[go: up one dir, main page]

WO2020004338A1 - Feuille métallique fixée à une résine - Google Patents

Feuille métallique fixée à une résine Download PDF

Info

Publication number
WO2020004338A1
WO2020004338A1 PCT/JP2019/024975 JP2019024975W WO2020004338A1 WO 2020004338 A1 WO2020004338 A1 WO 2020004338A1 JP 2019024975 W JP2019024975 W JP 2019024975W WO 2020004338 A1 WO2020004338 A1 WO 2020004338A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal foil
resin
group
resin layer
porous resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2019/024975
Other languages
English (en)
Japanese (ja)
Inventor
敦美 山邊
細田　朋也
渉 笠井
達也 寺田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to CN201980042799.1A priority Critical patent/CN112334301A/zh
Priority to JP2020527517A priority patent/JP7243724B2/ja
Priority to KR1020207029865A priority patent/KR102740113B1/ko
Publication of WO2020004338A1 publication Critical patent/WO2020004338A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
    • 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
    • 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
    • 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
    • B32B2327/00—Polyvinylhalogenides
    • B32B2327/12—Polyvinylhalogenides containing fluorine
    • B32B2327/18—PTFE, i.e. polytetrafluoroethylene
    • 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

Definitions

  • the present invention relates to a metal foil with resin.
  • a resin-coated metal foil having an insulating resin layer on the surface of the metal foil is used as a printed wiring board by processing the metal foil by etching or the like.
  • Printed wiring boards used for transmitting high-frequency signals are required to have excellent transmission characteristics.
  • a fluoropolymer such as polytetrafluoroethylene (PTFE) is known.
  • Patent Document 1 discloses a resin-attached metal foil having a fluoropolymer resin layer on the surface of a metal foil treated with a silane coupling agent.
  • Patent Document 2 discloses a resin-attached metal foil having a porous resin layer made of a fluoropolymer on the surface of the metal foil.
  • Patent Document 3 discloses a resin-attached metal foil having a resin layer made of a surface-modified fluoropolymer on the surface of the metal foil.
  • the resin-coated metal foils described in Patent Literatures 1 to 3 are prepared by adhering a metal foil and a fluoropolymer resin layer in order to suppress transmission loss due to a skin effect when used as a high-frequency printed wiring board.
  • the peel strength of the resin layer is increased.
  • a resin-attached metal foil in which a fluoropolymer resin layer having a large linear expansion coefficient is closely attached to a metal foil is likely to be warped due to expansion and contraction of the fluoropolymer.
  • the object of the present invention is to provide a resin-attached metal foil having a non-porous resin layer containing a fluoropolymer, which has a high peel strength, is hardly warped, and has excellent electric properties.
  • the present invention has the following aspects.
  • a warp rate of the resin-attached metal foil is 5% or less.
  • the tetrafluoroethylene-based polymer is a tetrafluoroethylene-based polymer having a temperature range exhibiting a storage elastic modulus of 0.1 to 5.0 MPa at 260 ° C. or lower and a melting point exceeding 260 ° C.
  • a polymer in which the tetrafluoroethylene-based polymer includes a unit based on tetrafluoroethylene and a unit based on at least one monomer selected from the group consisting of perfluoro (alkyl vinyl ether), hexafluoropropylene, and fluoroalkylethylene.
  • the metal foil with resin according to any one of [1] to [7].
  • the tetrafluoroethylene-based polymer is a polymer having at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, an amide group, an amino group, and an isocyanate group.
  • the present invention it is possible to provide a resin-attached metal foil having a non-porous resin layer containing a fluoropolymer, which has a high peel strength, is hardly warped, and has excellent electric properties.
  • the resin-attached metal foil of the present invention has a high peel strength of the non-porous resin layer containing the fluoropolymer and is hardly warped, and thus can be suitably used as a material for a high-frequency printed wiring board in which loss due to the skin effect is suppressed.
  • Example 3 is an SEM image of a cross section of the metal foil with resin of Example 1.
  • the “arithmetic average roughness (Ra)” is a value obtained by measuring the surface of the non-porous resin layer in a range of 1 ⁇ m 2 using an atomic force microscope (AFM).
  • "Ten-point average roughness (Rz JIS )” is a value specified in Annex JA of JIS B 0601: 2013.
  • the storage elastic modulus of a polymer is a value measured based on ISO 6721-4: 1994 (JIS K 7244-4: 1999).
  • the melting temperature (melting point) of a polymer is the temperature corresponding to the maximum value of the melting peak of a polymer measured by differential scanning calorimetry (DSC).
  • “Powder D50” is a 50% volume-based cumulative diameter of the powder determined by a laser diffraction / scattering method. That is, the particle size distribution of the powder is measured by the laser diffraction / scattering method, and the cumulative curve is obtained by setting the total volume of the powder particle population to 100%, and the particle diameter at the point where the cumulative volume becomes 50% on the cumulative curve. is there.
  • “D90 of the powder” is a 90% diameter based on the volume of the powder obtained in the same manner as in the above D50.
  • the "warp rate of the metal foil with resin” is obtained by cutting a square test piece of 180 mm square from the metal foil with resin and measuring the test piece according to JIS C 6471: 1995 (corresponding international standard IEC 249-1: 1982).
  • the “heat-resistant resin” is a polymer compound having a melting point of 280 ° C. or more, or a polymer compound having a maximum continuous use temperature of 121 ° C. or more specified in JIS C 4003: 2010 (IEC 60085: 2007).
  • the “unit” in the polymer may be an atomic group formed directly from one molecule of the monomer by the polymerization reaction, and the polymer obtained by the polymerization reaction is treated by a predetermined method to convert a part of the structure. It may be the above atomic group.
  • a unit based on the monomer A may be represented as a “monomer A unit”.
  • the non-porous resin layer in the present invention is a non-porous dense layer containing a tetrafluoroethylene-based polymer having a large coefficient of linear expansion (hereinafter also referred to as “TFE-based polymer”).
  • TFE-based polymer a tetrafluoroethylene-based polymer having a large coefficient of linear expansion
  • the resin-attached metal foil in which the non-porous resin layer is brought into contact with the metal foil is expected to have excellent electrical properties (such as a small relative dielectric constant and a low dielectric loss tangent) and excellent physical properties such as acid resistance (such as etching resistance). On the other hand, it was expected that there was a drawback that it was easily warped.
  • the present inventors if a void is present at a part of the interface between the metal foil and the non-porous resin layer of the resin-coated metal foil, the void becomes a buffer for absorbing the expansion and contraction of the TFE-based polymer, We thought that the warpage of the metal foil could be suppressed.
  • voids were present at a part of the interface, it was expected that the contact area between the metal foil and the non-porous resin layer was reduced, and the peel strength of the non-porous resin layer was also reduced.
  • the present inventors paid attention to the surface shape of the metal foil, and as a result of diligent studies, they found a resin-attached metal foil having excellent physical properties while maintaining the peel strength of the non-porous resin layer.
  • a transmission circuit is formed by etching the metal foil, and soldering is performed by reflow method under heating, so that a high-performance printed wiring board can be efficiently manufactured.
  • the metal foil with resin of the present invention is a non-porous resin containing a metal foil having an uneven surface and a tetrafluoroethylene-based polymer (hereinafter, also referred to as “TFE-based polymer”) in contact with the uneven surface of the metal foil. And a void is present at a part of the interface between the metal foil and the non-porous resin layer.
  • TFE-based polymer tetrafluoroethylene-based polymer
  • the metal foil may have an uneven surface on both surfaces, and may have a non-porous resin layer on both surfaces of the metal foil.
  • the layer structure of the metal foil with resin of the present invention includes metal foil / non-porous resin layer, metal foil / non-porous resin layer / metal foil, non-porous resin layer / metal foil / non-porous resin layer, and the like. No. “Metal foil / non-porous resin layer” indicates that a metal foil and a non-porous resin layer are laminated in this order, and the same applies to other layer configurations.
  • the peel strength between the metal foil and the non-porous resin layer in the metal foil with resin is preferably 5 N / cm or more, more preferably 7 N / cm or more.
  • the peel strength is preferably 50 N / cm or less.
  • the warp rate of the resin-attached metal foil of the present invention is preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less. In this case, the handleability when processing the metal foil with resin into a printed wiring board and the transmission characteristics of the obtained printed wiring board are excellent.
  • the void in the present invention may be present only at the interface between the metal foil and the non-porous resin layer, or may be present at the interface and the vicinity thereof, or at least at the interface. Is preferred.
  • the distance between the void and the interface is preferably greater than 0 nm and 500 nm or less, more preferably greater than 0 nm and 300 nm or less, and particularly preferably greater than 0 nm and 100 nm or less. preferable.
  • “Distance between void and interface” means the shortest distance between void and interface.
  • the void is preferably present in the concave portion of the uneven surface of the metal foil in the interface between the metal foil and the non-porous resin layer, from the viewpoint of suppressing the warpage of the metal foil with resin and balancing the electrical characteristics.
  • the resin-attached metal foil of the present invention has a structure in which a nonporous resin layer forms a projection (projection) in contact with a concave portion (dent) of the metal foil.
  • the void preferably exists at the interface between the depression of the metal foil and the non-porous resin layer in contact with the projection. The existence of such voids can be confirmed by analyzing the cross section of the resin-attached metal foil of the present invention with an SEM image.
  • the void may be present in each of the convex portion and the concave portion of the uneven surface of the metal foil, but in this case, the number of voids present in the convex portion is smaller than the number of voids present in the concave portion. Is preferred from the viewpoint of maintaining the peel strength between the metal foil and the non-porous resin layer. Further, from the viewpoint of the peel strength of the non-porous resin layer, it is preferable that the void does not exist in the convex portion of the uneven surface of the metal foil in the interface between the metal foil and the non-porous resin layer.
  • the metal foil in the present invention has an uneven surface.
  • the shape of the concave portion and the convex portion of the concave-convex surface is not particularly limited, and may be a column shape, a weight shape, a curved shape, or a constricted shape.
  • the aspect ratio of the concave portion of the uneven surface of the metal foil is preferably 0.01 or more, more preferably 1.0 or more, particularly preferably 2.0 or more, and preferably 3.0 or more. Most preferred.
  • the upper limit of the aspect ratio is usually 5.0.
  • the aspect ratio of the concave portion is obtained as a ratio of a distance from a lower end of each end of the concave portion to a deepest portion of the concave portion with respect to a distance between both ends forming the concave portion.
  • the shape of the void can be confirmed by processing a cross section of a metal foil with resin embedded with an epoxy resin by a cross section polisher and observing the cross section with a scanning electron microscope (SEM).
  • the ten-point average roughness (Rz JIS ) of the surface of the uneven surface of the metal foil is preferably 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more, and preferably 0.2 ⁇ m or more.
  • the ten-point average roughness is preferably 4 ⁇ m or less, more preferably 1.5 ⁇ m or less, and particularly preferably 0.5 ⁇ m or less.
  • a preferred embodiment of the ten-point average roughness is 0.2 to 4 ⁇ m, a more preferred embodiment is 0.3 to 3.4 ⁇ m, and a still more preferred embodiment is 0.7 to 1.5 ⁇ m.
  • the surface Rz JIS is equal to or more than the lower limit of the above range, the adhesiveness with the non-porous resin layer becomes good.
  • the thickness of the metal foil is not particularly limited as long as a sufficient function can be exhibited in the application of the resin-attached metal foil, and is preferably 1 to 30 ⁇ m, more preferably 5 to 25 ⁇ m, and more preferably 8 to 20 ⁇ m. It is particularly preferred that there is.
  • the uneven surface of the metal foil is preferably treated with a silane coupling agent.
  • the fact that the uneven surface of the metal foil is treated with the silane coupling agent means that the uneven surface of the metal foil is analyzed by X-ray fluorescence spectroscopy (XRF), and the silicon atom and the atom specific to the functional group of the silane coupling agent are used. (Nitrogen atom, sulfur atom, etc.).
  • the detection amounts of silicon atoms and the above atoms may be at least the detection limit, and are preferably detected at 0.01% by mass or more, respectively.
  • the silane coupling agent treatment of the uneven surface of the metal foil may be performed on the entire uneven surface of the metal foil, or may be performed on a part of the uneven surface of the metal foil. From the viewpoint of the adhesiveness between the metal foil and the non-porous resin layer, it is preferable that the metal foil be part of the uneven surface of the metal foil.
  • a part of the uneven surface of the metal foil is treated with the silane coupling agent, without distinction between the concave portion and the convex portion of the uneven surface of the metal foil, a part thereof is treated with the silane coupling agent.
  • a mode in which the convex portion of the uneven surface of the metal foil is treated with a silane coupling agent is treated with the silane coupling agent.
  • the cross section of the metal foil is subjected to elemental analysis by an energy dispersive X-ray spectrometer (EDS), and a silicon atom and an atom (nitrogen specific to a functional group of the silane coupling agent) are analyzed. Atoms, sulfur atoms, etc.).
  • the metal foil in which a part of the uneven surface is treated with the silane coupling agent is obtained, for example, by spray-drying the silane coupling agent on the uneven surface of the metal foil.
  • spray drying method include the treatment methods described in WO-A-2015 / 40988, [0061] to [0064].
  • a specific spray-drying method a treatment solution containing a silane coupling agent and a solvent (alcohol, toluene, hexane, etc.) and the concentration of the silane coupling agent is adjusted to 0.5 to 1.5% by mass. Is sprayed onto the uneven surface of the metal foil and heated at 100 to 130 ° C. for 1 to 10 minutes.
  • the silane coupling agent is an organic compound having a hydrolyzable silyl group and a reactive group other than the hydrolyzable silyl group (hereinafter, also referred to as “reactive group”).
  • Silanol groups (Si—OH) formed by hydrolysis of hydrolyzable silyl groups interact with the surface of the metal foil to fix the silane coupling agent on the surface of the metal foil, and the reactive group is formed of a non-porous resin. Interaction with the layer surface improves the adhesion between the metal foil and the non-porous resin layer.
  • an alkoxysilyl group is preferable, a trialkoxysilyl group is more preferable, and a trimethoxysilyl group or a triethoxysilyl group is particularly preferable.
  • Examples of the organic compound having an alkoxysilyl group and an amino group include aminoalkoxysilane, and specific examples thereof include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N-phenyl-3-amino Propyltrimethoxysilane and the like.
  • ketimines such as 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine
  • salts of aminoalkoxysilanes N-vinylbenzyl-2-aminoethyl-3) -Aminopropyltrimethoxysilane acetate
  • organic compound having an alkoxysilyl group and a mercapto group include mercaptoalkoxysilane, and specific examples thereof include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropyl (dimethoxy) methylsilane. And the like.
  • the material of the metal foil examples include copper, copper alloy, stainless steel, nickel, nickel alloy (including 42 alloy), aluminum, aluminum alloy, titanium, and titanium alloy.
  • a copper foil is preferable.
  • Specific examples of the copper foil include a rolled copper foil and an electrolytic copper foil.
  • the metal foil is preferably a metal foil having a metal foil main body and a rustproofing layer provided on the non-porous resin layer side of the metal foil main body. When the metal foil has a rust-proofing layer, the surface of the rust-proofing layer is treated with a silane coupling agent.
  • the rust-proofing layer is selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, and tantalum.
  • the rust preventive layer may include the element as a metal or an alloy, or may include the element as an oxide, a nitride, or a silicide.
  • a layer containing cobalt oxide, nickel oxide or metallic zinc from the viewpoint of suppressing the oxidation of the metal foil for a long time and suppressing the increase in the relative dielectric constant and the dielectric loss tangent of the non-porous resin layer are preferred, and a layer of metallic zinc is particularly preferred.
  • a heat-resistant layer may be formed on the metal foil. Examples of the heat-resistant layer include a layer containing the same element as the rust-proofing layer.
  • the non-porous resin layer in the present invention has substantially no voids except for voids existing in the vicinity of the interface.
  • a resin layer containing a molten resin is preferable, and a resin layer made of a molten resin is preferable.
  • the thickness of the non-porous resin layer is preferably 0.05 ⁇ m or more, more preferably 1 ⁇ m or more, and particularly preferably 2 ⁇ m or more.
  • the thickness is preferably 100 ⁇ m or less, more preferably 10 ⁇ m or less, and particularly preferably 7 ⁇ m or less.
  • a preferred embodiment of the thickness is 0.05 to 100 ⁇ m, and a more preferred embodiment is 6 to 60 ⁇ m.
  • the resin-attached metal foil has a non-porous resin layer on both sides of the metal foil, the composition and thickness of each non-porous resin layer are the same from the viewpoint of suppressing the warpage of the resin-attached metal foil. Is preferred.
  • the thickness of the non-porous resin layer can be set to be larger than the thickness of the metal foil.
  • the ratio of the thickness of the non-porous resin layer to the thickness of the metal foil is preferably from 0.01 to 10.0, more preferably from 0.05 to 7.5, and particularly preferably from 0.2 to 5.0.
  • the ratio of the thickness of the non-porous resin layer to the thickness of the metal foil is equal to or more than the lower limit of the above range, the electrical characteristics of the TFE-based polymer can be easily sufficiently exhibited. If the ratio of the thickness of the non-porous resin layer to the thickness of the metal foil is equal to or less than the upper limit of the above range, it is more difficult to warp.
  • the water contact angle on the surface of the non-porous resin layer is preferably from 70 to 100 °, particularly preferably from 70 to 90 °.
  • the water contact angle is an angle formed between a water droplet and the surface of the non-porous resin layer when pure water (about 2 ⁇ L) is placed on the surface of the non-porous resin layer of the metal foil with resin at 25 ° C.
  • the relative permittivity of the non-porous resin layer is preferably from 2.0 to 3.5, and more preferably from 2.0 to 3.0. In this case, both the electrical properties and adhesiveness of the non-porous resin layer are excellent, and a resin-attached metal foil can be suitably used for a printed wiring board or the like that requires a low dielectric constant.
  • Ra on the surface of the non-porous resin layer is less than the thickness of the non-porous resin layer, and preferably 1 to 10 nm. Within this range, it is easy to balance the adhesiveness and workability of another substrate.
  • the non-porous resin layer in the present invention contains a TFE-based polymer.
  • the TFE-based polymer is preferably a hot-melt TFE-based polymer.
  • the melting point of the TFE polymer is preferably higher than 260 ° C., more preferably higher than 260 ° C. and 320 ° C. or less, and particularly preferably 275 to 320 ° C.
  • the TFE-based polymer is baked while maintaining the adhesiveness based on its elasticity, so that a dense non-porous resin layer is more easily formed.
  • the TFE-based polymer preferably has a temperature region exhibiting a storage modulus of 0.1 to 5.0 MPa at 260 ° C. or lower.
  • the storage elastic modulus of the TFE-based polymer is preferably from 0.2 to 4.4 MPa, particularly preferably from 0.5 to 3.0 MPa.
  • the temperature range in which the TFE-based polymer exhibits such storage modulus is preferably from 180 to 260 ° C., particularly preferably from 200 to 260 ° C. In the temperature range, the TFE-based polymer tends to effectively exhibit adhesiveness based on its elasticity.
  • the TFE-based polymer is a polymer having TFE units.
  • the TFE-based polymer may be a homopolymer of TFE or a copolymer of TFE and another monomer copolymerizable with TFE (hereinafter also referred to as a comonomer).
  • the TFE-based polymer preferably has 75 to 100 mol% of TFE units and 0 to 25 mol% of units based on a comonomer, based on all units constituting the polymer.
  • Examples of the comonomer include perfluoro (alkyl vinyl ether) (hereinafter also referred to as “PAVE”), fluoroalkylethylene (hereinafter also referred to as “FAE”), hexafluoropropylene (hereinafter also referred to as “HFP”), olefin, and the like. Is mentioned.
  • TFE-based polymer examples include polytetrafluoroethylene, a copolymer of TFE and ethylene, a copolymer of TFE and propylene, a copolymer of TFE and PAVE, a copolymer of TFE and HFP, a copolymer of TFE and FAE, and a copolymer of TFE and chlorotrifluoroethylene.
  • a polymer containing a TFE unit and a unit based on at least one monomer selected from the group consisting of PAVE, HFP and FAE (hereinafter also referred to as “comonomer unit F”) is also exemplified.
  • the polymer preferably has 90 to 99 mol% of TFE units and 1 to 10 mol% of comonomer units F based on all units constituting the polymer.
  • the polymer may be composed of only the TFE unit and the comonomer unit F, and may further contain other units.
  • the TFE-based polymer from the viewpoint of the adhesiveness between the non-porous resin layer and the metal foil, selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, an amide group, an amino group and an isocyanate group.
  • a polymer having TFE units hereinafter, also referred to as “polymer F 1 ”) having at least one type of functional group (hereinafter, also referred to as “functional group”).
  • Functional groups may be contained in the units in the TFE-based polymers may be contained in the end groups of the main chain of the polymer F 1.
  • Examples of the latter polymer include a polymer having a functional group as a terminal group derived from a polymerization initiator, a chain transfer agent, or the like.
  • the polymer F 1 a polymer having the units and TFE units having a functional group are preferred.
  • the polymer F 1 in this case, further preferably has other units, particularly preferably has a comonomer unit F.
  • the functional group is preferably a carbonyl group-containing group from the viewpoint of adhesion between the non-porous resin layer and the metal foil.
  • Examples of the carbonyl group-containing group include a carbonate group, a carboxy group, a haloformyl group, an alkoxycarbonyl group, an acid anhydride residue (—C (O) OC (O) —), and a fatty acid residue.
  • Anhydride residues are preferred.
  • the unit having a functional group is preferably a unit based on a monomer having a functional group, and is a unit based on a monomer having a carbonyl group, a unit based on a monomer having a hydroxy group, a unit based on a monomer having an epoxy group, and an isocyanate group.
  • a unit based on a monomer having a carbonyl group is more preferable, and a unit based on a monomer having a carbonyl group-containing group is particularly preferable.
  • a cyclic monomer having an acid anhydride residue As the monomer having a carbonyl group-containing group, a cyclic monomer having an acid anhydride residue, a monomer having a carboxy group, a vinyl ester and a (meth) acrylate are preferable, and a cyclic monomer having an acid anhydride residue is particularly preferable.
  • a cyclic monomer itaconic anhydride, citraconic anhydride, 5-norbornene-2,3-dicarboxylic anhydride (also called hymic anhydride; hereinafter also referred to as “NAH”) and maleic anhydride are preferable.
  • Specific examples of such polymers F 1, are polymers described in WO 2018/16644 (X) can be mentioned.
  • the proportion of TFE units in the polymer F 1 is the total units constituting the polymer F 1, is preferably 90 to 99 mol%.
  • Proportion of PAVE units in the polymer F 1 is the total units constituting the polymer F 1, is preferably 0.5 to 9.97 mol%.
  • the proportion of units having functional groups in the polymer F 1 is the total units constituting the polymer F 1, is preferably 0.01 to 3 mol%.
  • the method for producing a resin-attached metal foil according to the present invention includes a powder dispersion containing a powder containing a TFE-based polymer (hereinafter also referred to as “F powder”) and a liquid medium on the uneven surface of the metal foil having an uneven surface. Is applied, the liquid medium is removed by heating the powder dispersion on the uneven surface of the metal foil, and then the F powder is baked to obtain the resin-attached metal foil of the present invention.
  • F powder a powder dispersion containing a powder containing a TFE-based polymer
  • the liquid medium is removed by heating the powder dispersion on the uneven surface of the metal foil, and then the F powder is baked to obtain the resin-attached metal foil of the present invention.
  • the liquid medium is a dispersion medium, which is a liquid medium that is inert at 25 ° C. and does not react with the F powder, has a lower boiling point than components other than the liquid medium contained in the powder dispersion, and is volatilized by heating or the like. Liquid media that can be removed are preferred.
  • liquid medium examples include water, alcohols (methanol, ethanol, isopropanol, etc.), nitrogen-containing compounds (N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.), sulfur-containing compounds (dimethyl Sulfoxides), ethers (diethyl ether, dioxane, etc.), esters (ethyl lactate, ethyl acetate, etc.), ketones (methyl ethyl ketone, methyl isopropyl ketone, cyclopentanone, cyclohexanone, etc.), glycol ethers (ethylene glycol monoisopropyl ether, etc.), Cellosolve (methyl cellosolve, ethyl cellosolve, etc.) and the like. Two or more liquid media may be used in combination.
  • liquid medium a liquid medium that does not volatilize instantaneously is preferable, a liquid medium having a boiling point of 80 to 275 ° C is preferable, and a liquid medium having a boiling point of 125 to 250 ° C is particularly preferable. Within this range, the stability of the wet film formed from the powder dispersion applied to the surface of the metal foil is high.
  • organic compounds are preferable, and cyclohexane (boiling point: 81 ° C.), 2-propanol (boiling point: 82 ° C.), 1-propanol (boiling point: 97 ° C.), 1-butanol (boiling point: 117 ° C.), 1-butanol Methoxy-2-propanol (boiling point: 119 ° C), N-methylpyrrolidone (boiling point: 202 ° C), ⁇ -butyrolactone (boiling point: 204 ° C), cyclohexanone (boiling point: 156 ° C) and cyclopentanone (boiling point: 131 ° C) are more preferable, and N-methylpyrrolidone, ⁇ -butyrolactone, cyclohexanone and cyclopentanone are particularly preferable.
  • the ⁇ F powder may contain components other than the TFE-based polymer as long as the effects of the present invention are not impaired, but it is preferable that the F-powder be mainly composed of the TFE-based polymer.
  • the content of the TFE-based polymer in the F powder is preferably 80% by mass or more, and particularly preferably 100% by mass.
  • the D50 of the F powder is preferably from 0.05 to 6.0 ⁇ m, more preferably from 0.1 to 3.0 ⁇ m, and particularly preferably from 0.2 to 3.0 ⁇ m. Within this range, the fluidity and dispersibility of the F powder are good, and the electrical properties (such as a low dielectric constant) and the heat resistance of the non-porous resin layer are most easily exhibited.
  • the D90 of the F powder is preferably 8 ⁇ m or less, more preferably 6 ⁇ m or less, and particularly preferably 5 ⁇ m or less.
  • the D90 of the powder is preferably at least 0.3 ⁇ m, particularly preferably at least 0.8 ⁇ m.
  • the fluidity and dispersibility of the F powder are good, and the electrical properties (such as a low dielectric constant) and the heat resistance of the non-porous resin layer are most easily exhibited.
  • the method for producing the F powder is not particularly limited, and the methods described in [0065] to [0069] of WO 2016/017801 can be employed.
  • the F powder if desired powder is commercially available, it may be used.
  • the proportion of the F powder in the powder dispersion is preferably 5 to 60% by mass, particularly preferably 35 to 50% by mass. Within this range, the relative dielectric constant and dielectric loss tangent of the non-porous resin layer can be easily controlled to be low. Further, the powder dispersion has high uniform dispersibility, and the non-porous resin layer has excellent mechanical strength.
  • the proportion of the liquid medium in the powder dispersion is preferably from 15 to 65% by mass, particularly preferably from 25 to 50% by mass. Within this range, the applicability of the powder dispersion is excellent, and poor appearance of the non-porous resin layer is unlikely to occur.
  • the powder dispersion may contain other materials as long as the effects of the present invention are not impaired. Other materials may or may not dissolve in the powder dispersion.
  • the other material may be a non-curable resin or a curable resin.
  • the non-curable resin include a heat-meltable resin and a non-meltable resin.
  • the heat-fusible resin include thermoplastic polyimide.
  • the non-fusible resin include a cured product of a curable resin.
  • the curable resin include a polymer having a reactive group, an oligomer having a reactive group, a low molecular compound, and a low molecular compound having a reactive group.
  • the reactive group include a carbonyl group-containing group, a hydroxy group, an amino group, and an epoxy group.
  • epoxy resin thermosetting polyimide, polyamic acid as a polyimide precursor, thermosetting acrylic resin, phenol resin, thermosetting polyester resin, thermosetting polyolefin resin, modified polyphenylene ether resin, polyfunctional Examples include a cyanate ester resin, a polyfunctional maleimide-cyanate ester resin, a polyfunctional maleimide resin, a vinyl ester resin, a urea resin, a diallyl phthalate resin, a melamine resin, a guanamine resin, and a melamine-urea cocondensation resin.
  • thermosetting polyimide polyimide precursor, epoxy resin, acrylic resin, bismaleimide resin and polyphenylene ether resin are preferable as thermosetting resin from the viewpoint of being useful for printed wiring board applications, and epoxy resin and polyphenylene ether are preferable. Resins are particularly preferred.
  • the epoxy resin examples include naphthalene type epoxy resin, cresol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, Cresol novolak type epoxy resin, phenol novolak type epoxy resin, alkylphenol novolak type epoxy resin, aralkyl type epoxy resin, biphenol type epoxy resin, dicyclopentadiene type epoxy resin, trishydroxyphenylmethane type epoxy compound, having phenol and phenolic hydroxyl group Epoxidized condensate with aromatic aldehyde, diglycidyl ether of bisphenol, diglycidyl ether of naphthalene diol, phenol Glycidyl ethers, diglycidyl ethers of alcohols, triglycidyl isocyanurate.
  • the bismaleimide resin a resin composition (BT resin) in which a bisphenol A-type cyanate ester resin and a bismaleimide compound are used in combination, which is described in JP-A-7-70315, described in WO2013 / 008667 And the background art.
  • Polyamic acid typically has a reactive group capable of reacting with the functional groups of the polymer F 1.
  • Examples of the diamine and polycarboxylic acid dianhydride forming a polyamic acid include [0020] of Japanese Patent No. 5766125, [0019] of Japanese Patent No. 5766125, and [0055] of Japanese Patent Application Laid-Open No. 2012-145676. , [0057] and the like.
  • aromatic diamines such as 4,4'-diaminodiphenyl ether and 2,2-bis [4- (4-aminophenoxy) phenyl] propane, and pyromellitic dianhydride, 3,3 ', 4,4 Polyamic acids comprising a combination with an aromatic polycarboxylic dianhydride such as '-biphenyltetracarboxylic dianhydride and 3,3', 4,4'-benzophenonetetracarboxylic dianhydride are preferred.
  • thermoplastic resin such as thermoplastic polyimide
  • thermoplastic polyimide a thermoplastic resin
  • thermoplastic polyimide a thermoplastic resin
  • styrene resin polycarbonate
  • thermoplastic polyimide polyarylate
  • polysulfone polyarylsulfone
  • aromatic polyamide aromatic polyetheramide
  • polyphenylene sulfide polyaryletherketone
  • Polyamide imide liquid crystalline polyester, polyphenylene ether and the like
  • thermoplastic polyimide, liquid crystalline polyester and polyphenylene ether are preferable.
  • a dispersant such as a styrene foam, a styrene foam, a styrene foam, a styrene foam, a styrene foam, a styrene foam, a styrene foam, a styrene foam, a styrene foam, a styrene foam, a styrene, sodium sulfate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium sulfate, sodium bicarbonate, sodium sulfate, sodium bicarbonate, sodium sulfate, sodium bicarbonate, sodium sulf
  • the method of applying the powder dispersion to the uneven surface of the metal foil may be any method that forms a stable wet film made of the powder dispersion on the uneven surface of the metal foil after application, such as a spray method, a roll coating method, and a spin coating method. Coating method, gravure coating method, microgravure coating method, gravure offset method, knife coating method, kiss coating method, bar coating method, die coating method, fountain Meyer bar method, slot die coating method and the like.
  • the TFE-based polymer After the powder dispersion is applied to the uneven surface of the metal foil, the TFE-based polymer has a storage elastic modulus of 0.1 to 5.0 MPa at a temperature within a temperature range (hereinafter, also referred to as “holding temperature”). It is preferable to hold the metal foil. The holding temperature indicates the temperature of the atmosphere.
  • the state of the wet film may be adjusted by heating the metal foil at a temperature lower than the temperature range. The adjustment of the state of the wet film is performed to such an extent that the liquid medium does not completely volatilize, and is usually performed to the extent that 50% by mass or less of the liquid medium is volatilized.
  • the holding after the application of the powder dispersion may be performed in one stage, or may be performed in multiple stages at different temperatures.
  • Examples of the holding method include a method using an oven, a method using a ventilation drying oven, and a method of irradiating heat rays such as infrared rays.
  • the atmosphere in the holding may be under normal pressure or reduced pressure.
  • the holding atmosphere may be any of an oxidizing gas atmosphere such as an oxygen gas atmosphere, a reducing gas atmosphere such as a hydrogen gas atmosphere, and an inert gas atmosphere such as a helium gas, a neon gas, an argon gas, and a nitrogen gas.
  • an atmosphere for the holding an atmosphere containing an oxygen gas is preferable from the viewpoint of improving the adhesiveness of the non-porous resin layer.
  • the oxygen gas concentration (by volume) in an atmosphere containing oxygen gas is preferably from 1 ⁇ 10 2 to 3 ⁇ 10 5 ppm, particularly preferably from 0.5 ⁇ 10 3 to 1 ⁇ 10 4 ppm. Within this range, it is easy to balance the adhesiveness of the non-porous resin layer and the suppression of oxidation of the metal foil.
  • the holding temperature is preferably from 150 to 260 ° C, particularly preferably from 200 to 260 ° C.
  • the holding time at the holding temperature is preferably from 0.1 to 10 minutes, particularly preferably from 0.5 to 5 minutes.
  • the powder dispersion contains a thermofusible resin
  • a non-porous resin layer composed of a mixture of a TFE-based polymer and a heat-fusible resin is formed.
  • a thermosetting resin a thermosetting resin
  • a TFE-based polymer is formed.
  • a non-porous resin layer composed of a cured product of the thermosetting resin is formed.
  • the heating method examples include a method using an oven, a method using a ventilation drying oven, and a method of irradiating heat rays such as infrared rays.
  • a heating plate In order to increase the smoothness of the surface of the non-porous resin layer, pressure may be applied with a heating plate, a heating roll, or the like.
  • a heating method a method of irradiating far-infrared rays is preferable because it can be fired in a short time and the far-infrared ray furnace is relatively compact.
  • the heating method may be a combination of infrared heating and hot air heating.
  • the effective wavelength band of the far infrared ray is preferably 2 to 20 ⁇ m, more preferably 3 to 7 ⁇ m, from the viewpoint of promoting uniform fusion of the TFE-based polymer.
  • the atmosphere in the firing may be under normal pressure or under reduced pressure.
  • the atmosphere in the firing may be any of an oxidizing gas atmosphere such as an oxygen gas, a reducing gas atmosphere such as a hydrogen gas, and an inert gas atmosphere such as a helium gas, a neon gas, an argon gas, and a nitrogen gas.
  • the atmosphere is preferably a reducing gas atmosphere or an inert gas atmosphere.
  • a gas atmosphere composed of an inert gas and having a low oxygen gas concentration is preferable, and a gas atmosphere composed of nitrogen gas and having an oxygen gas concentration (by volume) of less than 500 ppm is preferable.
  • the oxygen gas concentration (by volume) is particularly preferably 300 ppm or less. Further, the oxygen gas concentration (based on volume) is usually 1 ppm or more.
  • the firing temperature is preferably higher than 320 ° C., particularly preferably 330 to 380 ° C. In this case, the TFE-based polymer more easily forms a dense non-porous resin layer.
  • the holding time at the firing temperature is preferably from 30 seconds to 5 minutes, and particularly preferably from 1 to 2 minutes.
  • the resin layer of the resin-attached metal foil is a conventional insulating material (a cured product of a thermosetting resin such as polyimide), long-time heating is required to cure the thermosetting resin.
  • the non-porous resin layer can be formed by heating for a short time by fusing the TFE-based polymer.
  • the firing temperature can be lowered.
  • the resin-attached metal foil of the present invention has a small heat load on the metal foil when the non-porous resin layer is formed at the time of manufacturing, and has a small damage to the metal foil.
  • the surface of the non-porous resin layer Processing may be performed.
  • Surface treatment methods for the surface of the non-porous resin layer include annealing treatment, corona discharge treatment, atmospheric pressure plasma treatment, vacuum plasma treatment, UV ozone treatment, excimer treatment, chemical etching, silane coupling agent treatment, and fine rough surface. And the like.
  • the temperature in the annealing treatment is preferably from 80 to 190 ° C., particularly preferably from 120 to 180 ° C.
  • the pressure in the annealing treatment is preferably 0.001 to 0.030 MPa, particularly preferably 0.005 to 0.015 MPa.
  • the annealing time is preferably from 10 to 300 minutes, particularly preferably from 30 to 120 minutes.
  • Examples of the plasma irradiation apparatus in the plasma processing include a high-frequency induction method, a capacitive coupling electrode method, a corona discharge electrode-plasma jet method, a parallel plate type, a remote plasma type, an atmospheric pressure plasma type, an ICP type high density plasma type, and the like.
  • Examples of a gas used for the plasma treatment include an oxygen gas, a nitrogen gas, a rare gas (eg, argon), a hydrogen gas, and an ammonia gas, and a rare gas and a nitrogen gas are preferable.
  • Specific examples of the gas used for the plasma treatment include argon gas, a mixed gas of hydrogen gas and nitrogen gas, and a mixed gas of hydrogen gas, nitrogen gas, and argon gas.
  • the atmosphere in the plasma treatment is preferably an atmosphere having a volume fraction of a rare gas or a nitrogen gas of 70% by volume or more, and particularly preferably an atmosphere having a volume fraction of 100% by volume. Within this range, it is easy to form fine irregularities on the surface of the non-porous resin layer.
  • the metal foil with resin of the present invention described above has a high peel strength of the non-porous resin layer and is hardly warped. Therefore, it can be easily laminated with another substrate.
  • Other substrates include a heat-resistant resin film, a prepreg that is a precursor of a fiber-reinforced resin plate, a laminate having a heat-resistant resin film layer, a laminate having a prepreg layer, and the like.
  • the prepreg is a sheet-like substrate in which a thermosetting resin or a thermoplastic resin is impregnated into a base material (tow, woven fabric, or the like) of a reinforcing fiber (glass fiber, carbon fiber, or the like).
  • the heat-resistant resin film is a film containing at least one kind of heat-resistant resin, and may be a single-layer film or a multilayer film.
  • heat-resistant resin examples include polyimide, polyarylate, polysulfone, polyallylsulfone, aromatic polyamide, aromatic polyetheramide, polyphenylene sulfide, polyallyletherketone, polyamideimide, and liquid crystalline polyester.
  • the pressing temperature is preferably equal to or lower than the melting point of the TFE-based polymer, more preferably from 120 to 300 ° C, and particularly preferably from 160 to 220 ° C. Within this range, the non-porous resin layer and the prepreg can be firmly bonded while suppressing thermal deterioration of the prepreg.
  • the pressing temperature is preferably from 310 to 400 ° C. Within this range, the non-porous resin layer and the heat-resistant resin film can be firmly bonded while suppressing the thermal deterioration of the heat-resistant resin film.
  • the hot pressing is preferably performed under a reduced pressure atmosphere, and particularly preferably performed at a degree of vacuum of 20 kPa or less. Within this range, the incorporation of bubbles into the interface between the non-porous resin layer and the substrate in the laminate can be suppressed, and deterioration due to oxidation can be suppressed.
  • the pressure in the hot press is preferably 0.2 MPa or more. Further, the upper limit of the pressure is preferably 10 MPa or less. Within this range, the non-porous resin layer and the substrate can be firmly adhered while suppressing damage to the substrate.
  • the resin-attached metal foil and the laminate thereof of the present invention can be used as a flexible copper-clad laminate or a rigid copper-clad laminate for the production of printed wiring boards. Since the metal foil with resin of the present invention has a high peel strength of the non-porous resin layer and is hard to be warped, it can be suitably used as a material for a high-frequency printed wiring board in which loss due to a skin effect is suppressed.
  • a method of processing the metal foil of the resin-coated metal foil of the present invention into a transmission circuit (pattern circuit) having a predetermined pattern by an etching process or the like, or a method of electroplating the resin-coated metal foil of the present invention (semi-additive method (SAP)) ), A modified semi-additive method (MSAP method), etc.), a printed wiring board can be manufactured from the resin-attached metal foil of the present invention.
  • an interlayer insulating film may be formed over the transmission circuit, and the transmission circuit may be further formed over the interlayer insulating film.
  • the interlayer insulating film can be formed by, for example, the powder dispersion described above.
  • a solder resist may be laminated on a transmission circuit.
  • the solder resist can be formed by, for example, the powder dispersion described above.
  • a coverlay film may be laminated on a transmission circuit.
  • the cover lay film can be formed by, for example, the powder dispersion described above.
  • the relative dielectric constant and the dielectric loss tangent at 20 GHz were determined using -100 RHO (manufactured by Yamayo Testing Machine Co., Ltd.). (Warpage rate) A test piece was cut out from the metal foil with resin and measured. As the warpage ratio is smaller, lamination failure when laminating the metal foil with resin with another material can be suppressed, and a composite flat body (printed wiring board or the like) with suppressed warpage and high flatness can be obtained.
  • peel strength A position of 50 mm from one end in the length direction of a single-sided copper-clad laminate cut out into a rectangular shape (length 100 mm, width 10 mm) is fixed, and a pull-up speed of 50 mm / min is applied to a single-sided copper-clad laminate from one end in the length direction.
  • Polymer (1) a copolymer containing 97.9 mol%, 0.1 mol%, and 2.0 mol% of a unit based on TFE, a unit based on NAH and a unit based on PPVE in this order, and has a storage elasticity at 260 ° C.
  • Copper foil (1) a copper foil having an uneven surface, a ten-point surface roughness of the uneven surface being 1.1 ⁇ m, and the uneven surface being treated with a silane coupling agent (thickness 18 ⁇ m, silicon atomic weight on the foil surface) 0.05 mass%, sulfur atomic weight 0.01 mass%.)
  • Example 1 120 g of a powder (D50: 2.6 ⁇ m, D90: 7.1 ⁇ m) composed of the polymer (1), 12 g of a nonionic fluorinated surfactant (manufactured by Neos, Phantagent 710FL), and 234 g of methyl ethyl ketone
  • the solution is applied to the surface of the copper foil (1) treated with the silane coupling agent, dried under a nitrogen atmosphere at 100 ° C. for 15 minutes, further heated at 350 ° C. for 15 minutes, gradually cooled, and cooled from the polymer (1).
  • a non-porous resin layer (thickness: 7 ⁇ m) and a copper foil (1) were directly laminated to obtain a resin-attached metal foil.
  • the physical properties of the obtained resin-attached metal foil were measured, and a copper-clad laminate was manufactured using the same.
  • FIG. 1 shows an SEM image of the cross section.
  • SEM Hitachi High-Tech Co., SU8230, acceleration voltage 0.7 kV.
  • FIG. 1 shows an SEM image of the cross section.
  • the aspect ratio of the concave portion was 1.0 or more, and the warp ratio of the metal foil with resin was 3%.
  • the location of the void was clearly concentrated in the concave portion.
  • a plasma processing apparatus (AP-1000, manufactured by NORDSON MARCH), RF output: 300 W, gap between electrodes: 2 inches, introduced gas: argon gas, introduced gas amount: 50 cm 3 / min, pressure: 13 Pa, processing Time: The non-porous resin layer side of the metal foil with resin was subjected to plasma treatment under the condition of 1 minute. Ra on the surface of the non-porous resin layer after the plasma treatment was 8 nm.
  • an FR-4 sheet prepared by Hitachi Chemical Co., Ltd., reinforcing fiber: glass fiber, matrix resin: epoxy resin, product name: CEA-67N 0.2 t) (HAN), thickness: 0.2 mm
  • heat-pressed under vacuum temperature: 185 ° C., pressure: 3.0 MPa, time: 60 minutes
  • a single-sided copper-clad laminate in which the layer and the copper foil (1) were laminated in this order was obtained.
  • a single-sided copper-clad laminate was placed on each side of the FR-4 sheet so that a copper foil (1) was formed as the outermost layer.
  • the peel strength between the copper foil (1) and the non-porous resin layer in the obtained single-sided copper-clad laminate was 14 N / cm. Swelling and warpage of the non-porous resin layer were suppressed.
  • the electrical characteristics of the printed wiring board formed by forming a transmission circuit on the obtained double-sided copper-clad laminate were 4.5 or less in relative dielectric constant and 0.015 or less in dielectric loss tangent.

Landscapes

  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention a pour objet : une feuille métallique fixée à une résine qui a une couche de résine non poreuse incluant un fluoropolymère, qui présente une grande résistance au pelage, est difficile à voiler et présente d'excellentes caractéristiques électriques ; et un procédé de fabrication d'une carte de circuit imprimé à l'aide de la feuille métallique fixée à une résine. Cette feuille métallique fixée à une résine comprend : une feuille métallique ayant une surface non plane ; et une couche de résine non poreuse qui inclut un polymère à base de tétrafluoroéthylène et qui vient en butée contre la surface non plane de la feuille métallique, un vide étant présent dans une partie de l'interface entre la feuille métallique et la couche de résine non poreuse.
PCT/JP2019/024975 2018-06-27 2019-06-24 Feuille métallique fixée à une résine Ceased WO2020004338A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201980042799.1A CN112334301A (zh) 2018-06-27 2019-06-24 带树脂的金属箔
JP2020527517A JP7243724B2 (ja) 2018-06-27 2019-06-24 樹脂付金属箔
KR1020207029865A KR102740113B1 (ko) 2018-06-27 2019-06-24 수지 부착 금속박

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018-122106 2018-06-27
JP2018122106 2018-06-27

Publications (1)

Publication Number Publication Date
WO2020004338A1 true WO2020004338A1 (fr) 2020-01-02

Family

ID=68987186

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/024975 Ceased WO2020004338A1 (fr) 2018-06-27 2019-06-24 Feuille métallique fixée à une résine

Country Status (5)

Country Link
JP (1) JP7243724B2 (fr)
KR (1) KR102740113B1 (fr)
CN (1) CN112334301A (fr)
TW (1) TWI809135B (fr)
WO (1) WO2020004338A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022163065A1 (fr) * 2021-01-26 2022-08-04 東洋紡株式会社 Procédé de production d'un corps stratifié, corps stratifié et corps multicouche
JP2024515884A (ja) * 2021-06-08 2024-04-10 広州方邦電子股▲ふん▼有限公司 金属箔、キャリア付き金属箔、銅張積層板及びプリント回路板

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI796650B (zh) * 2021-03-16 2023-03-21 台虹科技股份有限公司 覆金屬積層板

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018016644A1 (fr) * 2016-07-22 2018-01-25 旭硝子株式会社 Composition liquide, procédé de fabrication de film et corps stratifié utilisant ladite composition liquide
WO2018043683A1 (fr) * 2016-09-01 2018-03-08 旭硝子株式会社 Stratifié métallique et son procédé de fabrication, et procédé de fabrication d'une carte de circuit imprimé
WO2018070437A1 (fr) * 2016-10-12 2018-04-19 旭硝子株式会社 Stratifié et son procédé de fabrication

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014192718A1 (fr) 2013-05-31 2014-12-04 住友電気工業株式会社 Corps composite métal et résine, matériau de câblage, et procédé de production de corps composite métal et résine
CN105393647A (zh) * 2013-05-31 2016-03-09 住友电气工业株式会社 射频印刷电路板和布线材料
JP2016046433A (ja) 2014-08-25 2016-04-04 住友電工ファインポリマー株式会社 プリント配線板及びプリント配線板用基板
JP6565936B2 (ja) * 2014-12-26 2019-08-28 Ａｇｃ株式会社 積層板およびフレキシブルプリント基板の製造方法
JP6665990B2 (ja) 2015-06-02 2020-03-13 住友電工プリントサーキット株式会社 高周波プリント配線板用基材、高周波プリント配線板、高周波プリント配線板用基材の製造方法及び高周波プリント配線板の製造方法
CN107708999A (zh) * 2015-08-25 2018-02-16 三井金属矿业株式会社 带树脂层的金属箔、覆金属层叠板和印刷电路板的制造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018016644A1 (fr) * 2016-07-22 2018-01-25 旭硝子株式会社 Composition liquide, procédé de fabrication de film et corps stratifié utilisant ladite composition liquide
WO2018043683A1 (fr) * 2016-09-01 2018-03-08 旭硝子株式会社 Stratifié métallique et son procédé de fabrication, et procédé de fabrication d'une carte de circuit imprimé
WO2018070437A1 (fr) * 2016-10-12 2018-04-19 旭硝子株式会社 Stratifié et son procédé de fabrication

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022163065A1 (fr) * 2021-01-26 2022-08-04 東洋紡株式会社 Procédé de production d'un corps stratifié, corps stratifié et corps multicouche
JPWO2022163065A1 (fr) * 2021-01-26 2022-08-04
JP7764854B2 (ja) 2021-01-26 2025-11-06 東洋紡株式会社 積層体の製造方法、積層体、及び、多層積層体
US12489044B2 (en) 2021-01-26 2025-12-02 Toyobo Co., Ltd. Method for producing layered body, layered body, and multilayered body
JP2024515884A (ja) * 2021-06-08 2024-04-10 広州方邦電子股▲ふん▼有限公司 金属箔、キャリア付き金属箔、銅張積層板及びプリント回路板
JP7771219B2 (ja) 2021-06-08 2025-11-17 広州方邦電子股▲ふん▼有限公司 金属箔、キャリア付き金属箔、銅張積層板及びプリント回路板

Also Published As

Publication number Publication date
CN112334301A (zh) 2021-02-05
JPWO2020004338A1 (ja) 2021-09-02
KR102740113B1 (ko) 2024-12-06
JP7243724B2 (ja) 2023-03-22
KR20210022533A (ko) 2021-03-03
TWI809135B (zh) 2023-07-21
TW202010636A (zh) 2020-03-16

Similar Documents

Publication Publication Date Title
US11370200B2 (en) Fluororesin film and laminate, and method for producing hot pressed laminate
EP3489299A1 (fr) Composition liquide, procédé de fabrication de film et corps stratifié utilisant ladite composition liquide
TWI824049B (zh) 分散液
KR102715822B1 (ko) 수지가 부착된 금속박의 제조 방법, 수지가 부착된 금속박, 적층체 및 프린트 기판
WO2020158604A1 (fr) Stratifié, procédé de production de celui-ci, procédé de production de stratifié composite, et procédé de production de film polymère
KR102715823B1 (ko) 수지 부착 금속박의 제조 방법 및 수지 부착 금속박
JP7243724B2 (ja) 樹脂付金属箔
JP7248022B2 (ja) 積層体の製造方法、及び積層体
JPWO2019235439A1 (ja) 分散液、樹脂付金属箔の製造方法、及びプリント基板の製造方法
JP7400722B2 (ja) 積層体、プリント基板及びその製造方法
JP2020055241A (ja) 樹脂付金属箔及び樹脂付金属箔の製造方法
JP2020083990A (ja) 複合体の製造方法及び複合体

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19824987

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2020527517

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19824987

Country of ref document: EP

Kind code of ref document: A1