WO2020119340A1 - 一种复合金属箔及其制备方法 - Google Patents

一种复合金属箔及其制备方法 Download PDF

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Publication number
WO2020119340A1
WO2020119340A1 PCT/CN2019/116090 CN2019116090W WO2020119340A1 WO 2020119340 A1 WO2020119340 A1 WO 2020119340A1 CN 2019116090 W CN2019116090 W CN 2019116090W WO 2020119340 A1 WO2020119340 A1 WO 2020119340A1
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Prior art keywords
layer
metal
metal foil
carrier
high temperature
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PCT/CN2019/116090
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English (en)
French (fr)
Inventor
苏陟
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广州方邦电子股份有限公司
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Priority to KR1020217021448A priority Critical patent/KR102541338B1/ko
Priority to US17/309,059 priority patent/US11582869B2/en
Priority to JP2021526419A priority patent/JP7305766B2/ja
Publication of WO2020119340A1 publication Critical patent/WO2020119340A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/04—Wires; Strips; Foils
    • 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
    • H05K1/0393—Flexible materials
    • 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
    • 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
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • 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
    • 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
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • 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
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • 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
    • H05K1/11—Printed elements for providing electric connections to or between printed circuits
    • H05K1/118—Printed elements for providing electric connections to or between printed circuits specially for flexible printed circuits, e.g. using folded portions
    • 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
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/14—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using spraying techniques to apply the conductive material, e.g. vapour evaporation
    • H05K3/16—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using spraying techniques to apply the conductive material, e.g. vapour evaporation by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • 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
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • H05K3/025—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates by transfer of thin metal foil formed on a temporary carrier, e.g. peel-apart copper
    • 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
    • H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
    • H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
    • 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
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals

Definitions

  • the invention relates to the technical field of materials, in particular to a composite metal foil and a preparation method thereof.
  • the substrate is a flexible printed circuit board (FPC) processing material, which is usually composed of a flexible insulating base film and a composite metal foil.
  • FPC flexible printed circuit board
  • the side of the composite metal foil (including the carrier layer and the metal foil layer) provided with the metal foil layer is pressed against the flexible insulating base film to obtain the substrate.
  • the carrier layer needs to be peeled off.
  • the composite metal foil and the flexible insulating base film are pressed together under high temperature conditions, the carrier layer and the metal foil layer are likely to diffuse together under high temperature conditions, resulting in the carrier layer and the metal foil layer bonding, making It is difficult to peel between the carrier layer and the metal foil layer.
  • the purpose of the embodiments of the present invention is to provide a composite metal foil and a preparation method thereof, which can avoid the mutual diffusion of the carrier layer of the composite metal foil and the metal foil layer of the composite metal foil at high temperature to cause adhesion, thereby making the carrier layer and the metal The foil layer is easy to peel.
  • embodiments of the present invention provide a composite metal foil, including a carrier layer, a barrier layer, a peeling layer, and a metal foil layer;
  • the carrier layer, the barrier layer, the peeling layer and the metal foil layer are stacked in this order.
  • the barrier layer includes a stacked metal adhesive layer and a high temperature resistant layer.
  • the metal adhesive layer is provided on the Between the carrier layer and the high temperature resistant layer.
  • the peel strength between the carrier layer and the barrier layer is greater than the peel strength between the peel layer and the metal foil layer.
  • the hundred-grid test grade between the carrier layer and the barrier layer is 0 or 1 or 2
  • the peel strength between the peeling layer and the metal foil layer is 0.001-2 N/cm.
  • the peel strength between the peeling layer and the metal foil layer is greater than or equal to the peel strength between the peeling layer and the barrier layer.
  • the high temperature resistant layer is an organic high temperature resistant layer, or the high temperature resistant layer is made of any one or more materials of tungsten, chromium, zirconium, titanium, nickel, molybdenum, cobalt, and graphite.
  • the high temperature resistant layer is a single layer alloy structure; or, the high temperature resistant layer is a multilayer structure composed of a single material layer or a multilayer structure composed of an alloy layer and a single material layer, wherein the single material
  • the layers are made of the same chemical element.
  • the metal bonding layer is made of any one or more materials in the first type of metal; or, the metal bonding layer is made of any one or more materials in the second type of metal; Alternatively, the metal bonding layer is made of any one or more materials in the first type of metal and any one or more materials in the second type of metal;
  • the first type of metal is a metal that is easily bonded to the carrier layer
  • the second type of metal is a metal that is easily bonded to the high temperature resistant layer
  • the first metal is copper or zinc
  • the second metal is nickel or iron or manganese
  • the metal bonding layer is a single metal layer made of the first metal or the second metal.
  • the metal bonding layer is a single-layer alloy structure made of the first metal and the second metal.
  • the metal bonding layer includes a single metal layer made of a first type of metal and connected to the carrier layer, and the metal bonding layer further includes a second type of metal and A single metal layer connected by a high temperature layer.
  • the metal bonding layer includes a multilayer structure composed of an alloy layer and a single metal layer; wherein, the alloy layer of the metal bonding layer is made of the first type metal and the second type metal
  • the single metal layer of the metal bonding layer is made of the first metal or the second metal.
  • the peeling layer is made of any one or more materials of nickel, silicon, molybdenum, graphite, titanium, and niobium; or, the peeling layer is made of an organic polymer material.
  • the thickness of the metal foil layer is less than or equal to 9 ⁇ m.
  • the metal foil layer is copper foil or aluminum foil; and/or, the carrier layer is carrier copper or carrier aluminum or an organic film.
  • the roughness Rz of the side of the carrier layer close to the metal foil layer is less than or equal to 5 ⁇ m; and/or the roughness Rz of the side of the metal foil layer far from the carrier layer is less than or equal to 3.0 ⁇ m.
  • a first oxidation prevention layer is provided on the side of the carrier layer close to the barrier layer; and/or a second oxidation prevention layer is provided on the side of the metal foil layer away from the barrier layer .
  • a composite metal foil provided by an embodiment of the present invention includes a carrier layer, a barrier layer, a peeling layer, and a metal foil layer stacked in this order.
  • the barrier layer includes a stacked metal adhesive layer and a high-temperature-resistant layer. Between the carrier layer and the high temperature resistant layer, a peeling layer is provided between the carrier layer and the metal foil layer to facilitate the peeling of the carrier layer, and a barrier layer is provided between the carrier layer and the metal foil layer to avoid the carrier layer from The metal foil layer diffuses at high temperature to cause adhesion, so that the carrier layer and the metal foil layer are easily peeled off; in addition, by providing a metal adhesive layer between the carrier layer and the high temperature resistant layer, the barrier layer is not easily connected to the carrier layer Separation to prevent peeling between the barrier layer and the carrier layer.
  • FIG. 1 is a schematic structural view of an embodiment of a composite metal foil provided by the present invention.
  • FIG. 2 is a schematic structural view of another embodiment of a composite metal foil provided by the present invention.
  • FIG. 3 is a schematic diagram of peeling off an embodiment of a composite metal foil provided by the present invention.
  • FIG. 5 is a schematic flowchart of an embodiment of a method for preparing a composite metal foil provided by the present invention
  • an embodiment of the present invention provides a composite metal foil, including a carrier layer 1, a barrier layer 2, a peeling layer 3 and a metal foil layer 4;
  • the carrier layer 1, the barrier layer 2, the peeling layer 3, and the metal foil layer 4 are stacked in this order, and the barrier layer 2 includes a metal adhesive layer 22 and a high temperature resistant layer 21 that are stacked.
  • the metal bonding layer 22 is provided between the carrier layer 1 and the high temperature resistant layer 21.
  • the present invention by providing a peeling layer 3 between the carrier layer 1 and the metal foil layer 4 to facilitate peeling of the carrier layer 1, and by providing a barrier layer 2 between the carrier layer 1 and the metal foil layer 4, To prevent the carrier layer 1 and the metal foil layer 4 from spreading at high temperature to cause adhesion, thereby making the carrier layer 1 and the metal foil layer 4 easy to peel; in addition, by providing a metal adhesive layer between the carrier layer 1 and the high temperature resistant layer 21 22, so that the barrier layer 2 is not easily separated from the carrier layer 1, thereby preventing peeling between the barrier layer 2 and the carrier layer 1.
  • the carrier layer 1 and the barrier layer 2 are peeled at the same time when using the composite metal foil, at a temperature of 20-400°C, the carrier layer 1 and the barrier layer
  • the peel strength between 2 is greater than the peel strength between the peel layer 3 and the metal foil layer 4.
  • the hundred-grid test grade between the carrier layer 1 and the barrier layer 2 is 0 or 1 or 2
  • the peel strength between the peeling layer 3 and the metal foil layer 4 is 0.001-2N/ cm.
  • the 100-degree test level in this embodiment is an ISO level, and the standard "GBT9286-1998 Paint and varnish paint film cross-cut test" can be referred to.
  • the 100-degree test level in this embodiment can correspond to the ASTM level
  • a hundred grid test level of 0 corresponds to an ASTM level of 5B
  • a hundred grid test level of 1 corresponds to an ASTM level of 4B
  • the Hundred Grid test rating can reflect the peel strength between the carrier layer 1 and the barrier layer 2. The higher the rating, the greater the peel strength between the carrier layer 1 and the barrier layer 2.
  • the hundred test levels between the carrier layer 1 and the barrier layer 2 are all in the first three levels, that is, the adhesion between the carrier layer 1 and the barrier layer 2 is relatively large, and the peeling layer 3
  • the peel strength with the metal foil layer 4 is very small, so the peel strength between the carrier layer 1 and the barrier layer 2 is always much greater than that between the peel layer 3 and the metal foil layer 4 Therefore, when the composite metal foil is used, the carrier layer 1, the barrier layer 2 and the peeling layer 3 can be easily peeled from the metal foil layer 4 at the same time.
  • the peel strength between the peeling layer 3 and the metal foil layer 4 is greater than or equal to the peel strength between the peeling layer 3 and the barrier layer 2. Since the peeling strength between the peeling layer 3 and the metal foil layer 4 is greater than or equal to the peeling strength between the peeling layer 3 and the barrier layer 2, when peeling the composite metal foil, the The peeling layer 3 can be partially or completely left on the metal foil layer 4 so as to prevent the metal foil layer 4 from being oxidized, thereby effectively protecting the metal foil layer 4.
  • the peeling strength between the peeling layer 3 and the metal foil layer 4 may also be smaller than the peeling strength between the peeling layer 3 and the barrier layer 2, so that when peeling the composite metal foil, The peeling layer 3 can partially or completely remain on the barrier layer 2 and peel off from the metal foil layer 4 simultaneously with the carrier layer 1 and the barrier layer 2, as shown in FIG. 4, I will not repeat them here.
  • the thickness of the barrier layer 2 is greater than or equal to Preferably, the thickness of the barrier layer 2 is preferably
  • the high temperature resistant layer 21 is an organic high temperature resistant layer 21, and when the high temperature resistant layer 21 is an organic high temperature resistant layer, it is selected from one of nitrogen-containing organic compounds, sulfur-containing organic compounds and carboxylic acids or A single material layer made of multiple types, or formed of multiple single material layers; alternatively, the high temperature resistant layer 21 is made of any one or more of tungsten, chromium, zirconium, titanium, nickel, molybdenum, cobalt, and graphite Made of various materials.
  • the high temperature resistant layer 21 is a single layer alloy structure; or, the high temperature resistant layer 21 is a multilayer structure composed of a single material layer or a multilayer structure composed of an alloy layer and a single material layer, wherein the single The material layer is made of the same chemical element.
  • the single-layer alloy structure is a single-layer structure made of an alloy material, for example, a single-layer structure made of tungsten-chromium alloy;
  • the high-temperature-resistant layer 21 is a multi-layer structure or alloy composed of a single material layer A multilayer structure composed of layers and a single material layer, for example, a multilayer structure composed of a tungsten metal layer and a chromium metal layer, or a multilayer structure composed of a tungsten-chromium alloy layer and a zirconium metal layer.
  • the metal bonding layer 22 is made of any one or more materials of the first type of metal Or, the metal bonding layer 22 is made of any one or more materials in the second type of metal; or, the metal bonding layer 22 is made of any one or more materials in the first type of metal and the first Made of any one or more materials of the second type of metal; wherein the first type of metal is a metal that is easy to bond with the carrier layer, and the second type of metal is a metal that is easy to stick with the high temperature resistant layer 21
  • the metal of the junction prevents peeling from between the carrier layer 1 and the barrier layer 2.
  • the first metal is copper or zinc
  • the second metal is nickel or iron or manganese.
  • the barrier layer 2 can be firmly connected to the carrier layer 1 to prevent peeling between the barrier layer 2 and the carrier layer 1.
  • the adhesion between the first type of metal and the carrier layer 1 is relatively strong, and the adhesion between the second type of metal and the high temperature resistant layer 21 is relatively strong, the The formed single metal layer is connected to the carrier layer 1, and at the same time, the single metal layer made of the second type of metal is connected to the high temperature resistant layer 21, so that the barrier layer 2 is not easily separated from the carrier layer 1 .
  • the structure of the metal bonding layer 22 may include but is not limited to the following situations: (1) The metal bonding layer 22 is a single metal layer made of the first type of metal; (2) The metal bonding layer 22 is a single metal layer made of the second metal; (3) The metal bonding layer 22 is made of the first metal and the second metal A single-layer alloy structure, such as a single-layer alloy structure made of copper-nickel alloy; (4) The metal bonding layer 22 includes a single metal layer made of the first type of metal and connected to the carrier layer 1 The metal bonding layer 22 further includes a single metal layer made of a second type of metal and connected to the high temperature resistant layer 21, for example, a multilayer structure composed of a copper metal layer and a nickel metal layer, and the copper metal layer is The carrier layer 1 is connected, and the nickel metal layer is connected to the high temperature resistant layer 21; (5) The metal bonding layer 22 includes a multilayer structure composed of an alloy layer and a single metal layer; wherein, the metal bonding layer 22 Of the alloy
  • the metal bonding layer 22 is composed of a first type of metal single layer structure 221 and a second type metal single layer structure 222, wherein the first type metal single layer structure 221 is a single metal layer made of the first type metal and connected to the carrier layer 1, the second The metalloid single layer structure 222 is a single metal layer made of the second metal and connected to the high temperature resistant layer 21.
  • a single-layer structure made of the first-type metal and/or the second-type metal single-layer structure 221 and a second-type metal single-layer structure 222 may also be provided Structure made of metal-like single-layer structure. Made by providing a single layer structure of the first metal and/or a single layer structure of the second metal between the first metal single layer structure 221 and the second metal single layer structure 222 In order to further improve the reliability of the connection between the barrier layer 2 and the carrier layer 1, so as to further prevent peeling between the barrier layer 2 and the carrier layer 1.
  • the peeling layer 3 is made of any one or more materials of nickel, silicon, molybdenum, graphite, titanium, and niobium; or, the peeling layer 3 is made of an organic polymer material .
  • the thickness of the peeling layer 3 is preferably Since it is difficult to form a uniform metal foil layer 4 when the peeling layer 3 is too thick, it is easy to cause a large number of pinholes in the metal foil layer 4 (when the metal foil layer 4 has pinholes, after it is etched into a line, Opening phenomenon will easily occur); when the peeling layer 3 is too thin, it is easy to cause it to be difficult to peel between the metal foil layer 4; therefore, the thickness of the peeling layer 3 is preferably Thus, it is ensured that a uniform metal foil layer 4 can be formed, a large number of pinholes are avoided in the metal foil layer 4, and at the same time, the peeling layer 3 and the metal foil layer 4 are easily peeled off.
  • the thickness of the metal foil layer 4 is less than or equal to 9 ⁇ m.
  • the thickness of the metal foil layer 4 may be 6 ⁇ m, 5 ⁇ m, 4 ⁇ m, or 2 ⁇ m, etc., so as to obtain an extremely thin metal foil layer 4 which is favorable for forming a fine circuit board.
  • a metal adhesive layer is provided 22, so that the metal adhesive layer 22 not only makes the barrier layer 2 and the carrier layer 1 have a strong peeling strength, but also effectively ensures that the carrier layer 1 can be peeled off from the metal foil layer 4 stably, thereby obtaining a complete electrode
  • the thin metal foil layer 4, and the surface of the carrier layer 1 is also treated with a metal bonding layer 22, so that the entire surface of the carrier layer 1 is more uniform and dense, which is beneficial for peeling off the carrier layer 1 to obtain a pinhole
  • the very thin metal foil layer 4 is few, which is beneficial to the subsequent circuit fabrication.
  • the metal foil layer 4 is preferably a copper foil or an aluminum foil; the carrier layer 1 may be a carrier copper, a carrier aluminum or an organic film, etc. Since the carrier layer 1 mainly plays a bearing role, a certain thickness is required. When the carrier layer 1 is copper or aluminum, the thickness of the carrier layer 1 is preferably 9-50 ⁇ m; when the carrier layer 1 is an organic thin film, the thickness of the carrier layer 1 is preferably 20-100 ⁇ m.
  • the roughness Rz of the side of the carrier layer 1 close to the metal foil layer 4 is less than or equal to 5 ⁇ m; and/or the side of the metal foil layer 4 away from the carrier layer 1
  • the roughness Rz is less than or equal to 3.0 ⁇ m.
  • the roughness Rz of the general copper foil is 0.5-3.0 ⁇ m; when the copper foil is used in high frequency, the roughness of the copper foil is set to less than 0.5 ⁇ m, so as to ensure the copper foil and other materials Under the premise of the adhesion between the copper foil, it can be used in high-frequency signal transmission circuit boards.
  • the carrier layer 1 in this embodiment is provided with a first oxidation prevention layer on the side close to the barrier layer 2; 1 A first anti-oxidation layer is provided on the side close to the barrier layer 2 to prevent the carrier layer 1 from oxidizing, thereby protecting the carrier layer 1.
  • a second anti-oxidation layer is provided on the side of the metal foil layer 4 away from the barrier layer 2 A second anti-oxidation layer is provided on the side to prevent the metal foil layer 4 from oxidizing, thereby protecting the metal foil layer 4.
  • an embodiment of the present invention also provides a preparation method for preparing the composite metal foil, including the following steps:
  • the peel strength between the carrier layer 1 and the barrier layer 2 is greater than the peel strength between the peel layer 3 and the metal foil layer 4.
  • the hundred test level between the carrier layer and the barrier layer is 0 or 1 or 2, and the peeling between the peeling layer 3 and the metal foil layer 4 The strength is 0.001-2N/cm.
  • the first type of metal is a metal that is easily bonded to the carrier layer 1
  • the second type of metal is a metal that is easily bonded to the high temperature resistant layer 21, preferably, the first type of metal
  • the metal is copper or zinc
  • the second metal is nickel or iron or manganese.
  • the step S12, the step S13 and the step S14 are preferably sputtering, the current of the sputtering method is preferably 6-12A, and the voltage is preferably 300-500V.
  • the metal bonding layer 22 and the high temperature resistant layer 21 formed by sputtering constitute the barrier layer 2 to ensure that a uniform and dense barrier layer 2 is obtained, and a uniform and dense peeling layer 3 is formed by sputtering, so that It is beneficial to improve the peeling stability of the composite metal foil and can effectively reduce the number of pinholes; in addition, the metal foil layer 4 is preferably formed by electroplating. Before the metal foil layer 4 is formed, it is uniformly formed by sputtering The dense barrier layer 2 and the peeling layer 3 are conducive to the uniform plating of the metal foil layer 4, so that the surface roughness of the formed metal foil layer 4 is relatively uniform, which is beneficial to the subsequent circuit manufacturing and manufacturing The metal foil layer 4 thinner.
  • forming the metal adhesive layer 22 on one side of the carrier layer 1 is specifically: forming a single metal layer on one side of the carrier layer 1; wherein, on the carrier layer 1
  • the single metal layer formed on one side is made of the first type metal or the second type metal.
  • forming the metal bonding layer 22 on the side of the carrier layer 1 may specifically be: forming a single-layer alloy structure on the side of the carrier layer 1; wherein, on the carrier The single-layer alloy structure formed on one side of the layer 1 is made of the first metal and the second metal.
  • forming the metal adhesive layer 22 on the side of the carrier layer 1 may specifically be: forming a multilayer structure on the side of the carrier layer 1; wherein, in the carrier layer The multilayer structure formed on one side of 1 includes a single metal layer made of the first type of metal and connected to the carrier layer 1, and the multilayer structure formed on one side of the carrier layer 1 further includes A single metal layer made of two types of metals and connected to the high temperature resistant layer 21.
  • forming the metal adhesive layer 22 on the side of the carrier layer 1 may specifically be: forming a multilayer structure on the side of the carrier layer; wherein, on the carrier layer 1
  • the multilayer structure formed on one side of the layer includes an alloy layer and a single metal layer.
  • the alloy layer of the multilayer structure formed on the side of the carrier layer 1 is made of the first type metal and the second type metal.
  • the single-metal layer of the multilayer structure formed on one side of the carrier layer 1 is made of the first metal or the second metal.
  • the high temperature resistant layer 21 may be an organic high temperature resistant layer 21; or, the high temperature resistant layer 21 is a single-layer alloy structure; or, the high temperature resistant layer 21 is a multi-layer structure composed of a single material layer Or a multilayer structure composed of an alloy layer and a single material layer, the single material layer is made of the same chemical element; wherein, the high temperature resistant layer 21 is an organic high temperature resistant layer, or the high temperature resistant layer 21 is made of tungsten , Chromium, zirconium, titanium, nickel, molybdenum, cobalt and graphite are made of any one or more materials.
  • the carrier layer 1 may be copper or aluminum.
  • the carrier layer 1 may be formed by electroplating, and the plating solution forming the carrier layer 1 may include a copper sulfate solution, wherein the copper content of the plating solution forming the carrier layer 1 is: 15-25 g/L, PH value 6-9; the plating solution forming the carrier layer 1 further includes additives, the additives include brightener sodium sulfonate, leveling agent thiourea and wetting agent polyethylene glycol, the brightener sodium sulfonate
  • the mass fraction is preferably 0.1-2 g/L
  • the mass fraction of the leveling agent thiourea is preferably 0.01-1 g/L
  • the mass fraction of the wetting agent polyethylene glycol is preferably 0.1-5 g/L.
  • the carrier layer 1 is roughened by means of acidic electroplating, wherein the plating solution for acidic copper plating may include a copper sulfate solution, and the copper content of the plating solution for acidic copper plating is 10-15 g/L , Acid content is 90-100g/L, molybdenum content is 600-800PPM.
  • the formation of the first anti-oxidation layer may be in the form of galvanized nickel alloy; in addition, after the formation of the first anti-oxidation layer on the roughened carrier layer 1, the first anti-oxidation layer may also be subjected to plasma
  • the voltage during plasma cleaning is preferably 1500-2500V, and the current is preferably 0.1-1.5A.
  • the formation of the carrier layer 1 in this embodiment further includes:
  • the carrier layer 1 is annealed under heat treatment conditions; wherein the heat treatment conditions are: a heat treatment temperature of 200-300°C, and a heating time of 30-300 minutes. Preferably, the heating time is 1 hour.
  • the carrier layer 1 is annealed under heat treatment conditions to suppress the crystal growth of the carrier layer 1 in the heating process, thereby delaying the diffusion of the carrier layer 1 in the heating process, thereby further preventing the carrier layer 1 and the metal foil layer 4 Adhesion occurs between.
  • the peeling layer 3 may be made of any one or more materials of nickel, silicon, molybdenum, graphite, titanium, and niobium.
  • the metal foil layer 4 may be copper foil or aluminum foil.
  • the metal foil layer 4 may be formed by electroplating, and the plating solution for forming the metal foil layer 4 may include a copper sulfate solution, wherein the copper content of the plating solution for forming the metal foil layer 4 is: 15-25g/L , PH value is 6-9;
  • the plating solution forming the metal foil layer 4 includes additives, the additives include brightener sodium sulfonate, leveling agent thiourea and wetting agent polyethylene glycol, the brightener sulfonate
  • the mass fraction of sodium is preferably 0.1-2g/L
  • the mass fraction of the leveling agent thiourea is preferably 0.01-1g/L
  • the mass fraction of the wetting agent polyethylene glycol is preferably 0.1-5g/L .
  • the plating solutions for preparing the carrier layer 1 and the metal foil layer 4 are set to be the same, so that the carrier layer 1 and the The metal foil layer 4 has the same stress and tension effects, so that the carrier layer 1 and the metal foil layer 4 have the same bending degree, thereby avoiding warping of the composite metal foil.
  • the method for preparing the composite metal foil further includes the steps of:
  • a second anti-oxidation layer is formed on the surface of the roughened metal foil layer 4 away from the carrier layer 1.
  • the side of the metal foil layer 4 away from the carrier layer 1 is roughened, which can be carried out by acid plating, wherein the plating solution for acid copper plating may include a copper sulfate solution for acid
  • the copper plating bath has a copper content of 10-15 g/L, an acid content of 90-100 g/L, and a molybdenum content of 600-800 PPM; wherein, the formation of the second anti-oxidation layer may be in the form of zinc-plated nickel alloy;
  • plasma cleaning may be performed on the second anti-oxidation layer, wherein the voltage during plasma cleaning is preferably 1500-2500V, and the current is preferably 0.1-1.5A.
  • a carrier layer 1 is formed by electroplating, and then the carrier layer 1 is roughened, and then a first oxidation prevention layer is formed on the carrier layer 1, and the carrier layer 1 is annealed under heat treatment conditions; wherein, The heat treatment conditions are: a heat treatment temperature of 250° C.
  • the carrier layer 1 is a copper carrier, and the plating solution forming the carrier layer 1 includes a copper sulfate solution, wherein the carrier layer 1 is formed
  • the copper content of the plating solution is: 20g/L, the PH value is 7;
  • the plating solution forming the carrier layer 1 further includes additives, the additives include brightener sodium sulfonate, leveling agent thiourea and wetting agent polyethylene Glycol, the mass fraction of the brightener sodium sulfonate is 0.8g/L, the mass fraction of the leveling agent thiourea is 0.5g/L, and the mass fraction of the wetting agent polyethylene glycol is 3g/ L.
  • the carrier layer 1 may be roughened by acid plating, wherein the plating solution for acid copper plating includes copper sulfate solution, and the copper content of the plating solution for acid copper plating is 13g/L.
  • the acid content is 95g/L and the molybdenum content is 700PPM.
  • the formation of the first oxidation prevention layer is in the form of zinc-plated nickel alloy.
  • a metal bonding layer 22 is formed on one side of the carrier layer 1 by sputtering; wherein, the metal bonding layer 22 is a structure composed of a copper metal layer and a nickel metal layer, and the copper metal layer is The carrier layer 1 is connected, and the nickel metal layer is connected to the high temperature resistant layer 21;
  • the metal bonding layer 22 and the high temperature resistant layer 21 constitute a barrier layer 2; wherein, the high temperature resistant layer 21 is tungsten- Single-layer alloy structure made of titanium alloy;
  • the plating solution for acid copper plating includes copper sulfate solution, the copper content of the acid copper plating solution is 13g/L, the acid content is 95g/L, and the molybdenum content is 700PPM; wherein,
  • the formation of the second anti-oxidation layer may be in the form of zinc-plated nickel alloy.
  • the high temperature resistant layer 21 is a single-layer alloy structure made of tungsten-nickel alloy.
  • the other processes and steps in this embodiment are the same as those in Embodiment 1, and no more details are provided here.
  • the high temperature resistant layer 21 is a single-layer alloy structure made of tungsten-molybdenum alloy.
  • the other processes and steps in this embodiment are the same as those in Embodiment 1, and no more details are provided here.
  • the high temperature resistant layer 21 is a single-layer alloy structure made of chromium-nickel alloy.
  • the other processes and steps in this embodiment are the same as those in Embodiment 1, and no more details are provided here.
  • the high temperature resistant layer 21 is a single-layer alloy structure made of zirconium-titanium alloy.
  • the other processes and steps in this embodiment are the same as those in Embodiment 1, and no more details are provided here.
  • the high temperature resistant layer 21 is a single-layer alloy structure made of titanium-nickel alloy.
  • the other processes and steps in this embodiment are the same as those in Embodiment 1, and no more details are provided here.
  • the high temperature resistant layer 21 is a single-layer alloy structure made of titanium-molybdenum alloy.
  • the other processes and steps in this embodiment are the same as those in Embodiment 1, and no more details are provided here.
  • the high temperature resistant layer 21 is a single-layer alloy structure made of titanium-cobalt alloy.
  • the other processes and steps in this embodiment are the same as those in Embodiment 1, and no more details are provided here.
  • the high temperature resistant layer 21 is a single-layer alloy structure made of nickel-molybdenum alloy.
  • the other processes and steps in this embodiment are the same as those in Embodiment 1, and no more details are provided here.
  • the high temperature resistant layer 21 is a single-layer alloy structure made of molybdenum-cobalt alloy.
  • the other processes and steps in this embodiment are the same as those in Embodiment 1, and no more details are provided here.
  • the high temperature resistant layer 21 is a structure made of a tungsten metal layer and a graphite layer, and the tungsten metal layer is connected to the metal bonding layer 22, and the graphite layer and the peeling layer 3 Connect.
  • the other processes and steps in this embodiment are the same as those in Embodiment 1, and no more details are provided here.
  • the high temperature resistant layer 21 is a structure made of a chromium metal layer and a graphite layer, and the chromium metal layer is connected to the metal bonding layer 22, and the graphite layer and the peeling layer 3 Connect.
  • the other processes and steps in this embodiment are the same as those in Embodiment 1, and no more details are provided here.
  • the high temperature resistant layer 21 is a structure made of a nickel metal layer and a graphite layer, and the nickel metal layer is connected to the metal bonding layer 22, and the graphite layer and the peeling layer 3 Connect.
  • the other processes and steps in this embodiment are the same as those in Embodiment 1, and no more details are provided here.
  • the high temperature resistant layer 21 is a structure made of a tungsten-nickel alloy and a chromium metal layer, and the tungsten-nickel alloy is connected to the metal bonding layer 22, and the chromium metal layer is The peeling layer 3 is connected.
  • the other processes and steps in this embodiment are the same as those in Embodiment 1, and no more details are provided here.
  • the high temperature resistant layer 21 is a structure made of a nickel-molybdenum alloy and a chromium metal layer, and the nickel-molybdenum alloy is connected to the metal bonding layer 22, and the chromium metal layer is The peeling layer 3 is connected.
  • the other processes and steps in this embodiment are the same as those in Embodiment 1, and no more details are provided here.
  • the high temperature resistant layer 21 is a structure made of a molybdenum-cobalt alloy and a chromium metal layer, and the molybdenum-cobalt alloy is connected to the metal bonding layer 22, and the chromium metal layer is The peeling layer 3 is connected.
  • the other processes and steps in this embodiment are the same as those in Embodiment 1, and no more details are provided here.
  • the high temperature resistant layer 21 is a structure made of titanium-nickel alloy and chromium metal layer, and the titanium-nickel alloy is connected to the metal bonding layer 22, and the chromium metal layer is The peeling layer 3 is connected.
  • the other processes and steps in this embodiment are the same as those in Embodiment 1, and no more details are provided here.
  • a carrier layer 1 is formed by electroplating, and then the carrier layer 1 is roughened, and then a first oxidation prevention layer is formed on the carrier layer 1, and the carrier layer 1 is annealed under heat treatment conditions; wherein, The heat treatment conditions are: a heat treatment temperature of 250° C.
  • the carrier layer 1 is a copper carrier, and the plating solution forming the carrier layer 1 includes a copper sulfate solution, wherein the carrier layer 1 is formed
  • the copper content of the plating solution is: 20g/L, the PH value is 7;
  • the plating solution forming the carrier layer 1 further includes additives, the additives include brightener sodium sulfonate, leveling agent thiourea and wetting agent polyethylene Glycol, the mass fraction of the brightener sodium sulfonate is 0.8g/L, the mass fraction of the leveling agent thiourea is 0.5g/L, and the mass fraction of the wetting agent polyethylene glycol is 3g/ L.
  • the carrier layer 1 may be subjected to the first roughening treatment by acid plating, wherein the plating solution for acid copper plating includes copper sulfate solution, and the copper content of the plating solution for acid copper plating is 13 g /L, the acid content is 95g/L, and the molybdenum content is 700PPM.
  • the formation of the first oxidation prevention layer is in the form of zinc-plated nickel alloy.
  • a metal bonding layer 22 is formed on one side of the carrier layer 1 by sputtering; wherein, the metal bonding layer 22 is a structure composed of a copper metal layer and a nickel metal layer, and the copper metal layer is The carrier layer 1 is connected, the nickel metal layer is connected to the high temperature resistant layer 21, and the thickness of the metal bonding layer 22 is
  • a high temperature resistant layer 21 is formed on the metal bonding layer 22 by sputtering, and the metal bonding layer 22 and the high temperature resistant layer 21 constitute a barrier layer 2; wherein, the high temperature resistant layer 21 is titanium metal Layer, the thickness of the high temperature resistant layer 21 is
  • peeling layer 3 is a graphite layer with a thickness of
  • S46 Perform a second roughening treatment on the side of the metal foil layer 4 away from the carrier layer 1, and use acid plating on the side of the roughened metal foil layer 4 away from the carrier layer 1 Forming a second anti-oxidation layer; wherein the plating solution for acid copper plating includes a copper sulfate solution, the plating solution for acid copper plating has a copper content of 13g/L, an acid content of 95g/L, and a molybdenum content of 700PPM; Wherein, the formation of the second anti-oxidation layer may be in the form of galvanized nickel alloy.
  • Embodiment 18 The difference between this embodiment and Embodiment 18 is that the metal bonding layer 22 is a copper metal layer.
  • the other processes and steps in this embodiment are the same as those in Embodiment 1, and no more details are provided here.
  • the difference between this embodiment and embodiment 18 is that the composition of the plating solution forming the carrier layer 1 and the metal foil layer 4 is the same, and the copper content in the plating solution is 20g/L, the PH value is 7, and the additives include brightener sodium sulfonate, Leveling agent thiourea and wetting agent polyethylene glycol, the mass fraction of brightener sodium sulfonate is 0.8g/L, leveling agent thiourea mass fraction is 0.5g/L, wetting agent polyethylene glycol The mass fraction is 3g/L.
  • Embodiment 18 The difference between this embodiment and Embodiment 18 is that the metal adhesive layer 22, the barrier layer 2 and the peeling layer 3 are formed by evaporation plating.
  • Embodiment 18 The difference between this embodiment and Embodiment 18 is that the temperature of the annealing treatment is 150°C and the heating time is 120 minutes.
  • Embodiment 18 The difference between this embodiment and Embodiment 18 is that the first roughening process and the second roughening process are not performed.
  • Embodiment 1 The difference between this embodiment and Embodiment 1 is that after the carrier layer 1 is formed, the barrier layer 2 is not fabricated, but the peeling layer 3 is directly formed on the carrier layer 1.
  • the other processes and steps in this embodiment are the same as those in Embodiment 1, and no more details are provided here.
  • Embodiment 1 The difference between this embodiment and Embodiment 1 is that after the metal bonding layer 22 is formed, the high temperature resistant layer 21 is not formed, but the peeling layer 3 is directly formed on the metal bonding layer 22.
  • the other processes and steps in this embodiment are the same as those in Embodiment 1, and no more details are provided here.
  • Embodiment 1 The difference between this embodiment and Embodiment 1 is that after the carrier layer 1 is formed, the metal bonding layer 22 is not formed, but the high temperature resistant layer 21 is directly formed on the carrier layer 1.
  • the other processes and steps in this embodiment are the same as those in Embodiment 1, and no more details are provided here.
  • Table 1 shows that the composite metal foils prepared in Examples 1-23 were directly tested under normal temperature conditions (such as 16-27°C, with 25°C as an example), or at different temperatures (200°C and 340°C, respectively) ) After being laminated with the flexible insulating base film, the test results of multiple tests are conducted under normal temperature conditions, and the measured peel strength between the carrier layer 1 and the barrier layer 2 and the peel layer 3 Peel strength with the metal foil layer 4.
  • normal temperature conditions such as 16-27°C, with 25°C as an example
  • different temperatures 200°C and 340°C, respectively
  • the carrier layer 1 and the metal foil layer 4 will mutually diffuse to some extent under high temperature conditions, which results in a certain degree of adhesion between the carrier layer 1 and the metal foil layer 4, therefore, the The peel strength between the carrier layer 1 and the barrier layer 2 and the peel strength between the peel layer 3 and the metal foil layer 4 increase with increasing temperature, but, as can be seen from Table 1 In the composite metal foils prepared in Examples 1-17, no matter under normal temperature or high temperature conditions, the test level between the carrier layer 1 and the barrier layer 2 is in the top three levels, that is, the carrier layer The adhesion between 1 and the barrier layer 2 is relatively large, and the peel strength between the peeling layer 3 and the metal foil layer 4 is very small, thus making the carrier layer 1 and the barrier layer 2 The peel strength between is always much greater than the peel strength between the peel layer 3 and the metal foil layer 4, therefore, when using the composite metal foil, the carrier layer 1, the barrier can be conveniently The layer 2 and the peeling layer 3 are peeled from the metal foil layer 4 at the same time.
  • Comparing Examples 18 to 23 it can be known that the process conditions of the preparation process of the metal foil are limited within the preferred range of the present application, which is beneficial to improve the overall performance of the metal foil.
  • the intermetallic diffusion of the composite metal foils prepared in Comparative Examples 1-3 under high temperature conditions is more serious, which results in a greater degree of adhesion between the carrier layer 1 and the metal foil layer 4, resulting in the use of
  • a composite metal foil and a preparation method thereof provided by an embodiment of the present invention, wherein the composite metal foil includes a carrier layer 1, a barrier layer 2, a peeling layer 3, and a metal foil layer 4 that are sequentially stacked, and the barrier layer 2 includes The metal adhesive layer 22 and the high-temperature-resistant layer 21 that are stacked are provided between the carrier layer 1 and the high-temperature-resistant layer 21, and the peeling layer 3 is provided between the carrier layer 1 and the metal foil layer 4 in order to After the carrier layer 1 is peeled off, and a barrier layer 2 is provided between the carrier layer 1 and the metal foil layer 4, the carrier layer 1 and the metal foil layer 4 are prevented from adhering to each other at high temperature to cause adhesion, so that the carrier layer 1 and the metal The foil layer 4 is easy to peel; in addition, by providing a metal adhesive layer 22 between the carrier layer 1 and the high temperature resistant layer 21, the barrier layer 2 is not easily separated from the carrier layer 1, thereby preventing the barrier layer 2 from being separated from the carrier layer 1 Peeling occurs

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Abstract

一种复合金属箔及其制备方法。该复合金属箔包括载体层（1）、阻隔层（2）、剥离层（3）和金属箔层（4）；载体层（1）、阻隔层（2）、剥离层（3）和金属箔层（4）依次层叠设置，阻隔层（2）包括层叠设置的金属粘结层（22）和耐高温层（21），金属粘结层（22）设于载体层（1）和耐高温层（21）之间，通过在载体层（1）和金属箔层（4）之间设置剥离层（3），以便于剥离载体层（1），并通过在载体层（1）和金属箔层（4）之间设置阻隔层（2），以避免载体层（1）与金属箔层（4）在高温时相互扩散造成粘结，从而使得载体层（1）与金属箔层（4）易于剥离；此外，通过在载体层（1）和耐高温层（21）之间设置金属粘结层（22），以使得阻隔层（2）不易于与载体层（1）分离，从而防止阻隔层（2）与载体层（1）之间发生剥离。

Description

一种复合金属箔及其制备方法 技术领域
本发明涉及材料技术领域，特别是涉及一种复合金属箔及其制备方法。
背景技术
目前，基板是挠性印制电路板(Flexible Printed Circuit board，FPC)的加工材料，其通常由挠性绝缘基膜与复合金属箔组成的。在现有技术中制备基板时，通常先将复合金属箔(包括载体层和金属箔层)设有金属箔层的一侧与挠性绝缘基膜进行压合，从而得到基板，在使用基板时，需要将载体层剥离。但是，由于复合金属箔与挠性绝缘基膜进行压合时需要在高温条件下，而载体层与金属箔层在高温条件下容易发生相互扩散，从而导致载体层与金属箔层粘结，使得载体层与金属箔层之间难以剥离。
发明内容
本发明实施例的目的是提供一种复合金属箔及其制备方法，其能够避免复合金属箔的载体层与复合金属箔的金属箔层在高温时相互扩散造成粘结，从而使得载体层与金属箔层易于剥离。
为了解决上述技术问题，本发明实施例提供一种复合金属箔，包括载体层、阻隔层、剥离层和金属箔层；
所述载体层、所述阻隔层、所述剥离层和所述金属箔层依次层叠设置，所述阻隔层包括层叠设置的金属粘结层和耐高温层，所述金属粘结层设于所述载体层和所述耐高温层之间。
作为优选方案，在20-400℃温度下，所述载体层与所述阻隔层之间的剥离强度大于所述剥离层与所述金属箔层之间的剥离强度。
作为优选方案，所述载体层与所述阻隔层之间的百格测试等级为0或1或2，所述剥离层与所述金属箔层之间的剥离强度为0.001-2N/cm。
作为优选方案，所述剥离层与所述金属箔层之间的剥离强度大于或等于所述剥离层与所述阻隔层之间的剥离强度。
作为优选方案，所述耐高温层为有机耐高温层，或者，所述耐高温层由钨、铬、锆、钛、镍、钼、钴和石墨中的任意一种或多种材料制成。
作为优选方案，所述耐高温层为单层合金结构；或，所述耐高温层为单材料层构成的多层结构或合金层和单材料层构成的多层结构，其中，所述单材料层由同一种化学元素制成。
作为优选方案，所述金属粘结层由第一类金属中任意一种或多种材料制成；或者，所述金属粘结层由第二类金属中任意一种或多种材料制成；或者，所述金属粘结层由第一类金属中任意一种或多种材料和第二类金属中任意一种或多种材料制成；
其中，所述第一类金属为易于与所述载体层粘结的金属，所述第二类金属为易于与所述耐高温层粘结的金属。
作为优选方案，所述第一类金属为铜或锌，所述第二类金属为镍或铁或锰。
作为优选方案，所述金属粘结层为所述第一类金属或所述第二类金属制成的单金属层。
作为优选方案，所述金属粘结层为所述第一类金属和所述第二类金属制成的单层合金结构。
作为优选方案，所述金属粘结层包括由第一类金属制成并与所述载体层连接的单金属层，所述金属粘结层还包括由第二类金属制成并与所述耐高温层连接的单金属层。
作为优选方案，所述金属粘结层包括合金层和单金属层构成的多层结构；其中，所述金属粘结层的合金层由所述第一类金属和所述第二类金属制成，所述金属粘结层的单金属层由所述第一类金属或所述第二类金属制成。
作为优选方案，所述剥离层由镍、硅、钼、石墨、钛和铌中的任意一种或多种材料制成；或，所述剥离层由有机高分子材料制成。
作为优选方案，所述金属箔层的厚度小于或等于9μm。
作为优选方案，所述金属箔层为铜箔或铝箔；和/或，所述载体层为载体铜或载体铝或有机薄膜。
作为优选方案，所述载体层靠近所述金属箔层的一面的粗糙度Rz为小于或等于5μm；和/或，所述金属箔层远离所述载体层的一面的粗糙度Rz为小于或等于3.0μm。
作为优选方案，所述载体层靠近所述阻隔层的一侧上设有第一防氧化层；和/或，所述金属箔层远离所述阻隔层的一侧上设有第二防氧化层。
本发明实施例提供的一种复合金属箔，包括依次层叠设置的载体层、阻隔层、剥离层和金属箔层，阻隔层包括层叠设置的金属粘结层和耐高温层，金属粘结层设于载体层和耐高温层之间，通过在载体层和金属箔层之间设置剥离层，以便于剥离载体层，并通过在载体层和金属箔层之间设置阻隔层，以避免载体层与金属箔层在高温时相互扩散造成粘结，从而使得载体层与金属箔层易于剥离；此外，通过在载体层和耐高温层之间设置金属粘结层，以使得阻隔层不易于与载体层分离，从而防止阻隔层与载体层之间发生剥离。
附图说明
图1是本发明提供的复合金属箔的一个实施例的结构示意图；
图2是本发明提供的复合金属箔的另一个实施例的结构示意图；
图3是本发明提供的复合金属箔的实施例的剥离示意图；
图4是本发明提供的复合金属箔的实施例的另一个剥离示意图；
图5是本发明提供的复合金属箔的制备方法的一个实施例的流程示意图；
其中，1、载体层；2、阻隔层；21、耐高温层；22、金属粘结层；221、第一类金属单层结构；222、第二类金属单层结构；3、剥离层；4、金属箔层。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
请参阅图1所示，为了解决上述技术问题，本发明实施例提供一种复合金属箔，包括载体层1、阻隔层2、剥离层3和金属箔层4；
所述载体层1、所述阻隔层2、所述剥离层3和所述金属箔层4依次层叠设置，所述阻隔层2包括层叠设置的金属粘结层22和耐高温层21，所述金属粘结层22设于所述载体层1和所述耐高温层21之间。
在本发明实施例中，通过在载体层1和金属箔层4之间设置剥离层3，以便于剥离载体层1，并通过在载体层1和金属箔层4之间设置阻隔层2，以避免载体层1与金属箔层4在高温时相互扩散造成粘结，从而使得载体层1与金属箔层4易于剥离；此外，通过在载体层1和耐高温层21之间设置金属粘结层22，以使得阻隔层2不易于与载体层1分离，从而防止阻隔层2与载体层1之间发生剥离。
在本发明实施例中，为了确保在使用所述复合金属箔时将载体层1、阻隔层2和剥离层3同时剥离，在20-400℃温度下，所述载体层1与所述阻隔层2之间的剥离强度大于所述剥离层3与所述金属箔层4之间的剥离强度。优选地，所述载体层1与所述阻隔层2之间的百格测试等级为0或1或2，所述剥离层3与所述金属箔层4之间的剥离强度为0.001-2N/cm。本实施例中的所述百格测试等级为ISO等级，可参考标准《GBT9286-1998色漆和清漆漆膜的划格试验》，此外，本实施例中的百格测试等级可对应于ASTM等级，比如百格测试等级为0对应于ASTM等级为5B，百格测试等级为1对应于ASTM等级为4B，以此类推，在此不做更多的赘述。百格测试等级能够体现所述载体层1与所述阻隔层2之间的剥离强度，等级越靠前，则所述载体层1与所述阻隔层2之间的剥离强度越大。所述载体层1与所述阻隔层2之间的百格测试等级都在前三级，即所述载体层1与所述阻隔层2之间的附着力比较大，而所述剥离层3与所述金属箔层4之间的剥离强度非常小，因此使得所述载体层1与所述阻隔层2之间的剥离强度始终远远大于所述剥离层3与所述金属箔层4之间的剥离强度，因此， 在使用所述复合金属箔时，能够方便地将所述载体层1、所述阻隔层2和所述剥离层3同时从所述金属箔层4上剥离。
如图3所示，在本发明实施例中，所述剥离层3与所述金属箔层4之间的剥离强度大于或等于所述剥离层3与所述阻隔层2之间的剥离强度。由于所述剥离层3与所述金属箔层4之间的剥离强度大于或等于所述剥离层3与所述阻隔层2之间的剥离强度，因此，在剥离所述复合金属箔时，所述剥离层3能够部分或全部留在所述金属箔层4上，从而能够防止所述金属箔层4氧化，进而有效地保护了所述金属箔层4。当然，所述剥离层3与所述金属箔层4之间的剥离强度也可以小于所述剥离层3与所述阻隔层2之间的剥离强度，以使得在剥离所述复合金属箔时，所述剥离层3能够部分或全部留在所述阻隔层2上，并随着所述载体层1和所述阻隔层2同时从所述金属箔层4上剥离，如图4所示，在此不做更多的赘述。
请参阅图1所示，所述阻隔层2的厚度大于或等于
Figure PCTCN2019116090-appb-000001
优选地，所述阻隔层2的厚度优选为
Figure PCTCN2019116090-appb-000002
其中，所述耐高温层21为有机耐高温层21，且当所述耐高温层21为有机耐高温层时，其选自含氮有机化合物、含硫有机化合物及羧酸中的一种或多种制成的单材料层形成，或由多个单材料层形成；或者，所述耐高温层21由钨、铬、锆、钛、镍、钼、钴和石墨中的任意一种或多种材料制成。优选地，所述耐高温层21为单层合金结构；或，所述耐高温层21为单材料层构成的多层结构或合金层和单材料层构成的多层结构，其中，所述单材料层由同一种化学元素制成。具体地，所述单层合金结构为由合金材料制成的单层结构，例如，钨-铬合金制成的单层结构；所述耐高温层21为单材料层构成的多层结构或合金层和单材料层构成的多层结构，例如，钨金属层和铬金属层构成的多层结构，或者，钨-铬合金层和锆金属层构成的多层结构。
结合图1和图2所示，为了防止所述阻隔层2与所述载体层1之间剥离分层，所述金属粘结层22由第一类金属中任意一种或多种材料制成；或者，所述金属粘结层22由第二类金属中任意一种或多种材料制成；或者，所述金属粘结层22由第一类金属中任意一种或多种材料和第二类金属中任意一种或多种材料制成；其中，所述第一类金属为易于与所述载体层粘结的金属，所述第二类金属为易于与所述耐高温层21粘结的金属，从而防止从载体层1与阻隔层2之间剥离。优选地，所述第一类金属为铜或锌，所述第二类金属为镍或铁或锰。通过设置所述金属粘结层22，以使得所述阻隔层2能够牢靠地与所述载体层1连接，从而防止所述阻隔层2与所述载体层1之间发生剥离。此外，由于第一类金属与所述载体层1之间的粘结力比较强，第二类金属与所述耐高温层21之间的粘结力比较强，因此通过将由第一类金属制成的单金属层与所述载体层1连接，同时将由第二类金属制成的单金属层与所述耐高温层21连接，以使得所述阻隔层2不易于与所述载体层1分离。
在本发明实施例中，所述金属粘结层22的结构可包括但不限于以下几种情况：(1)所述金属粘结层22为所述第一类金属制成的单金属层；(2)所述金属粘结层22为所述第二类金属制成单金属层；(3)所述金属粘结层22为所述第一类金属和所述第二类金属制成的单层合金结构，例如铜-镍合金制成的单层合金结构；(4)所述金属粘结层22包括由第一类金属制成并与所述载体层1连接的单金属层，所述金属粘结层22还包括由第二类金属制成并与所述耐 高温层21连接的单金属层，例如，铜金属层与镍金属层构成的多层结构，且铜金属层与所述载体层1连接，镍金属层与所述耐高温层21连接；(5)所述金属粘结层22包括合金层和单金属层构成的多层结构；其中，所述金属粘结层22的合金层由所述第一类金属和所述第二类金属制成，所述金属粘结层22的单金属层由所述第一类金属或所述第二类金属制成；比如，铜-镍合金制成的合金层以及锰制成的单金属层。
下面以上述的情况(4)对所述金属粘结层22的结构进行详细描述，请参阅图2所示，在本实施例中，所述金属粘结层22由第一类金属单层结构221和第二类金属单层结构222制成，其中，所述第一类金属单层结构221为由第一类金属制成并与所述载体层1连接的单金属层，所述第二类金属单层结构222为由第二类金属制成并与所述耐高温层21连接的单金属层。
在本发明实施例中，在所述第一类金属单层结构221和第二类金属单层结构222之间还可以设置由所述第一类金属的单层结构和/或所述第二类金属的单层结构制成的结构。通过在所述第一类金属单层结构221和第二类金属单层结构222之间设置由所述第一类金属的单层结构和/或所述第二类金属的单层结构制成的结构，以进一步提高所述阻隔层2与所述载体层1之间连接的牢靠性，从而进一步防止所述阻隔层2与所述载体层1之间发生剥离。
在本发明实施例中，所述剥离层3由镍、硅、钼、石墨、钛和铌中的任意一种或多种材料制成；或，所述剥离层3由有机高分子材料制成。其中，所述剥离层3的厚度优选为
Figure PCTCN2019116090-appb-000003
由于当所述剥离层3过厚时难以形成均匀的金属箔层4，从而容易导致金属箔层4上产生大量针孔(当金属箔层4上具有针孔时，在其蚀刻成线路后，将容易出现断路现象)；当所述剥离层3过薄时，容易导致其与金属箔层4之间难以剥离；因此通过将所述剥离层3的厚度优选为
Figure PCTCN2019116090-appb-000004
从而确保了能够形成均匀的金属箔层4，避免了在金属箔层4上产生大量针孔，同时使得所述剥离层3与所述金属箔层4之间易于剥离。
在本实施例中，所述金属箔层4的厚度小于或等于9μm。为满足线路板微细线路制作的要求，优选地，所述金属箔层4的厚度可为6μm、5μm、4μm或2μm等，从而得到有利于形成微细线路线路板的极薄金属箔层4。此外，为了能够从载体层1上剥离获得针孔少且完整地极薄金属箔层4(特别是厚度为2μm、4μm等的金属箔层)，在本实施例中，设置了金属粘结层22，从而利用金属粘结层22不仅使得阻隔层2与载体层1之间具有较强的剥离强度，有效确保了载体层1能够稳定地从金属箔层4上剥离下来，进而得到完整的极薄金属箔层4，而且还利用金属粘结层22对载体层1的表面进行了处理，以使得载体层1的整个表面更加均一、致密，从而有利于从载体层1上剥离获得针孔较少的极薄金属箔层4，进而有利于后续电路的制作。此外，所述金属箔层4优选为铜箔或铝箔；所述载体层1可以是载体铜、载体铝或有机薄膜等，由于载体层1主要起承载作用，因此需要一定的厚度，当所述载体层1为载体铜或载体铝时，所述载体层1的厚度优选为9-50μm；当所述载体层1为有机薄膜时，所述载体层1的厚度优选为20-100μm。
在本发明实施例中，所述载体层1靠近所述金属箔层4的一面的粗糙度Rz为小于或等于5μm；和/或，所述金属箔层4远离所述载体层1的一面的粗糙度Rz为小于或等于3.0μm。当 金属箔层4为铜箔时，铜箔的粗糙度越大，其与其它材料之间的粘结力越大，但是当铜箔的粗糙度过大，其将无法应用在高频信号传输用线路板中，因此一般的铜箔的粗糙度Rz为0.5-3.0μm；当铜箔在高频应用时，通过将铜箔的粗糙度设置为小于0.5μm，从而在确保铜箔与其它材料之间的粘结力的前提下，使得铜箔能够应用于高频信号传输用线路板。
在本发明实施例中，为了防止所述载体层1氧化，本实施例中的所述载体层1靠近所述阻隔层2的一侧上设有第一防氧化层；通过在所述载体层1靠近所述阻隔层2的一侧上设有第一防氧化层，以防止所述载体层1氧化，从而保护所述载体层1。为了防止所述金属箔层4氧化，所述金属箔层4远离所述阻隔层2的一侧上设有第二防氧化层，通过在所述金属箔层4远离所述阻隔层2的一侧上设有第二防氧化层，以防止所述金属箔层4氧化，从而保护所述金属箔层4。
请参阅图5所示，为了解决相同的技术问题，本发明实施例还提供一种用于制备所述复合金属箔的制备方法，包括以下步骤：
S11，形成载体层1；
S12，在所述载体层1的一侧上形成金属粘结层22；
S13，在所述金属粘结层22上形成耐高温层21，所述金属粘结层22和所述耐高温层21构成阻隔层2；
S14，在所述阻隔层2上形成剥离层3；
S15，在所述剥离层3上形成金属箔层4。
为了确保在使用所述复合金属箔时，能够方便地将所述载体层1、所述阻隔层2和所述剥离层3同时从所述金属箔层4上剥离，在本发明实施例中，在20-400℃温度下，所述载体层1与所述阻隔层2之间的剥离强度大于所述剥离层3与所述金属箔层4之间的剥离强度。优选地，在20-400℃温度下，所述载体层与所述阻隔层之间的百格测试等级为0或1或2，所述剥离层3与所述金属箔层4之间的剥离强度为0.001-2N/cm。
在本发明实施例中，第一类金属为易于与所述载体层1粘结的金属，第二类金属为易于与所述耐高温层21粘结的金属，优选地，所述第一类金属为铜或锌，所述第二类金属为镍或铁或锰。
由于采用电镀方式容易导致所述阻隔层2和所述剥离层3的粗糙度受到电镀时电流的影响，从而使得形成所述阻隔层2和所述剥离层3的表面粗糙度非常不均一，从而导致后续形成所述金属箔层4的表面粗糙度也不均一，继而不利于形成优良的剥离稳定性及针孔数量，同时也不利于后续电路的制作。基于此，在本发明实施例中，所述步骤S12、所述步骤S13和步骤S14优选采用溅射的方式，溅射方式的电流优选采用6-12A，电压优选采用300-500V。通过溅射形成的所述金属粘结层22和所述耐高温层21构成所述阻隔层2，以确保得到均匀致密的阻隔层2，并通过溅射形成均匀致密的剥离层3，从而有利于提高复合金属箔的剥离稳定 性并且能够有效地减少针孔的数量；此外，所述金属箔层4优选采用电镀的方式来形成，在形成所述金属箔层4之前，通过溅射形成均匀致密的阻隔层2和剥离层3，有利于所述金属箔层4均匀电镀，从而使得形成的所述金属箔层4的表面粗糙度比较均一，进而有利于后续电路的制作，并且有利于制作更薄的所述金属箔层4。
在本发明实施例中，在所述载体层1的一侧上形成金属粘结层22具体为：在所述载体层1的一侧上形成单金属层；其中，在所述载体层1的一侧上形成的单金属层由第一类金属或第二类金属制成。
在本发明实施例中，在所述载体层1的一侧上形成金属粘结层22具体还可以是：在所述载体层1的一侧上形成单层合金结构；其中，在所述载体层1的一侧上形成的单层合金结构由第一类金属和第二类金属制成。
在本发明实施例中，在所述载体层1的一侧上形成金属粘结层22具体还可以是：在所述载体层1的一侧上形成多层结构；其中，在所述载体层1的一侧上形成的多层结构包括由第一类金属制成并与所述载体层1连接的单金属层，在所述载体层1的一侧上形成的多层结构还包括由第二类金属制成并与所述耐高温层21连接的单金属层。
在本发明实施例中，在所述载体层1的一侧上形成金属粘结层22具体还可以是：在所述载体层的一侧上形成多层结构；其中，在所述载体层1的一侧上形成的多层结构包括合金层和单金属层，在所述载体层1的一侧上形成的多层结构的合金层由第一类金属和第二类金属制成，在所述载体层1的一侧上形成的多层结构的单金属层由第一类金属或第二类金属制成。
所述耐高温层21可以是有机耐高温层21；或，所述耐高温层21所述耐高温层为单层合金结构；或，所述耐高温层21为单材料层构成的多层结构或合金层和单材料层构成的多层结构，所述单材料层由同一种化学元素制成；其中，所述耐高温层21为有机耐高温层，或者，所述耐高温层21由钨、铬、锆、钛、镍、钼、钴和石墨中的任意一种或多种材料制成。
在本发明实施例中，所述形成载体层1后还包括以下步骤：
S111，将所述载体层1进行粗糙化，得到粗糙化后的载体层1；
S112，在粗糙化后的载体层1上形成第一防氧化层；
其中，所述载体层1可以是载体铜或载体铝。所述载体层1可以采用电镀来形成，形成所述载体层1的镀液可以包括硫酸铜溶液，其中，形成所述载体层1的镀液的铜含量为：15-25g/L，PH值为6-9；形成所述载体层1的镀液还包括添加剂，所述添加剂包括光亮剂磺酸钠、整平剂硫脲和润湿剂聚乙二醇，所述光亮剂磺酸钠的质量分数优选为0.1-2g/L，所述整平剂硫脲的质量分数优选为0.01-1g/L，所述润湿剂聚乙二醇的质量分数优选为0.1-5g/L。将所述载体层1进行粗糙化，可以通过酸性电镀的方式，其中，用于酸性镀铜的镀液可以包括硫酸铜溶液，用于酸性镀铜的镀液的铜含量为10-15g/L，酸含量为90-100g/L，钼含量为600-800PPM。其中，形成所述第一防氧化层可以采用镀锌镍合金的形式；此外，在粗糙化后 的载体层1上形成第一防氧化层后，还可以对所述第一防氧化层进行等离子清洗(plasma)，其中，进行等离子清洗时的电压优选采用1500-2500V，电流优选采用0.1-1.5A。
在本发明实施例中，为了进一步防止载体层1和金属箔层4之间发生粘结，本实施例中的所述形成载体层1后还包括：
S113，将所述载体层1以热处理条件进行退火处理；其中，所述热处理条件为：热处理温度为200-300℃，加热时间为30-300分钟。优选地，所述加热时间为1小时。通过将所述载体层1以热处理条件进行退火处理，以抑制加热工序中的载体层1的结晶生长，从而延迟加热工序中的载体层1的扩散，进而进一步防止载体层1和金属箔层4之间发生粘结。
在本发明实施例中，所述剥离层3可以由镍、硅、钼、石墨、钛和铌中的任意一种或多种材料制成。
在本发明实施例中，所述金属箔层4可以是铜箔或铝箔。所述金属箔层4可以采用电镀来形成，形成所述金属箔层4的镀液可以包括硫酸铜溶液，其中，形成所述金属箔层4的镀液的铜含量为：15-25g/L，PH值为6-9；形成所述金属箔层4的镀液包括添加剂，所述添加剂包括光亮剂磺酸钠、整平剂硫脲和润湿剂聚乙二醇，所述光亮剂磺酸钠的质量分数优选为0.1-2g/L，所述整平剂硫脲的质量分数优选为0.01-1g/L，所述润湿剂聚乙二醇的质量分数优选为0.1-5g/L。在本发明实施例中，为了避免复合金属箔翘曲，本实施例中将制备所述载体层1和所述金属箔层4的镀液设置为相同，以使得所述载体层1和所述金属箔层4的应力作用和拉力作用相同，从而使得所述载体层1和所述金属箔层4的弯折度相同，进而避免了复合金属箔翘曲。
在本发明实施例中，所述复合金属箔的制备方法还包括步骤：
S31，将所述金属箔层4远离所述载体层1的一面进行粗糙化处理。
S32，在粗糙化后的所述金属箔层4远离所述载体层1的一面上形成第二防氧化层。
其中，所述将所述金属箔层4远离所述载体层1的一面进行粗糙化处理，可以通过酸性电镀的方式，其中，用于酸性镀铜的镀液可以包括硫酸铜溶液，用于酸性镀铜的镀液的铜含量为10-15g/L，酸含量为90-100g/L，钼含量为600-800PPM；其中，形成所述第二防氧化层可以采用镀锌镍合金的形式；此外，在形成第二防氧化层后，还可以对所述第二防氧化层进行等离子清洗(plasma)，其中，进行等离子清洗时的电压优选采用1500-2500V，电流优选采用0.1-1.5A。
下述提供以下实施例用于说明复合金属箔的制备方法，具体如下：
实施例1
S41，采用电镀方式形成载体层1，再将所述载体层1进行粗糙化，然后在载体层1上形成第一防氧化层，并将所述载体层1以热处理条件进行退火处理；其中，所述热处理条件为：热处理温度为250℃，加热时间为1小时；所述载体层1为载体铜，形成所述载体层1的镀液 包括硫酸铜溶液，其中，形成所述载体层1的镀液的铜含量为：20g/L，PH值为7；形成所述载体层1的镀液还包括添加剂，所述添加剂包括光亮剂磺酸钠、整平剂硫脲和润湿剂聚乙二醇，所述光亮剂磺酸钠的质量分数为0.8g/L，所述整平剂硫脲的质量分数为0.5g/L，所述润湿剂聚乙二醇的质量分数为3g/L。此外，将所述载体层1进行粗糙化，可以通过酸性电镀的方式，其中，用于酸性镀铜的镀液包括硫酸铜溶液，用于酸性镀铜的镀液的铜含量为13g/L，酸含量为95g/L，钼含量为700PPM。其中，形成所述第一防氧化层采用镀锌镍合金的形式。
S42，通过溅射在所述载体层1的一侧上形成金属粘结层22；其中，所述金属粘结层22为铜金属层与镍金属层构成的结构，且铜金属层与所述载体层1连接，镍金属层与所述耐高温层21连接；
S43，通过溅射在所述金属粘结层22上形成耐高温层21，所述金属粘结层22和所述耐高温层21构成阻隔层2；其中，所述耐高温层21为钨-钛合金制成的单层合金结构；
S44，通过溅射在所述阻隔层2上形成剥离层3；其中，所述剥离层3为石墨层；
S45，采用电镀方式在所述剥离层3上形成金属箔层4；其中，所述金属箔层4为铜箔；形成所述金属箔层4采用的镀液与所述载体层1采用的镀液相同；
S46，将所述金属箔层4远离所述载体层1的一面进行粗糙化处理，并采用酸性电镀的方式在粗糙化后的所述金属箔层4远离所述载体层1的一面上形成第二防氧化层；其中，用于酸性镀铜的镀液包括硫酸铜溶液，用于酸性镀铜的镀液的铜含量为13g/L，酸含量为95g/L，钼含量为700PPM；其中，形成所述第二防氧化层可以采用镀锌镍合金的形式。
实施例2
本实施例与实施例1的区别在于，所述耐高温层21为钨-镍合金制成的单层合金结构。本实施例的其它工艺及步骤与实施例1相同，在此不做更多的赘述。
实施例3
本实施例与实施例1的区别在于，所述耐高温层21为钨-钼合金制成的单层合金结构。本实施例的其它工艺及步骤与实施例1相同，在此不做更多的赘述。
实施例4
本实施例与实施例1的区别在于，所述耐高温层21为铬-镍合金制成的单层合金结构。本实施例的其它工艺及步骤与实施例1相同，在此不做更多的赘述。
实施例5
本实施例与实施例1的区别在于，所述耐高温层21为锆-钛合金制成的单层合金结构。本实施例的其它工艺及步骤与实施例1相同，在此不做更多的赘述。
实施例6
本实施例与实施例1的区别在于，所述耐高温层21为钛-镍合金制成的单层合金结构。本实施例的其它工艺及步骤与实施例1相同，在此不做更多的赘述。
实施例7
本实施例与实施例1的区别在于，所述耐高温层21为钛-钼合金制成的单层合金结构。本实施例的其它工艺及步骤与实施例1相同，在此不做更多的赘述。
实施例8
本实施例与实施例1的区别在于，所述耐高温层21为钛-钴合金制成的单层合金结构。本实施例的其它工艺及步骤与实施例1相同，在此不做更多的赘述。
实施例9
本实施例与实施例1的区别在于，所述耐高温层21为镍-钼合金制成的单层合金结构。本实施例的其它工艺及步骤与实施例1相同，在此不做更多的赘述。
实施例10
本实施例与实施例1的区别在于，所述耐高温层21为钼-钴合金制成的单层合金结构。本实施例的其它工艺及步骤与实施例1相同，在此不做更多的赘述。
实施例11
本实施例与实施例1的区别在于，所述耐高温层21为钨金属层和石墨层制成的结构，且钨金属层与所述金属粘结层22连接，石墨层与所述剥离层3连接。本实施例的其它工艺及步骤与实施例1相同，在此不做更多的赘述。
实施例12
本实施例与实施例1的区别在于，所述耐高温层21为铬金属层和石墨层制成的结构，且铬金属层与所述金属粘结层22连接，石墨层与所述剥离层3连接。本实施例的其它工艺及步骤与实施例1相同，在此不做更多的赘述。
实施例13
本实施例与实施例1的区别在于，所述耐高温层21为镍金属层和石墨层制成的结构，且镍金属层与所述金属粘结层22连接，石墨层与所述剥离层3连接。本实施例的其它工艺及步骤与实施例1相同，在此不做更多的赘述。
实施例14
本实施例与实施例1的区别在于，所述耐高温层21为钨-镍合金和铬金属层制成的结构，且钨-镍合金与所述金属粘结层22连接，铬金属层与所述剥离层3连接。本实施例的其它工艺及步骤与实施例1相同，在此不做更多的赘述。
实施例15
本实施例与实施例1的区别在于，所述耐高温层21为镍-钼合金和铬金属层制成的结构，且镍-钼合金与所述金属粘结层22连接，铬金属层与所述剥离层3连接。本实施例的其它工艺及步骤与实施例1相同，在此不做更多的赘述。
实施例16
本实施例与实施例1的区别在于，所述耐高温层21为钼-钴合金和铬金属层制成的结构，且钼-钴合金与所述金属粘结层22连接，铬金属层与所述剥离层3连接。本实施例的其它工艺及步骤与实施例1相同，在此不做更多的赘述。
实施例17
本实施例与实施例1的区别在于，所述耐高温层21为钛-镍合金和铬金属层制成的结构，且钛-镍合金与所述金属粘结层22连接，铬金属层与所述剥离层3连接。本实施例的其它工艺及步骤与实施例1相同，在此不做更多的赘述。
实施例18
S41，采用电镀方式形成载体层1，再将所述载体层1进行粗糙化，然后在载体层1上形成第一防氧化层，并将所述载体层1以热处理条件进行退火处理；其中，所述热处理条件为：热处理温度为250℃，加热时间为1小时；所述载体层1为载体铜，形成所述载体层1的镀液包括硫酸铜溶液，其中，形成所述载体层1的镀液的铜含量为：20g/L，PH值为7；形成所述载体层1的镀液还包括添加剂，所述添加剂包括光亮剂磺酸钠、整平剂硫脲和润湿剂聚乙二醇，所述光亮剂磺酸钠的质量分数为0.8g/L，所述整平剂硫脲的质量分数为0.5g/L，所述润湿剂聚乙二醇的质量分数为3g/L。此外，将所述载体层1进行第一粗糙化处理，可以通过酸性电镀的方式，其中，用于酸性镀铜的镀液包括硫酸铜溶液，用于酸性镀铜的镀液的铜含量为13g/L，酸含量为95g/L，钼含量为700PPM。其中，形成所述第一防氧化层采用镀锌镍合金的形式。
S42，通过溅射在所述载体层1的一侧上形成金属粘结层22；其中，所述金属粘结层22为铜金属层与镍金属层构成的结构，且铜金属层与所述载体层1连接，镍金属层与所述耐高温层21连接，金属粘结层22的厚度为
Figure PCTCN2019116090-appb-000005
S43，通过溅射在所述金属粘结层22上形成耐高温层21，所述金属粘结层22和所述耐高温层21构成阻隔层2；其中，所述耐高温层21为钛金属层，耐高温层21的厚度为
Figure PCTCN2019116090-appb-000006
S44，通过溅射在所述阻隔层2上形成剥离层3；其中，所述剥离层3为石墨层，厚度为
Figure PCTCN2019116090-appb-000007
S45，采用电镀方式在所述剥离层3上形成金属箔层4；其中，所述金属箔层4为铜箔；形成所述金属箔层4采用的镀液与所述载体层1采用的镀液相同，厚度为4μm；
S46，将所述金属箔层4远离所述载体层1的一面进行第二粗糙化处理，并采用酸性电镀的方式在粗糙化后的所述金属箔层4远离所述载体层1的一面上形成第二防氧化层；其中，用于酸性镀铜的镀液包括硫酸铜溶液，用于酸性镀铜的镀液的铜含量为13g/L，酸含量为95g/L，钼含量为700PPM；其中，形成所述第二防氧化层可以采用镀锌镍合金的形式。
实施例19
本实施例与实施例18的区别在于，金属粘结层22为铜金属层。本实施例的其它工艺及步骤与实施例1相同，在此不做更多的赘述。
实施例20
本实施例与实施例18的区别在于，形成载体层1和金属箔层4的镀液组成相同，且镀液中铜含量为20g/L，PH值为7，添加剂包括光亮剂磺酸钠、整平剂硫脲和润湿剂聚乙二醇，光亮剂磺酸钠的质量分数为0.8g/L，整平剂硫脲的质量分数为0.5g/L，润湿剂聚乙二醇的质量分数为3g/L。
实施例21
本实施例与实施例18的区别在于，金属粘结层22、阻隔层2及剥离层3采用蒸发镀方式形成。
实施例22
本实施例与实施例18的区别在于，退火处理的温度为150℃，加热时间为120分钟。
实施例23
本实施例与实施例18的区别在于，不进行第一粗糙化处理和第二粗糙化处理。
对比例1
本实施例与实施例1的区别在于，在形成所述载体层1之后，不制作所述阻隔层2，而是直接在所述载体层1上形成剥离层3。本实施例的其它工艺及步骤与实施例1相同，在此不做更多的赘述。
对比例2
本实施例与实施例1的区别在于，在形成所述金属粘结层22之后，不制作所述耐高温层21，而是直接在所述金属粘结层22上形成剥离层3。本实施例的其它工艺及步骤与实施例1相同，在此不做更多的赘述。
对比例3
本实施例与实施例1的区别在于，在形成所述载体层1之后，不制作所述金属粘结层22，而是直接在所述载体层1上形成耐高温层21。本实施例的其它工艺及步骤与实施例1相同，在此不做更多的赘述。
表1是对实施例1-23所制备的复合金属箔直接在常温条件下(比如16-27℃，以25℃为例)进行多次测试，或者分别在不同温度下(200℃和340℃)与挠性绝缘基膜进行压合后，再在常温条件下进行多次测试的测试结果，测得的所述载体层1与所述阻隔层2之间的剥离强度以及所述剥离层3与所述金属箔层4之间的剥离强度。
表1
Figure PCTCN2019116090-appb-000008
Figure PCTCN2019116090-appb-000009
由于所述载体层1与所述金属箔层4在高温条件下会发生一定程度的相互扩散，从而导致所述载体层1与所述金属箔层4发生一定程度的粘结，因此，所述载体层1与所述阻隔层2之间的剥离强度以及所述剥离层3与所述金属箔层4之间的剥离强度随着温度的升高而升高，但是，由表1可以看出，在实施例1-17所制备的复合金属箔不管在常温或高温条件下，所述载体层1与所述阻隔层2之间的百格测试等级都在前三级，即所述载体层1与所述阻隔层2之间的附着力比较大，而所述剥离层3与所述金属箔层4之间的剥离强度非常小，因此使得所述载体层1与所述阻隔层2之间的剥离强度始终远远大于所述剥离层3与所述金属箔层4之间的剥离强度，因此，在使用所述复合金属箔时，能够方便地将所述载体层1、所述阻隔层2和所述剥离层3同时从所述金属箔层4上剥离。比较实施例18至23可知，金属箔的制备过程的工艺条件限定在本申请优选的范围内有利于提高金属箔的综合性能。而对比例1-3制备的复合金属箔在高温条件下发生的相互扩散情况比较严重，因此导致所述载体层1与所述金属箔层4发生较大程度的粘结，从而导致在使用所述复合金属箔时，不便于将所述载体层1、所述阻隔层2和所述剥离层3同时从所述金属箔层4上剥离。
综上，本发明实施例提供的一种复合金属箔及其制备方法，其中，复合金属箔包括依次层叠设置的载体层1、阻隔层2、剥离层3和金属箔层4，阻隔层2包括层叠设置的金属粘结层22和耐高温层21，金属粘结层22设于载体层1和耐高温层21之间，通过在载体层1和金属箔层4之间设置剥离层3，以便于剥离载体层1，并通过在载体层1和金属箔层4之间设置阻隔层2，以避免载体层1与金属箔层4在高温时相互扩散造成粘结，从而使得载体层1与金 属箔层4易于剥离；此外，通过在载体层1和耐高温层21之间设置金属粘结层22，以使得阻隔层2不易于与载体层1分离，从而防止阻隔层2与载体层1之间发生剥离。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和替换，这些改进和替换也应视为本发明的保护范围。

Claims (25)

  1. 一种复合金属箔，其特征在于，包括载体层、阻隔层、剥离层和金属箔层；
    所述载体层、所述阻隔层、所述剥离层和所述金属箔层依次层叠设置，所述阻隔层包括层叠设置的金属粘结层和耐高温层，所述金属粘结层设于所述载体层和所述耐高温层之间。
  2. 如权利要求1所述的复合金属箔，其特征在于，在20-400℃温度下，所述载体层与所述阻隔层之间的剥离强度大于所述剥离层与所述金属箔层之间的剥离强度。
  3. 如权利要求2所述的复合金属箔，其特征在于，所述载体层与所述阻隔层之间的百格测试等级为0或1或2，所述剥离层与所述金属箔层之间的剥离强度为0.001-2N/cm。
  4. 如权利要求1所述的复合金属箔，其特征在于，所述剥离层与所述金属箔层之间的剥离强度大于或等于所述剥离层与所述阻隔层之间的剥离强度。
  5. 如权利要求1所述的复合金属箔，其特征在于，所述耐高温层为有机耐高温层，或者，所述耐高温层由钨、铬、锆、钛、镍、钼、钴和石墨中的任意一种或多种材料制成。
  6. 如权利要求1所述的复合金属箔，其特征在于，所述耐高温层为单层合金结构；或，所述耐高温层为单材料层构成的多层结构或合金层和单材料层构成的多层结构，其中，所述单材料层由同一种化学元素制成。
  7. 如权利要求1所述的复合金属箔，其特征在于，所述金属粘结层由第一类金属中任意一种或多种材料制成；或者，所述金属粘结层由第二类金属中任意一种或多种材料制成；或者，所述金属粘结层由第一类金属中任意一种或多种材料和第二类金属中任意一种或多种材料制成；
    其中，所述第一类金属为易于与所述载体层粘结的金属，所述第二类金属为易于与所述耐高温层粘结的金属。
  8. 如权利要求7所述的复合金属箔，其特征在于，所述第一类金属为铜或锌，所述第二类金属为镍或铁或锰。
  9. 如权利要求7所述的复合金属箔，其特征在于，所述金属粘结层为所述第一类金属或所述第二类金属制成的单金属层。
  10. 如权利要求7所述的复合金属箔，其特征在于，所述金属粘结层为所述第一类金属和所述第二类金属制成的单层合金结构。
  11. 如权利要求7所述的复合金属箔，其特征在于，所述金属粘结层包括由第一类金属制成并与所述载体层连接的单金属层，所述金属粘结层还包括由第二类金属制成并与所述耐高温层连接的单金属层。
  12. 如权利要求7所述的复合金属箔，其特征在于，所述金属粘结层包括合金层和单金属层构成的多层结构；其中，所述金属粘结层的合金层由所述第一类金属和所述第二类金属制成，所述金属粘结层的单金属层由所述第一类金属或所述第二类金属制成。
  13. 如权利要求1-12任一项所述的复合金属箔，其特征在于，所述剥离层由镍、硅、钼、石墨、钛和铌中的任意一种或多种材料制成；或，所述剥离层由有机高分子材料制成。
  14. 如权利要求1-12任一项所述的复合金属箔，其特征在于，所述金属箔层的厚度小于或等于9μm。
  15. 如权利要求1-12任一项所述的复合金属箔，其特征在于，所述金属箔层为铜箔或铝箔；和/或，所述载体层为载体铜或载体铝或有机薄膜。
  16. 如权利要求1-12任一项所述的复合金属箔，其特征在于，所述载体层靠近所述金属箔层的一面的粗糙度Rz为小于或等于5μm；和/或，所述金属箔层远离所述载体层的一面的粗糙度Rz为小于或等于3.0μm。
  17. 如权利要求1-12任一项所述的复合金属箔，其特征在于，所述载体层靠近所述阻隔层的一侧上设有第一防氧化层；和/或，所述金属箔层远离所述阻隔层的一侧上设有第二防氧化层。
  18. 一种权利要求1至17中任一项所述的复合金属箔的制备方法，其特征在于，所述制备方法包括：
    S11，形成载体层(1)；
    S12，在所述载体层(1)的一侧上形成金属粘结层(22)；
    S13，在所述金属粘结层(22)上形成耐高温层(21)，所述金属粘结层(22)和所述耐高温层(21)构成阻隔层(2)；
    S14，在所述阻隔层(2)上形成剥离层(3)；
    S15，在所述剥离层(3)上形成金属箔层(4)。
  19. 根据权利要求18所述的制备方法，其特征在于，所述步骤S12、所述步骤S13和步骤S14均采用溅射的方式进行；
    优选地，所述步骤S12、所述步骤S13和步骤S14中溅射过程的电流分别独立地选自6～12A，电压分别独立地选自采用300～500V。
  20. 根据权利要求18或19所述的制备方法，其特征在于，在进行所述步骤S12之前，所述步骤S11还包括：
    S111，将所述载体层(1)进行第一粗糙化处理，得到粗糙化后的载体层(1)；
    S112，在粗糙化后的载体层(1)上形成第一防氧化层；
    优选地，所述载体层(1)为铜金属层或铝金属层。
  21. 根据权利要求18所述的制备方法，其特征在于，所述载体层(1)采用电镀的方式形成，其中形成所述载体层使用的第一镀液包括15～25g/L硫酸铜，0.1～2g/L磺酸钠，0.01～1g/L硫脲以及0.1～5g/L聚乙二醇，PH值为6～9。
  22. 根据权利要求20所述的制备方法，其特征在于，所述第一粗糙化处理过程采用第一电镀液进行酸性电镀的方式进行，其中所述第一电镀液包括铜离子含量为10～15g/L，酸含量为90～100g/L，钼离子含量为600～800PPM；
    优选地，采用镀锌镍合金的方式形成所述第一防氧化层。
  23. 根据权利要求18至22中任一项所述的制备方法，其特征在于，在形成所述金属粘结层(22)之前，所述制备方法还包括：
    S113，将所述载体层(1)进行退火处理；其中，所述退火处理过程的热处理温度为200～300℃，加热时间为30～300分钟；优选地，所述加热时间为1小时。
  24. 根据权利要求22所述的制备方法，其特征在于，所述制备方法还包括采用电镀法形成所述金属箔层(4)；
    优选地，形成所述金属箔层(4)的过程中采用的第二电镀液与所述第一电镀液的组成相同。
  25. 根据权利要求24所述的制备方法，其特征在于，所述制备方法还包括：
    S31，将所述金属箔层(4)远离所述载体层(1)的一面进行第二粗糙化处理；
    S32，在粗糙化后的所述金属箔层(4)远离所述载体层(1)的一面上形成第二防氧化层；
    优选地，所述第一粗糙化处理步骤采用第二酸性镀液进行酸性电镀的方式进行，其中，所述第二酸性镀液中，铜离子含量为10～15g/L，酸含量为90～100g/L及钼离子含量为600～800PPM；
    优选地，采用镀锌镍合金的方式形成所述第二防氧化层。
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