direct contact with each other. In this case, the physical properties of the present resin-coated metal foil, such as the low dielectric constant and the low dielectric loss tangent, based on the F polymer, are easily expressed in a well-balanced manner. In addition, the present resin-coated metal foil is easily prevented from warping or peeling, and the transmission loss in the high frequency range is easily improved.
  • the thickness of the first resin layer and the second resin layer is measured by a contact thickness gauge DG-525H (manufactured by Ono Sokki Co., Ltd.) using a probe AA-026 ( ⁇ 10 mm, SR7).
  • the warpage rate of this resin-coated metal foil is preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less. In this case, peeling at the interface between the metal foil and the first resin layer due to heating is further suppressed. In addition, this resin-coated metal foil has excellent handling properties when processed into a printed circuit board, and the resulting printed circuit board has excellent transmission characteristics.
  • the dielectric constant (relative dielectric constant) of the resin-coated metal foil is preferably 2.0 to 3.0.
  • the dielectric loss tangent of the resin-coated metal foil is preferably 0.0001 to 0.003.
  • the dielectric loss tangent of the resin-coated metal foil is preferably less than 0.003, more preferably 0.0025 or less, and even more preferably 0.002 or less.
  • the absolute value of the linear expansion coefficient of the resin-coated metal foil is preferably 30 ppm/° C. or less, and more preferably 15 ppm/° C. or less. In this case, the resin-coated metal foil is effectively prevented from warping, regardless of the temperature of the atmosphere in which the resin-coated metal foil is placed.
  • the lower limit of the absolute value of the linear expansion coefficient of the resin-coated metal foil is 0 ppm/° C.
  • the peel strength between the first resin layer and the second resin layer in the resin-coated metal foil is preferably 10 N/cm or more, more preferably 15 N/cm or more.
  • the peel strength is preferably 100 N/cm or less.
  • the resin-coated metal foil can be suitably used as a printed circuit board material.
  • the first resin layer in the resin-coated metal foil may be formed from a resin film containing an F polymer. Specifically, the resin film containing an F polymer that will be the first resin layer is placed on the surface of the metal foil, and a layer containing a styrene-based elastomer and a modified PPE resin that will be the second resin layer is placed on the surface of the resin film containing the F polymer as a lamination surface, and preferably laminated by heat pressing to form the metal foil, the first resin layer, and the second resin layer, thereby producing the resin-coated metal foil 1.
  • the resin film containing an F polymer and the inorganic filler that will be the first resin layer is placed on the surface of the metal foil, and a layer containing an aromatic resin and the inorganic filler that will be the second resin layer is placed on the surface of the resin film containing the F polymer and the inorganic filler as a lamination surface, and preferably laminated by heat pressing to form the metal foil, the first resin layer, and the second resin layer, thereby producing the resin-coated metal foil 2.
  • the first resin layer in the resin-coated metal foil is preferably a molten sintered body of F polymer particles (hereinafter also referred to as "F particles”).
  • the first resin layer in the resin-coated metal foil is preferably formed from a liquid composition (hereinafter also referred to as “the liquid composition") containing F polymer particles (hereinafter also referred to as "F particles”) and a dispersion medium.
  • the resin-coated metal foil 1 is preferably produced by disposing the liquid composition on the surface of a metal foil, heating the liquid composition to form a first resin layer containing a molten sintered body of F polymer and having a thickness ratio of 0.5 or more to the thickness of the metal foil, disposing a layer containing a modified PPE resin and a styrene-based elastomer on the surface of the first resin layer as a lamination surface, and laminating the layers by hot pressing to form a second resin layer.
  • the layer containing a modified PPE resin and a styrene-based elastomer is preferably a prepreg containing a styrene-based elastomer and having the modified PPE resin as a matrix resin.
  • the resin-coated metal foil 2 is preferably produced by disposing the liquid composition further containing the inorganic filler on the surface of the metal foil and heating it to form a first resin layer containing a molten sintered body of the F polymer and the inorganic filler, disposing a layer containing an aromatic resin and the inorganic filler on the surface of the first resin layer as a lamination surface, and laminating them by hot pressing to form a second resin layer.
  • the layer containing an aromatic resin and the inorganic filler is preferably a prepreg containing the inorganic filler and having a modified PPE resin as a matrix resin.
  • the F particles preferably have an average particle size (D50) of 0.3 ⁇ m or more and less than 10 ⁇ m.
  • the D50 of the F particles is preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more.
  • the D50 of the F particles is preferably less than 10 ⁇ m, more preferably 8 ⁇ m or less.
  • the liquid composition is likely to have excellent dispersibility and processability, and the first resin layer formed from the liquid composition is likely to have excellent physical properties such as heat resistance, electrical properties (low linear expansion coefficient, low dielectric constant and low dielectric tangent), and surface appearance.
  • the F particles are particles containing an F polymer, and preferably consist of an F polymer.
  • the F particles may be used alone or in combination of two or more kinds.
  • the F particles are made of a mixture of PTFE particles and particles of heat-fusible F polymer having oxygen-containing polar group. That is, it is preferable that the F polymer constituting the first resin layer is made of a fused sintered body of a mixture of polytetrafluoroethylene (PTFE) particles and particles of heat-fusible F polymer having oxygen-containing polar group.
  • PTFE polytetrafluoroethylene
  • the content of the PTFE particles in the mixture of the PTFE particles and the particles of the heat-fusible F polymer having an oxygen-containing polar group is preferably 50 to 90 mass%, more preferably 75 to 90 mass%.
  • the details of the inorganic filler are the same as those of the inorganic filler contained in the first resin layer and the second resin layer described above, and the suitable inorganic filler type and the suitable content range are also the same.
  • the dispersion medium contained in the present liquid composition is preferably at least one selected from the group consisting of water, amides, ketones and esters.
  • the amide include N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropanamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N,N-diethylformamide, hexamethylphosphoric triamide, and 1,3-dimethyl-2-imidazolidinone.
  • ketone examples include acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, methyl isopentyl ketone, 2-heptanone, cyclopentanone, cyclohexanone, and cycloheptanone.
  • ester examples include methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl 3-ethoxypropionate, ⁇ -butyrolactone, and ⁇ -valerolactone.
  • the liquid composition may further contain another resin different from the F polymer.
  • Such another resin may be contained in the liquid composition as non-hollow particles, or may be dissolved or dispersed in the dispersion medium constituting the liquid composition.
  • the other resin is preferably an aromatic polymer, for example, the above-mentioned aromatic polymer that may be contained in the first resin layer.
  • the aromatic polymer is preferably a polyimide or a precursor thereof, and more preferably at least one polyimide or a precursor thereof selected from the group consisting of aromatic polyimide, aromatic polyamic acid, aromatic polyamideimide, and a precursor of aromatic polyamideimide.
  • the polyimide or a precursor thereof is preferably contained in the liquid composition as a varnish dissolved in a dispersion medium.
  • the content thereof relative to the F particles is preferably 1 to 25% by mass.
  • the liquid composition may further contain a surfactant.
  • the surfactant is preferably a nonionic surfactant.
  • nonionic surfactants include glycol-based surfactants, acetylene-based surfactants, silicone-based surfactants, and fluorine-based surfactants.
  • the liquid composition may further contain additives such as thixotropic agents, viscosity regulators, defoamers, dehydrating agents, plasticizers, weather resistance agents, antioxidants, heat stabilizers, lubricants, antistatic agents, brighteners, colorants, conductive agents, release agents, and flame retardants.
  • additives such as thixotropic agents, viscosity regulators, defoamers, dehydrating agents, plasticizers, weather resistance agents, antioxidants, heat stabilizers, lubricants, antistatic agents, brighteners, colorants, conductive agents, release agents, and flame retardants.
  • the content of F particles in the present liquid composition is preferably 25% by mass or more, more preferably 30% by mass or more, and is preferably 75% by mass or less, more preferably 60% by mass or less.
  • the viscosity of the liquid composition is preferably 10 mPa ⁇ s or more, more preferably 100 mPa ⁇ s or more.
  • the viscosity of the liquid composition is preferably 10,000 mPa ⁇ s or less, more preferably 3,000 mPa ⁇ s or less.
  • the liquid composition has excellent coatability and is easy to form a resin layer having a desired thickness.
  • the liquid composition having a viscosity in this range is easy to highly express the physical properties of the F polymer in the resin layer formed therefrom.
  • the liquid composition is preferably applied to the surface of the metal foil to first form a coating layer of the liquid composition on the surface of the metal foil.
  • Methods for applying the liquid composition include coating, droplet ejection, and immersion, with roll coating, knife coating, bar coating, die coating, and spraying being preferred.
  • the metal foil having the coating layer is heated to remove the dispersion medium constituting the liquid composition.
  • Heating for removing the dispersion medium is preferably performed at 100 to 200°C for 0.1 to 30 minutes. In this heating, it is not necessary to completely remove the dispersion medium, but it is sufficient to remove it to the extent that the layer formed by the packing of the F particles can maintain a self-supporting film.
  • air may be blown onto the surface to promote removal of the dispersion medium by air drying.
  • the heating for baking the F polymer is preferably carried out in a temperature range equal to or higher than the melting temperature of the F polymer, specifically, at 340 to 400° C. for 0.1 to 30 minutes.
  • the heating device for each heating may be an oven or a ventilated drying furnace.
  • the heat source in the device may be a contact type heat source (hot air, hot plate, etc.) or a non-contact type heat source (infrared rays, etc.).
  • Each heating may be carried out under normal pressure (atmospheric pressure) or under reduced pressure.
  • the atmosphere in each heating step may be either an air atmosphere or an inert gas atmosphere (helium gas, neon gas, argon gas, nitrogen gas, etc.).
  • a first resin layer containing an F polymer is formed on the surface of the metal foil, the thickness ratio of which to the thickness of the metal foil is greater than 0.33.
  • the ratio of the thickness of the first resin layer to the thickness of the metal foil is preferably 0.7 or more and 2.0 or less.
  • a layer containing an aromatic resin is formed on the surface of the first resin layer as a lamination surface, to obtain the resin-coated copper foil.
  • a layer containing a modified PPE resin and a styrene-based elastomer preferably a prepreg containing a styrene-based elastomer and having a modified PPE resin as a matrix resin, is arranged on the surface of the first resin layer as a lamination surface, and laminated by hot pressing to form a second resin layer, to obtain the resin-coated metal foil.
  • a layer containing an aromatic resin preferably a prepreg containing a modified PPE resin as a matrix resin and the inorganic filler, is arranged on the surface of the first resin layer as a lamination surface, and laminated by hot pressing to form a second resin layer, to obtain the resin-coated metal foil 2.
  • the heat press temperature is preferably equal to or lower than the melting point of the F polymer, more preferably 120 to 300° C., and even more preferably 140 to 240° C.
  • the heat pressing is preferably carried out at a vacuum of 20 kPa or less from the viewpoint of preventing air bubbles from entering the interfaces between the metal foil, the first resin layer, and the second resin layer, and preventing deterioration due to oxidation.
  • the pressure in the heat press is preferably 0.2 to 10 MPa from the viewpoint of laminating the first resin layer and the second resin layer with good interlayer adhesion while suppressing damage to the prepreg.
  • the resin-coated metal foil is useful for antenna parts, printed circuit boards, aircraft parts, automobile parts, etc., and is particularly useful as a printed circuit board material such as flexible printed circuit boards and rigid printed circuit boards.
  • the printed circuit board formed from the resin-coated metal foil 1 has, in this order, a transmission circuit made of a metal material, a first resin layer containing an F polymer, and a second resin layer derived from a polyphenylene ether resin (preferably a prepreg having a polyphenylene ether resin as a matrix resin), the ratio of the thickness of the first resin layer to the thickness of the metal material being greater than 0.33, the polyphenylene ether resin being a modified polyphenylene ether resin having a polymerizable carbon-carbon double bond, and the second resin layer containing a styrene-based elastomer.
  • the printed circuit board formed from the resin-coated metal foil 2 has, in this order, a transmission circuit made of a metal material, a first resin layer containing an F polymer, and a second resin layer derived from an aromatic resin (preferably a prepreg having a polyphenylene ether resin as a matrix resin), the ratio of the thickness of the first resin layer to the thickness of the metal material being greater than 0.33, and the first resin layer and the second resin layer each contain an inorganic filler having an average particle size of 15 ⁇ m or less that has been surface-treated with a silane coupling agent.
  • the printed circuit board can be manufactured, for example, by processing the metal layer of the resin-coated metal foil into a conductor circuit (pattern circuit) of a predetermined pattern by etching or the like, or by processing the resin-coated metal foil into a pattern circuit by electrolytic plating (semi-additive process (SAP process), modified semi-additive process (MSAP process), etc.).
  • SAP process spin-additive process
  • MSAP process modified semi-additive process
  • a printed circuit board after forming a pattern circuit, an interlayer insulating film may be formed on the pattern circuit, and a conductor circuit may be further formed on the interlayer insulating film.
  • a solder resist may be laminated on the pattern circuit, or a coverlay film may be laminated on the pattern circuit.
  • the present invention is not limited to the configurations of the above-mentioned embodiments.
  • the resin-coated metal foil may have any other configuration in addition to the configurations of the above-mentioned embodiments, or may be replaced with any configuration that produces a similar effect.
  • Copper foil 1 Electrolytic copper foil (manufactured by Fukuda Metal Foil and Powder Industries Co., Ltd., "CF-T49A-DS-HD2", thickness: 12 ⁇ m)
  • F Polymer F Particles 1: Particles of F Polymer 1 (melting temperature: 300° C., glass transition point: 85° C.) containing TFE units, NAH units and PPVE units in the order of 97.9 mol%, 0.1 mol% and 2.0 mol% and having 1,000 carbonyl group-containing groups per 1 ⁇ 10 6 main chain carbon atoms (D50: 2.4 ⁇ m, Tg: 85° C., specific surface area: 9 m 2 /g).
  • Example of liquid composition production (part 1) [Production Example 1-1] F particles 1, PAI, and water were mixed using a planetary centrifugal mixer to produce liquid composition 1-1 having an F particle 1 content of 33 mass % and a polyamideimide precursor content of 3 mass %. [Production Example 2-1] F particles 1 and water were mixed using a planetary centrifugal mixer to produce liquid composition 2-1 containing 33% by mass of F particles 1.
  • the prepreg 1-1 obtained in Production Example 3 was laminated as a second resin layer on the surface of the first resin layer of the laminate 1-1, and pressed at 185°C for 60 minutes under a pressure of 3.0 MPa in vacuum to obtain a resin-coated copper foil 1-1 having, in that order, a copper foil 1, a first resin layer containing an F polymer, and a second resin layer.
  • Examples 1-2 to 1-7 The same operation as in Example 1-1 was carried out except that the type of liquid composition used to form the first resin layer, or the type and thickness of the prepreg used as the second resin layer were changed as shown in Table 1, to obtain resin-coated copper foils 1-1 to 1-7 each having copper foil 1, a first resin layer, and a second resin layer in this order.
  • the configurations of each resin-coated copper foil are shown in Table 1.
  • the signal transmission loss of the resin-coated copper foil obtained in each example was measured by the following method. Signals up to 67 GHz were processed using a vector network analyzer (Keysight Technologies, E8361A) and measured with a GSG high frequency contact probe (Picoprobe, 250 ⁇ m pitch). The transmission line formed on the printed circuit board was a conductor-backed coplanar waveguide, and the characteristic impedance of the line was 50 ⁇ . Gold flash plating was applied to the surface of the copper conductor of the printed circuit board. TRL calibration (Thru-Reflect-Line calibration) was used as the calibration method. The length of the line was 100 mm, and the transmission loss per unit length was measured.
  • the S-parameter (hereinafter also referred to as the S value), which is one of the circuit network parameters used to express the characteristics of high-frequency electronic circuits and high-frequency electronic components. The closer the S value is to 0, the smaller the transmission loss is.
  • S value For each resin-coated copper foil, the S value at a frequency of 28 GHz of -2.5 [dB/100 mm] or more, showing low transmission loss, was evaluated as " ⁇ ", the S value less than -2.5 and -2.0 [dB/100 mm] or more was evaluated as " ⁇ ”, and the S value less than -2.0 [dB/100 mm] was evaluated as "X”.
  • Table 1 Note that the transmission loss of resin-coated copper foil 1-3 was not evaluated because of its large warpage.
  • Liquid composition production example (part 2) [Production Example 1-a] F particles 1, silica 1, and water were mixed using a planetary centrifugal mixer to produce liquid composition 1-a containing 33% by mass of F particles 1 and 33% by mass of silica 1. [Production Example 2-a] F particles 1, silica 2, and water were mixed using a planetary centrifugal mixer to produce liquid composition 2-a containing 33% by mass of F particles 1 and 33% by mass of silica 2.
  • [Production Example 5-a] A prepreg 3-a (thickness 100 ⁇ m) containing silica 3 and having PPE2 as a matrix was obtained in the same manner as in Production Example 3, except that silica 3 was used instead of silica 2.
  • [Production Example 6-a] A prepreg 4-a (thickness 100 ⁇ m) containing silica 4 and having PPE2 as a matrix was obtained in the same manner as in Production Example 3, except that silica 4 was used instead of silica 2.
  • [Production Example 7-a] A prepreg 5-a (thickness 100 ⁇ m) containing silica 5 and having PPE2 as a matrix was obtained in the same manner as in Production Example 3, except that silica 5 was used instead of silica 2.
  • the prepreg 1-a obtained in Production Example 3-a was laminated as a second resin layer on the surface of the first resin layer of the laminate 1-a, and pressed at 185°C for 60 minutes under a pressure of 3.0 MPa in vacuum to obtain a resin-coated copper foil 1-a having, in that order, a copper foil 1, a first resin layer containing an F polymer, and a second resin layer.
  • Examples 2-a to 5-a The same operation as in Example 1-a was carried out except that the type of liquid composition used to form the first resin layer or the type of prepreg used as the second resin layer was changed as shown in Table 1, to obtain resin-coated copper foils 2-a to 8-a each having copper foil 1, a first resin layer, and a second resin layer in this order.
  • the configuration of each resin-coated copper foil is shown in Table 2.
  • the results of the above-mentioned evaluation of each resin-coated copper foil are also shown in Table 2.
  • the resin-coated metal foil of the present invention is suppressed from warping due to heating, has excellent interlayer adhesion, and has excellent heat resistance, mechanical properties, electrical properties, etc. based on the physical properties of the F polymer and aromatic resin, and further has small transmission loss in the high frequency range. Therefore, it can be effectively used for printed circuit boards, etc. in various mobile communication devices such as mobile phones that are compatible with high speed and high frequency.
  • the entire contents of the specifications, claims and abstracts of Japanese Patent Application No. 2023-094917 and Japanese Patent Application No. 2023-094918 filed on June 8, 2023 are hereby incorporated by reference as the disclosure of the specification of the present invention.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)

Abstract

Une feuille métallique équipée d'une résine comprend une feuille métallique, une première couche de résine contenant un polymère à base de tétrafluoroéthylène, et une seconde couche de résine dérivée d'une résine aromatique, dans l'ordre indiqué. Le rapport de l'épaisseur de la première couche de résine à l'épaisseur de la feuille métallique est supérieur à 0,33. Au moins la résine aromatique est une résine d'éther de polyphénylène modifiée ayant une double liaison carbone-carbone polymérisable, et la seconde couche de résine contient un élastomère à base de styrène, ou au moins la première couche de résine et la seconde couche de résine contiennent chacune une charge inorganique qui est soumise à un traitement de surface à l'aide d'un agent de couplage au silane et a un diamètre de particule moyen inférieur à 15 µm.
PCT/JP2024/020017 2023-06-08 2024-05-31 Feuille métallique équipée d'une résine Ceased WO2024253037A1 (fr)

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WO2018155418A1 (fr) * 2017-02-22 2018-08-30 ナミックス株式会社 Substrat de câblage multicouche et dispositif à semi-conducteur
WO2018212285A1 (fr) * 2017-05-18 2018-11-22 Ａｇｃ株式会社 Film et stratifié de résine d'hydrocarbure fluoré, et procédé de production d'un stratifié thermiquement pressé
JP2021515823A (ja) * 2018-11-23 2021-06-24 エルジー・ケム・リミテッド 樹脂組成物、これを含むプリプレグ、これを含む積層板、およびこれを含む樹脂付着金属箔
JP2022161530A (ja) * 2021-04-09 2022-10-21 エルジー・ケム・リミテッド 熱硬化性樹脂組成物、その硬化物及びプリプレグ、硬化物又はプリプレグの硬化物を備えた積層板、金属箔張積層板、並びにプリント配線板
JP2022163625A (ja) * 2021-04-14 2022-10-26 Ａｇｃ株式会社 改質分散液の製造方法及び分散液
JP2022169444A (ja) * 2021-04-27 2022-11-09 国立大学法人 東京大学 接合体、基板、接合体の製造方法、及び、基板の製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021004316A (ja) 2019-06-26 2021-01-14 パナソニックＩｐマネジメント株式会社 樹脂組成物、プリプレグ、プリプレグの製造方法、積層板及びプリント配線板

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018155418A1 (fr) * 2017-02-22 2018-08-30 ナミックス株式会社 Substrat de câblage multicouche et dispositif à semi-conducteur
WO2018212285A1 (fr) * 2017-05-18 2018-11-22 Ａｇｃ株式会社 Film et stratifié de résine d'hydrocarbure fluoré, et procédé de production d'un stratifié thermiquement pressé
JP2021515823A (ja) * 2018-11-23 2021-06-24 エルジー・ケム・リミテッド 樹脂組成物、これを含むプリプレグ、これを含む積層板、およびこれを含む樹脂付着金属箔
JP2022161530A (ja) * 2021-04-09 2022-10-21 エルジー・ケム・リミテッド 熱硬化性樹脂組成物、その硬化物及びプリプレグ、硬化物又はプリプレグの硬化物を備えた積層板、金属箔張積層板、並びにプリント配線板
JP2022163625A (ja) * 2021-04-14 2022-10-26 Ａｇｃ株式会社 改質分散液の製造方法及び分散液
JP2022169444A (ja) * 2021-04-27 2022-11-09 国立大学法人 東京大学 接合体、基板、接合体の製造方法、及び、基板の製造方法

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