CN103085384A - A metal exterior material having a resin film and a method for manufacturing the same - Google Patents
A metal exterior material having a resin film and a method for manufacturing the same Download PDFInfo
- Publication number
- CN103085384A CN103085384A CN2012104396297A CN201210439629A CN103085384A CN 103085384 A CN103085384 A CN 103085384A CN 2012104396297 A CN2012104396297 A CN 2012104396297A CN 201210439629 A CN201210439629 A CN 201210439629A CN 103085384 A CN103085384 A CN 103085384A
- Authority
- CN
- China
- Prior art keywords
- metal
- tunicle
- resin molding
- zinc
- matrix material
- 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.)
- Granted
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 138
- 239000011347 resin Substances 0.000 title claims abstract description 138
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 123
- 239000002184 metal Substances 0.000 title claims abstract description 119
- 239000000463 material Substances 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 66
- 238000004519 manufacturing process Methods 0.000 title claims description 27
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 100
- 239000011701 zinc Substances 0.000 claims abstract description 100
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 98
- 239000000758 substrate Substances 0.000 claims abstract description 83
- 238000007747 plating Methods 0.000 claims abstract description 80
- 238000012545 processing Methods 0.000 claims abstract description 69
- 238000006073 displacement reaction Methods 0.000 claims abstract description 52
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- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 8
- 239000010935 stainless steel Substances 0.000 claims abstract description 7
- 238000000465 moulding Methods 0.000 claims description 91
- 239000011159 matrix material Substances 0.000 claims description 90
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 39
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 32
- 238000000576 coating method Methods 0.000 claims description 30
- 239000011248 coating agent Substances 0.000 claims description 29
- 230000015572 biosynthetic process Effects 0.000 claims description 22
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- 229910045601 alloy Inorganic materials 0.000 claims description 14
- 239000000956 alloy Substances 0.000 claims description 14
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- 229910017052 cobalt Inorganic materials 0.000 claims description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 13
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- 230000008569 process Effects 0.000 abstract description 12
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- -1 polyethylene Polymers 0.000 description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 32
- 238000001035 drying Methods 0.000 description 29
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 26
- 206010013786 Dry skin Diseases 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 239000007788 liquid Substances 0.000 description 23
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 20
- 229910000368 zinc sulfate Inorganic materials 0.000 description 18
- 229960001763 zinc sulfate Drugs 0.000 description 18
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 16
- 239000003792 electrolyte Substances 0.000 description 16
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- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 12
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- 235000011121 sodium hydroxide Nutrition 0.000 description 12
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- UPMFZISCCZSDND-JJKGCWMISA-M sodium gluconate Chemical class [Na+].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O UPMFZISCCZSDND-JJKGCWMISA-M 0.000 description 6
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 6
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- XWROUVVQGRRRMF-UHFFFAOYSA-N F.O[N+]([O-])=O Chemical compound F.O[N+]([O-])=O XWROUVVQGRRRMF-UHFFFAOYSA-N 0.000 description 3
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 description 3
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
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- 239000011787 zinc oxide Substances 0.000 description 3
- 238000000864 Auger spectrum Methods 0.000 description 2
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 241000209140 Triticum Species 0.000 description 2
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- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 description 2
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Images
Classifications
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- 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
- B32B15/085—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 polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D22/00—Shaping without cutting, by stamping, spinning, or deep-drawing
- B21D22/20—Deep-drawing
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/18—Layered products comprising a layer of metal comprising iron or steel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/12—Deep-drawing
-
- 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
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2311/00—Metals, their alloys or their compounds
- B32B2311/22—Nickel or cobalt
-
- 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
- B32B2311/00—Metals, their alloys or their compounds
- B32B2311/30—Iron, e.g. steel
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
Abstract
The invention provides a metal exterior material having a resin film. According to the metal exterior material, even when the resin film is laminated or a resin coated film is formed on a base material such as aluminum or stainless steel, and then is put into strict forming such as deep drawing processing, thinning processing or tensile processing, high sealing property that prevents the laminated film or the resin coated film from peeling is given to the material, and even if the material is in long-term contact with acid or resolution, the material can have excellent resistance to chemical reagent for keeping the high seal property. The solve the problem, the metal exterior material having a resin film has base material metal (1), a substrate covering film (2) disposed on one face or two faces of the base material metal (1), and the laminated film or resin coated film (3) disposed on the substrate covering film (2), wherein the substrate covering film (2) is a covering film is a metallic zinc covering film or a metallic zinc-contained covering film. The metallic zinc covering film or the metallic zinc-contained covering film is preferably formed by using a displacement plating method or an electroplating process.
Description
Technical field
The present invention relates to metal-made exterior material and manufacture method thereof with resin molding.Specifically, even relate in the situation that contact metal-made exterior material and the manufacture method thereof with resin molding of the adaptation that also can keep matrix material metal and laminated film or resin coating film with electrolyte.
More particularly, relate to a kind of metal-made exterior material with resin molding etc., even at matrix material metal overlayer pressurizing resin film or formation resin coating films such as aluminium or stainless steels, in the situation that carry out thereafter the harsh shaping processing such as deep-draw processing, attenuate processing or stretch-draw (stretch draw) processing, also can give the high adaptation that this laminated film or resin coating film are peeled off, even and contact for a long time with acid or solvent etc., also have the resistance to chemical reagents of the excellence that can keep high adaptation.
Background technology
Lamination process be with resinous film (below; being called resin molding or laminated film) heating is pressed together on the processing method of metal material surface; be to protect the surface or give one of the method for coating that design is the metal material surface of purpose, can be used for various fields.With the surface that resin combination is coated in metal material and dry and method that form resin coating film is compared, the generation of the waste gas such as the solvent that lamination process produces when drying or carbon dioxide or greenhouse gases is few.Therefore; consider from the viewpoint of environmental protection; the preferred lamination process of using, its purposes enlarges, and has been used to such as main body or cover material, containers for food use or the dry cell container etc. of the food take aluminium sheet material, steel sheet material, Packaging Aluminum Foil or stainless steel foil etc. as raw material with tank.
Particularly nearest, exterior material as the portable lithium rechargeable battery that uses in mobile phone, electronic notebook, notebook computer or video camera etc., the metallic plates such as the preferred aluminium sheet that service property (quality) is light and barrier is high or corrosion resistant plate have used lamination process to the surface of such metallic plate.In addition, studying the lithium rechargeable battery as the drive energy of electric automobile or hybrid vehicle, and as its exterior material, also the metallic plate through lamination process is being studied.
Direct and metal material applying, then add hot pressing for the laminated film of such lamination process.Therefore, compare with application of resin composition and the dry common resin coating film that forms, have can suppress raw-material waste, pin hole (defective part) reaches the advantages such as excellent in workability less.As the material of laminated film, usually use the polyamide-based resins such as the polyolefin such as the polyester resins such as PETG and PEN, polyethylene and polypropylene, nylon.
When the laminated film lamination process is upper on the surface of metal material (following also referred to as " metal surface "), in order to improve adaptation between laminated film and metal surface and the corrosion resistance of metal surface, cleaning by degreasing to be carried out in the metal surface, then usually implement chemical conversion processing such as chromium phosphate hydrochlorate etc.But such chemical conversion is processed need to implement matting after processing, to remove remaining treatment fluid, carries out wastewater treatment for the rinse water of being discharged by this matting and wants Expenses Cost.Especially chemical conversion processing such as chromium phosphate hydrochlorate etc. owing to having used chromyl treatment fluid, therefore, in recent years for the worry to environment, has the trend of avoidance.
On the other hand, if the metal surface is not implemented the processing such as chemical conversion processing when carrying out lamination process, exist laminated film to peel off from the metal surface or the problem of the easy corrosion of metal material.For example, for exterior material of lithium rechargeable battery etc., will the high processing of degree of being subject to processing in its manufacturing process.It is lithium complex that the electrolyte of lithium rechargeable battery uses the organic solvent such as ethyl carbonate or diethyl carbonate and the fluorine such as lithium hexafluoro phosphate or LiBF4.Therefore, if use for a long time such exterior material, be not only as electrolytical organic solvent, moisture in atmosphere also can immerse in container, itself and electrolyte react and generation hydrofluoric acid, thereby can produce following problem: this hydrofluoric acid sees through laminated film and metal surface and laminated film is peeled off, and can erode metallic surfaces.In addition, before lamination, metal material is preheated (200 ~ 300 ℃) sometimes, thereby can have tunicle deteriorated problem that adaptation is reduced under the effect of heat.
packaging material as the packing lithium secondary battery, the various laminated body that organic solvent or hydrofluoric acid had tolerance have been proposed, for example, in patent documentation 1, a kind of laminated body has been proposed, it is by outermost layer/barrier layer/innermost layer, perhaps consisted of by outermost layer/barrier layer/intermediate layer/innermost layer, wherein, innermost layer face side surface to described barrier layer carries out degreasing, perhaps remove oxide on surface, and implemented phosphate coating, by chromate, fluorides compound or organo-silicon compound, the organic titanium compounds, the formation of the acid resistance tunicle that the organo-aluminium compounds consists of and/or by silanes, the organic titanium class, the coupling processing that the material of organo-aluminium class forms etc.According to this technology, the formation of following laminated body can be provided, namely, as the stack membrane that uses in the shell of taking in polymer battery, its barrier to steam and other gas is excellent, in addition, excellent aspect the layers cementing intensity of anti-content physical property and laminated body, and have the mechanical strength take endurable permeability etc. as representative, at high temperature also can use in addition, also very stable to electrolyte.
In addition, in patent documentation 2, following lithium ion battery packaging material have been proposed, its one side at sealant has stacked gradually adhering resin layer, the first chemical conversion processing layer, aluminium foil layer, the second chemical conversion processing layer, bond layer and base material layer at least, wherein, aluminium foil layer has carried out etched aluminium foil by the two sides and has formed, and the first chemical conversion processing layer and the second chemical conversion processing layer are formed by the zinc oxide tunicle.According to this technology, a kind of lithium ion battery packaging material of high productivity can be provided, this lithium ion battery need not use the chromium that might cause environmental pressure with packaging material, can obtain excellent electrolyte resistance, hydrofluoric acid resistance, and can form easily the chemical conversion processing layer on the two sides of aluminium foil.
In addition; in patent documentation 3; following technology has been proposed; it relates to the stacked plastic layer press mold that forms that closes of plastics basement membrane, metal forming and functional plastic; wherein; metal forming at least towards the one side of functional plastic layer, functional plastic layer towards the one side of metal forming and the inside of functional plastic layer, perhaps wherein any, utilize physical vaporous deposition to form at least 1 layer of metal-made protective layer as the chromium layer.According to this technology, can improve the adaptation of each interlayer, preferably conduct is used as the plastic layer press mold of the covering of lithium ion polymer battery or lithium polymer battery.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2001-35453 communique
Patent documentation 2: TOHKEMY 2011-76887 communique
Patent documentation 3: Japanese Unexamined Patent Application Publication 2009-544492 communique
Summary of the invention
The problem that invention will solve
But the technology that proposes in patent documentation 1 ~ 3 is all for the laminated film of packing lithium secondary battery, is not subject to the high processing of degree of finish as previously described.Therefore, use for a long time afterwards in the situation that this laminated film is carried out the high processing of degree of finish, and do not know whether still have high electrolyte resistance.
the object of the invention is to, a kind of metal-made exterior material and manufacture method thereof with resin molding is provided, described metal-made exterior material with resin molding is at the matrix material metal overlayer pressurizing resin film such as aluminium or stainless steel or form resin coating film (following also referred to as " resin molding "), then carry out deep-draw processing, in the situation of the shaping processing that attenuate processing or stretch-draw processing etc. are harsh, also can give the high adaptation that this laminated film or resin coating film are peeled off, in addition, even contact for a long time with acid or solvent etc., the resistance to chemical reagents that also has the excellence that can keep high adaptation.
The method of dealing with problems
The metal-made exterior material with resin molding of the present invention that is used for addressing the above problem is characterised in that, it has: the matrix material metal, be located at this matrix material metal one or both sides the substrate tunicle and be located at laminated film or resin coating film on this substrate tunicle, wherein, described substrate tunicle is metallic zinc tunicle or the tunicle that contains metallic zinc.
According to this invention, by the tunicle that the metallic zinc tunicle is set or contains metallic zinc as the substrate tunicle between matrix material metal and resin molding, can obtain following result: demonstrate the high adaptation that laminated film or resin coating film are peeled off, even and contact also for a long time with acid or solvent etc. and can keep high adaptation.
In metal-made exterior material with resin molding of the present invention, preferred described laminated film or resin coating film contain polyolefin or acid modified polyolefin.
In metal-made exterior material with resin molding of the present invention, preferred described matrix material metal is to be selected from any in aluminium or its alloy, stainless steel, copper or its alloy and nickel or its alloy.
In metal-made exterior material with resin molding of the present invention, the described tunicle that contains metallic zinc can consist of in the mode that comprises the one kind or two or more element in chosen from Fe, nickel and cobalt.
According to this invention, comprise the tunicle that contains metallic zinc of the one kind or two or more element in chosen from Fe, nickel and cobalt as the substrate tunicle by setting, for example in the situation that utilization displacement plating forms the replacement amount that the substrate tunicle can reduce the matrix material metal, can improve in addition the mechanical strength of this substrate tunicle.
Metal-made exterior material with resin molding of the present invention can be implemented deep-draw processing, attenuate processing or stretch-draw processing and consist of.
According to this invention, even in the situation that the metal-made exterior material that arranges after resin molding has been implemented the harsh shapings processing such as deep-draw processing, attenuate processing or stretch-draw processing, do not make the high adaptation that resin molding peels off and contact the resistance to chemical reagents that yet can keep high adaptation for a long time with acid or solvent etc. even can possess yet.
The manufacture method of the metal-made exterior material with resin molding of the present invention that is used for addressing the above problem is characterised in that, it has: utilize displacement plating method or galvanoplastic form as the metallic zinc tunicle of substrate tunicle on the one or both sides of matrix material metal or contain the operation of the tunicle of metallic zinc; And the operation that forms laminated film or resin coating film on described substrate tunicle.
According to this invention, replacing plating method or galvanoplastic by utilization forms as the metallic zinc tunicle of substrate tunicle on the one or both sides of matrix material metal or contains the tunicle of metallic zinc, then form laminated film or resin coating film on the substrate tunicle, can obtain following result: the metal-made exterior material with resin molding of manufacturing demonstrates the high adaptation that laminated film or resin coating film are peeled off, even and contact also for a long time with acid or solvent etc. and can keep high adaptation.
The manufacture method of the metal-made exterior material with resin molding of the present invention can have following formation: further have any manufacturing procedure more than 1 or 2 that is selected from deep-draw processing, attenuate processing and stretch-draw processing.
The manufacture method of the metal-made exterior material with resin molding of the present invention can have following formation: before the formation operation of described substrate tunicle, further have to remove the operation of the oxide tunicle of described matrix material metal surface.
According to this invention, therefore the operation due to the oxide tunicle that also had to remove the matrix material metal surface before the formation operation of substrate tunicle can further improve the adaptation between matrix material metal and substrate tunicle.
The effect of invention
According to metal-made exterior material and the manufacture method thereof with resin molding of the present invention, by the tunicle that the metallic zinc tunicle is set or contains metallic zinc as the substrate tunicle between matrix material metal and resin molding, can obtain following result: demonstrate the high adaptation that laminated film or resin coating film are peeled off, even and contact also for a long time with acid or solvent etc. and can keep high adaptation.Even in the situation that the metal-made exterior material with resin molding that possesses above-mentioned effect is implemented the harsh shaping processing such as deep-draw processing, attenuate processing and stretch-draw processing, also can obtain following effect: can give the high adaptation that this laminated film or resin coating film are peeled off, even and contact for a long time with acid or solvent etc., also can have the resistance to chemical reagents of the excellence that keeps high adaptation.
Description of drawings
[Fig. 1] is the mode sectional drawing that an example of the metal-made exterior material with resin molding of the present invention is shown.
Symbol description
1 matrix material metal
2 substrate tunicles (metallic zinc tunicle or contain the tunicle of metallic zinc)
3 resin moldings (laminated film or resin coating film)
The 10 metal-made exterior materials with resin molding
The specific embodiment
Below, metal-made exterior material and the manufacture method thereof with resin molding of the present invention described.Need to prove, technical scope of the present invention is not limited by the mode of the following description and accompanying drawing.
[with the metal-made exterior material of resin molding]
As shown in Figure 1, metal-made exterior material 10 with resin molding of the present invention has: matrix material metal 1, be located at this matrix material metal 1 one or both sides substrate tunicle 2 and be located at laminated film on this substrate tunicle 2 or resin coating film (below, as long as no particularly pointing out, refer to " resin molding 3 ").In addition, it is characterized in that, this substrate tunicle 2 is metallic zinc tunicle or the tunicle that contains metallic zinc.Need to prove, in Fig. 1, although in the one side of matrix material metal 1, substrate tunicle 2 and resin molding 3 are set, also substrate tunicle 2 and resin molding 3 can be set on the two sides of matrix material metal 1.
Below, formation of the present invention is elaborated.
(matrix material metal)
Matrix material metal 1 is light sheet material or the paper tinsel of metal that becomes the matrix material (base) of the metal-made exterior material 10 with resin molding of the present invention.As the material of matrix material metal 1, can enumerate any metal that is selected from aluminium or its alloy, stainless steel, copper or its alloy and nickel or its alloy.Above-mentioned matrix material metal 1 can be both commercially available product, can be also that sheet material with given thickness carries out hot rolling or cold rolling and material that obtain.The thickness of matrix material metal 1 is not particularly limited, and is for example about 0.01mm ~ 2.0mm.And, in the situation that utilize displacement plating described later that substrate tunicle 2 is set, because matrix material metal 1 is subject to etching, therefore to consider that this etch quantity comes design thickness.
In addition, also other metal or alloy can be set on these metal or alloy.As other the formation method of metal or alloy, can enumerate plating (electroplate, electroless plating apply) method, evaporation coating method, clad method etc.As an example, can enumerate nickel-clad copper that has carried out electronickelling and obtain on copper or copper alloy etc.
(substrate tunicle)
The metallic zinc tunicle is the layer that only is made of metallic zinc, and the tunicle that contains metallic zinc is by film formed layer by the metal that comprises metallic zinc.So-called " comprising " refers to comprise zinc metallic element in addition, as such metallic element, can enumerate the one kind or two or more iron group metal in chosen from Fe, nickel and cobalt.The tunicle that contains metallic zinc that comprises these iron group metals has following advantage: can improve the mechanical strengths such as hardness and can suppress the etch quantity of matrix material metal 1 when displacement plating described later.The content that contains the iron group metal in the tunicle of metallic zinc is preferably the scope of 0.5 quality % ~ 15 quality %.The tunicle that contains metallic zinc that comprises the iron family element of above-mentioned scope has advantages of as follows: consider from the viewpoint of the etch quantity that can suppress matrix material metal 1, even excessively do not thicken the thickness of substrate tunicle 2, also can form fully the substrate tunicle with electrolyte resistance driving fit retentivity.Need to prove, the metallic zinc tunicle of this moment is all metallic zinc except inevitable impurity component (comprising micro-oxide components).
Can utilize displacement plating method or galvanoplastic to form as the metallic zinc tunicle of substrate tunicle 2 or the tunicle that contains metallic zinc.
The displacement plating method is the size according to the oxidation-reduction potential of zinc ion contained in the oxidation-reduction potential of the matrix material metal 1 that contacts with the displacement plating solution and plating solution, the redox reaction that the reduction that utilizes chemical reaction that the oxidation dissolution of matrix material metal 1 and zinc ion occur is simultaneously separated out utilizes the separating out of the simultaneous zinc of dissolving (also referred to as etching) with matrix material metal 1 to form substrate tunicle 2.Therefore, the displacement plating method depends on the size of the oxidation-reduction potential of the matrix material metal 1 of replacing in plating solution and the metal ion that can separate out, to be applicable to the method that redox environment has obtained the situation of adjustment, in described redox environment, matrix material metal 1 residual electronics occurs and the chemical reaction of oxidation dissolution and the metal ion that occurs in liquid are accepted this electronics and the chemical reaction of separating out that reduces.In addition, the one kind or two or more situation that contains in plating solution in chosen from Fe, nickel and cobalt is also identical, depends on the size of matrix material metal 1 and the oxidation-reduction potential of the metal ion that can separate out, and it is included in or is not included in substrate tunicle 2.Such displacement plating method can form the substrate tunicle 2 of uniform thickness due to the shape regardless of matrix material metal 1, and is therefore very convenient, compares in addition firmlyer with the substrate tunicle 2 that utilizes galvanoplastic to form, and the mechanical strengths such as hot strength are excellent.
Adopt the formation of substrate tunicle 2 of displacement plating method by making matrix material metal 1 contact to carry out with alkaline or acid displacement plating solution.Which kind of for using alkalescence or acid displacement plating solution, can suitably select according to whether replacing plating with the size of the oxidation-reduction potential of metal ion because of the matrix material metal 1 in the displacement plating solution.The method of " contact " can enumerate matrix material metal 1 in displacement the dipping in plating solution, to matrix material metal 1 spray injection displacement plating solution etc.
The displacement plating solution is not particularly limited, can enumerate the alkalescence displacement plating solution that uses in embodiment described later for example (being called the zincic acid salt bath, take zinc sulfate and NaOH as principal component), acid displacement plating solution (take zinc sulfate and acid ammonium fluoride or hydrofluoric acid as principal component) etc.And, in these displacement plating solutions, also can contain as required the additives such as polishing material, complexant, reducing agent, pH adjusting agent, buffer, for example can enumerate gluconic acid sodium salt, other additive.In addition, in the situation that the one kind or two or more metal in also containing chosen from Fe, nickel and cobalt in substrate tunicle 2, at random coordinating example such as ferrous sulfate, nickelous sulfate, cobaltous sulfate etc. in the displacement plating solution.
Need to prove, each above-mentioned salt is illustration, as long as can form as the metallic zinc tunicle of target or contain the tunicle of metallic zinc at the one or both sides of matrix material metal 1, also can use the zinc salt beyond above-mentioned, various slaines etc.In addition, the liquid composition of displacement plating solution also is not particularly limited.For example in the situation that the zincic acid salt bath is generally zinc sulfate 8 ~ 16g/L, NaOH 90 ~ 150g/L.
Galvanoplastic are methods of on matrix material metal 1, the metal ion authoritative restore in electroplate liquid being separated out applying electric current between the matrix material metal 1 that contacts with electroplate liquid and the opposite electrode that similarly contacts with electroplate liquid (also referred to as to electrode).
Adopt the formation of the substrate tunicle 2 of galvanoplastic to be undertaken by apply curtage under the state that makes zinc electroplate liquid contact matrix material metal 1 and opposite electrode.As opposite electrode, can use zine plate or insoluble electrode (such as carbon electrode, coat the titanium electrode of platinum etc.).In addition, in the situation that form with the electroplate liquid that contains the metal ingredient beyond the zinc composition tunicle that contains metallic zinc, also can use comprise with the tunicle that contains metallic zinc in the opposite electrode of ratio of metal ingredient same amount beyond contained zinc.So, can supply with the amount corresponding with the reduction of metal ingredient electroplate liquid from opposite electrode.Such galvanoplastic are different from the displacement plating method, without chemical reaction, therefore can only easily form the substrate tunicle 2 of required thickness by controlling curtage.In addition, because to compare speed of separating out fast with the displacement plating method, therefore can realize formation at a high speed.
The zinc electroplate liquid is not particularly limited, and for example can enumerate the zinc sulfate plating solution that uses in embodiment described later.Need to prove, in electroplate liquid, also can add as required the additives such as polishing material, complexant, pH adjusting agent, buffer.In addition, in the situation that the one kind or two or more metal in also containing chosen from Fe, nickel and cobalt in substrate tunicle 2, at random coordinating example such as ferrous sulfate, nickelous sulfate, cobaltous sulfate etc. in electroplate liquid.
Utilize the thickness of the substrate tunicle 2 that above-mentioned each method forms to be generally 0.01 μ m ~ 0.70 μ m and (be equivalent to approximately 0.10g/m in total adhesion amount
2~ about 5.0g/m
2), be preferably 0.03 μ m ~ 0.28 μ m and (be equivalent to approximately 0.2g/m in total adhesion amount
2~ about 2.0g/m
2).If the thickness of substrate tunicle 2 less than 0.01 μ m, can't obtain enough electrolyte resistance driving fit retentivities sometimes.On the other hand, if the thickness of substrate tunicle 2 surpasses 0.70 μ m, although electrolyte resistance driving fit retentivity is excellent, the film forming meeting spended time of substrate tunicle 2, thus have the poor situation of productivity.Need to prove total adhesion amount 1g/m of substrate tunicle 2
2The thickness that is equivalent to substrate tunicle 2 is 0.14 μ m approximately.
and, although in the situation that the tunicle that the metallic zinc tunicle is set or contains metallic zinc can keep the reason of electrolyte resistance adaptation to it be unclear that now as substrate tunicle 2, but roughly can think it to be due to following reason: in the situation that the metal-made exterior material 10 with resin molding of the present invention be impregnated in LiPF6 etc. as in electrolyte solution, can confirm the P elements that concentrates between substrate tunicle 2 and resin molding 3, therefore when dipping the zinc composition in substrate tunicle 2 under as the effect of the hydrofluoric acid of the hydrolysate of LiPF6 and stripping, this zinc composition with similarly generate insoluble salt as the phosphorus compound reaction of the hydrolysate of LiPF6, so such insoluble salt just becomes the essential factor that keeps the electrolyte resistance adaptation.
(resin molding)
The form setting of the resin coating film that resin molding 3 forms with the form of the laminated film that forms at laminated resin made membrane on substrate tunicle 2 or with coating resin on substrate tunicle 2.Resin molding 3 is by polyolefin, acid modified polyolefin or form as the resin combination that principal component comprises with them.Even such resin molding 3 can prevent also that matrix material metal 1 is corroded or etch and arranging in order to contact for a long time with acid or solvent etc.
As polyolefin, can enumerate the polyethylene such as high density polyethylene (HDPE), low density polyethylene (LDPE); The copolymer of ethene and alpha-olefin; With homopolymers, random copolymer or the block copolymer polypropylene as raw material; The copolymers of propylene and alpha-olefin etc. can use to be selected from one kind or two or more in the middle of them.Acid modified polyolefin can obtain by polyolefin is carried out graft modification with maleic anhydride etc.
For the lamination process that is used for arranging laminated film, can enumerate lamination methods, dry lamination method, extruding layer platen press or co-extrusion laminating method etc.
The formation of the resin molding 3 of employing lamination methods is undertaken by the surface heat crimping resin molding 3 of basad tunicle 2.Temperature and pressure when carrying out thermo-compressed etc. can be according to the character Set arbitrarily of resin molding 3.And, also bond layer can be set as required on the surface of resin molding 3, this bond layer is utilized as the thermo-compressed layer.As such bond layer, can enumerate the layer that is formed by resin combinations such as epoxy resin, phenolic resins, acrylic resin, polyurethane resins, can arrange by being coated with such resin and drying etc.
Adopt the formation of the resin molding 3 of dry lamination method form bond layer by the surface at substrate tunicle 2 and carry out at the surperficial normal temperature crimping resin molding 3 of this bond layer.As bond layer, can enumerate the resin combinations such as polyesters bonding agent, polyethylene kind bonding agent, polyethers bonding agent, cyanoacrylate bonding agent, polyurethanes bonding agent, organic titanium class bonding agent, polyether-polyurethane class bonding agent, epoxies bonding agent, polyester-polyurethane class bonding agent, isocyanates bonding agent, TPO bonding agent, bond layer can be coated on above-mentioned resin combination the surface of substrate tunicle 2 and carry out drying and form.
The formation of the resin molding 3 of employing extruding layer platen press or co-extrusion laminating method can be by directly extruding the resin after melting cooling carrying out after the surface of substrate tunicle 2.Extruding and when cooling, for example can use the flat-die method or melt extrude the equipment of forming process at resin.
(with the metal-made exterior material of resin molding)
For such formation with for the metal-made exterior material 10 of resin molding, be implemented as required thereafter deep-draw processing, attenuate processing or stretch-draw processing, be configured as given shape and be used for various uses.For example, the exterior material as the portable lithium rechargeable battery that uses in mobile phone, electronic notebook, notebook computer or video camera etc. uses.In addition, the framework that also can be used as the such pocket machine of smart mobile phone or panel computer is used.In addition, the exterior material of the lithium rechargeable battery of all right driving energy as being used as electric automobile or hybrid vehicle uses.
As mentioned above, according to the metal-made exterior material 10 with resin molding of the present invention,, do not make the high adaptation that resin molding 3 peels off and contact the result that yet can keep high adaptation for a long time with acid or solvent etc. even can obtain demonstrating as the substrate tunicle 2 between matrix material metal 1 and resin molding 3 by the tunicle that the metallic zinc tunicle is set or contains metallic zinc.Even in the situation that the metal-made exterior material 10 with resin molding that possesses such effect is implemented the harsh shaping processing such as deep-draw processing, attenuate processing or stretch-draw processing, also can obtain following effect: can give the high adaptation that this resin molding 3 is peeled off, even and contact for a long time with acid or solvent etc., also have the resistance to chemical reagents of the excellence that can keep high adaptation.
[with the manufacture method of the metal-made exterior material of resin molding]
The manufacture method of the metal-made exterior material 10 with resin molding of the present invention has: utilize displacement plating method or galvanoplastic to form at the one or both sides of matrix material metal 1 resin molding that forms operation and form laminated film or resin coating film on this substrate tunicle 2 as the metallic zinc tunicle of substrate tunicle 2 or the substrate tunicle that contains the tunicle of metallic zinc and form operation.Need to prove, so-called " having " refers to, also can have the substrate tunicle and form operation and resin molding formation operation operation in addition.For example, also can have any 1 or 2 above operations that pretreatment procedure described later, manufacturing procedure and oxide tunicle are removed operation etc.
As shown in the explanation in the explanation hurdle of above-mentioned " with the metal-made exterior material of resin molding ", the descriptions thereof are omitted following for the preparation of matrix material metal 1 or the manufacturing procedures such as formation operation, deep-draw processing that form formation operation, the resin molding 3 of operation, substrate tunicle 2 for the details of each operation.In this manufacture method, the operation of the oxide tunicle that is used for removing matrix material metal 1 surface can be set further before forming substrate tunicle 2 also.Removing such as utilizing of oxide tunicle used the common acid of the acid such as sulfuric acid, nitric acid, hydrochloric acid, nitric acid hydrofluoric acid to clean to carry out.As sour cleaning method, can enumerate impregnated cleaning or injecting type cleaning etc.In addition, also can carry out as required ungrease treatment as common pre-treatment.Need to prove, water cleans and usually is disposed between each operation.
For for the metal-made exterior material 10 of resin molding, process in the manufacturing procedures such as deep-draw processing, attenuate processing or stretch-draw processing as required thereafter.Utilize such manufacturing procedure, be configured as given shape and be used for various uses.
above, manufacture method according to the metal-made exterior material 10 with resin molding of the present invention, utilize displacement plating method or galvanoplastic form as the metallic zinc tunicle of substrate tunicle 2 or contain the tunicle of metallic zinc at the one or both sides of matrix material metal 1, thereafter, form resin molding 3 (laminated film or resin coating film) on this substrate tunicle 2, thus, obtained following result: the metal-made exterior material 10 with resin molding of manufacturing demonstrates the high adaptation that resin molding 3 is peeled off, even and contact also for a long time with acid or solvent etc. and can keep high adaptation.
Embodiment
Below, the present invention will be described in more detail to utilize embodiment and comparative example.The present invention is not limited by following embodiment.Need to prove, in the following description, " part " is " mass parts ", and " quality % " and " % by weight " synonym below also are expressed as " % " sometimes simply.
[matrix material metal]
Used following metallic plate or metal forming as the matrix material metal.
1a: aluminium sheet (JIS code name: A1100P, fine aluminium, thick 0.3mm)
1b: alloy foil (JIS code name: A8079, thick 0.03mm)
1c: stainless steel foil (JIS code name: SUS304, thick 0.1mm)
1d: copper coin (JIS code name: C1020P, oxygen-free copper, thick 0.3mm)
1e: nickel plate (purity 99 quality % above, thick 0.3mm)
1f: nickel plating copper coin (electroplating ambrose alloy, the oxygen-free copper of copper coin: C1020P, thick 0.3mm, nickel plating thickness 2 μ m)
[the formation method of substrate tunicle]
Utilize method shown below to form the substrate tunicle at the matrix material metallic surface.
(2a: alkalescence displacement plating)
Made ZINC SULFATE HEPTAHYDRATE 16.87 parts of (take zinc), 116 parts, NaOH, 20 parts of gluconic acid sodium salts and remainders alkalescence displacement plating solution of 1000 parts altogether as water.With the matrix material metal in this plating solution 30 ℃ of 30 seconds of dipping, after washing, use electric furnace 80 ℃ of heat dryings 1 minute.
(2b: alkalescence displacement plating)
Make ZINC SULFATE HEPTAHYDRATE 16.87 parts (in zinc), ferrous sulfate pentahydrate 1.16 parts of (take iron), 116 parts, NaOH, 20 parts of gluconic acid sodium salts and remainders and be the alkalescence displacement plating solution of 1000 parts of amounting to of water.With the matrix material metal in this plating solution 30 ℃ of 30 seconds of dipping, after washing, use electric furnace 80 ℃ of heat dryings 1 minute.
(2c: alkalescence displacement plating)
Make ZINC SULFATE HEPTAHYDRATE 16.87 parts (in zinc), nickel sulfate hexahydrate compound 2.0 parts of (take nickel), 116 parts, NaOH, 20 parts of gluconic acid sodium salts and remainders and be the alkalescence displacement plating solution of 1000 parts of amounting to of water.With the matrix material metal in this plating solution 30 ℃ of 30 seconds of dipping, after washing, use electric furnace 80 ℃ of heat dryings 1 minute.
(2d: alkalescence displacement plating)
Make ZINC SULFATE HEPTAHYDRATE 16.87 parts (in zinc), cobaltous sulfate heptahydrate 3.0 parts of (take cobalt), 116 parts, NaOH, 20 parts of gluconic acid sodium salts and remainders and be the alkalescence displacement plating solution of 1000 parts of amounting to of water.With the matrix material metal in this plating solution 30 ℃ of 30 seconds of dipping, after washing, use electric furnace 80 ℃ of heat dryings 1 minute.
(2e: alkalescence displacement plating)
Make ZINC SULFATE HEPTAHYDRATE 16.87 parts (in zinc), ferrous sulfate pentahydrate 1.16 parts (in iron), nickel sulfate hexahydrate compound 0.23 part of (take nickel), 116 parts, NaOH, 20 parts of gluconic acid sodium salts and remainder and be the alkalescence displacement plating solution of 1000 parts of amounting to of water.With the matrix material metal in this plating solution 30 ℃ of 30 seconds of dipping, after washing, use electric furnace 80 ℃ of heat dryings 1 minute.
(2f: alkalescence displacement plating)
Make ZINC SULFATE HEPTAHYDRATE 16.87 parts (in zinc), ferrous sulfate pentahydrate 1.16 parts (in iron), cobaltous sulfate heptahydrate 1.06 parts of (take cobalt), 116 parts, NaOH, 20 parts of gluconic acid sodium salts and remainders and be the alkalescence displacement plating solution of 1000 parts of amounting to of water.With the matrix material metal in this plating solution 30 ℃ of 30 seconds of dipping, after washing, use electric furnace 80 ℃ of heat dryings 1 minute.
(2g: acid displacement plating)
Made the following acidity displacement plating solution that amounts to 1000 parts, that is, 10 parts of ZINC SULFATE HEPTAHYDRATEs (in zinc), 7.65 parts of acid ammonium fluorides, and remainder is water, also uses the sodium hydrate aqueous solution of 10 quality % to be adjusted into pH3.0.With the matrix material metal in this plating solution 30 ℃ of 30 seconds of dipping, after washing, use electric furnace 80 ℃ of heat dryings 1 minute.
(2h: acid displacement plating)
Made the following acidity displacement plating solution of 1000 parts altogether, namely, 13 parts of ZINC SULFATE HEPTAHYDRATEs (in zinc), 3.6 parts of ferrous sulfate pentahydrates (in iron), 55 12.1 parts of quality % hydrofluoric acid aqueous solutions, and remainder is water, also uses the sodium hydrate aqueous solution of 10 quality % to be adjusted into pH2.0.With the matrix material metal in this plating solution 30 ℃ of 30 seconds of dipping, after washing, use electric furnace 80 ℃ of heat dryings 1 minute.
(2i: acid displacement plating)
Made the following acidity displacement plating solution of 1000 parts altogether, namely, 13 parts of ZINC SULFATE HEPTAHYDRATEs (in zinc), 0.8 part of nickel sulfate hexahydrate compound (in nickel), 55 12.1 parts of quality % hydrofluoric acid aqueous solutions, and remainder is water, also uses the sodium hydrate aqueous solution of 10 quality % to be adjusted into pH3.0.With the matrix material metal in this plating solution 30 ℃ of 30 seconds of dipping, after washing, use electric furnace 80 ℃ of heat dryings 1 minute.
(2j: acid displacement plating)
Made the following acidity displacement plating solution of 1000 parts altogether, namely, 13 parts of ZINC SULFATE HEPTAHYDRATEs (in zinc), 2.1 parts of cobaltous sulfate heptahydrates (in cobalt), 55 9.7 parts of quality % hydrofluoric acid aqueous solutions, and remainder is water, also uses the sodium hydrate aqueous solution of 10 quality % to be adjusted into pH3.0.With the matrix material metal in this plating solution 30 ℃ of 30 seconds of dipping, after washing, use electric furnace 80 ℃ of heat dryings 1 minute.
(2k: acid displacement plating)
Made the following acidity displacement plating solution of 1000 parts altogether, namely, 13 parts of ZINC SULFATE HEPTAHYDRATEs (in zinc), 2.5 parts of ferrous sulfate pentahydrates (in iron), 0.3 part of nickel sulfate hexahydrate compound (in nickel), 55 12.1 parts of quality % hydrofluoric acid aqueous solutions, and remainder is water, also uses the ammonia spirit of 10 quality % to be adjusted into pH2.5.With the matrix material metal in this plating solution 30 ℃ of 30 seconds of dipping, after washing, use electric furnace 80 ℃ of heat dryings 1 minute.
(2l: acid displacement plating)
Made the following acidity displacement plating solution of 1000 parts altogether, namely, 13 parts of ZINC SULFATE HEPTAHYDRATEs (in zinc), 1.5 parts of ferrous sulfate pentahydrates (in iron), 0.4 part of cobaltous sulfate heptahydrate (in cobalt), 55 12.1 parts of quality % hydrofluoric acid aqueous solutions, and remainder is water, also uses the ammonia spirit of 10 quality % to be adjusted into pH3.0.With the matrix material metal in this plating solution 30 ℃ of 30 seconds of dipping, after washing, use electric furnace 80 ℃ of heat dryings 1 minute.
(2m: zinc is electroplated)
Made the following zinc electroplate liquid of 1000 parts, that is, 91.6 parts of ZINC SULFATE HEPTAHYDRATEs (in zinc), 200 parts, sodium sulphate, and remainder is water, also uses the ammonia spirit of 10 quality % to be adjusted into pH4.0.The matrix material metal impregnation in this plating solution, is used zine plate to electrode, at 30 ℃ with 5A/dm
2Current density carry out the catholyte in 10 seconds.Then wash, use electric furnace 80 ℃ of lower heat dryings 1 minute.
(2n: zinc is electroplated)
Made the following zinc electroplate liquid of 1000 parts altogether, that is, and 32.7 parts of ZINC SULFATE HEPTAHYDRATEs (in zinc), 27.5 parts of ferrous sulfate pentahydrates (in iron), 200 parts, sodium sulphate, and remainder is water, also uses the ammonia spirit of 10 quality % to be adjusted into pH3.5.The matrix material metal impregnation in this plating solution, is used zine plate to electrode, at 30 ℃ with 5A/dm
2Current density carry out the catholyte in 10 seconds.Then wash, use electric furnace 80 ℃ of lower heat dryings 1 minute.
(2o: zinc is electroplated)
Made the following zinc electroplate liquid of 1000 parts altogether, that is, and 32.7 parts of ZINC SULFATE HEPTAHYDRATEs (in zinc), 25 parts of nickel sulfate hexahydrate compounds (in nickel), 200 parts, sodium sulphate, and remainder is water, also uses the ammonia spirit of 10 quality % to be adjusted into pH3.5.The matrix material metal impregnation in this plating solution, is used zine plate to electrode, at 30 ℃ with 5A/dm
2Current density carry out the catholyte in 10 seconds.Then wash, use electric furnace 80 ℃ of lower heat dryings 1 minute.
(2p: zinc is electroplated)
Made the following zinc electroplate liquid of 1000 parts altogether, that is, and 32.7 parts of ZINC SULFATE HEPTAHYDRATEs (in zinc), 25 parts of cobaltous sulfate heptahydrates (in cobalt), 200 parts, sodium sulphate, and remainder is water, also uses the ammonia spirit of 10 quality % to be adjusted into pH4.0.The matrix material metal impregnation in this plating solution, is used zine plate to electrode, at 30 ℃ with 5A/dm
2Current density carry out the catholyte in 10 seconds.Then wash, use electric furnace 80 ℃ of lower heat dryings 1 minute.
(2q: zinc is electroplated)
Made the following zinc electroplate liquid of 1000 parts altogether, namely, 32.7 parts of ZINC SULFATE HEPTAHYDRATEs (in zinc), 27.5 parts of ferrous sulfate pentahydrates (in iron), 25 parts of nickel sulfate hexahydrate compounds (in nickel), 200 parts, sodium sulphate, and remainder is water, also uses the ammonia spirit of 10 quality % to be adjusted into pH3.5.The matrix material metal impregnation in this plating solution, is used zine plate to electrode, at 30 ℃ with 5A/dm
2Current density carry out the catholyte in 10 seconds.Then wash, use electric furnace 80 ℃ of lower heat dryings 1 minute.
(2r: zinc is electroplated)
Made the following zinc electroplate liquid of 1000 parts altogether, namely, 32.7 parts of ZINC SULFATE HEPTAHYDRATEs (in zinc), 27.5 parts of ferrous sulfate pentahydrates (in iron), 25 parts of cobaltous sulfate heptahydrates (in cobalt), 200 parts, sodium sulphate, and remainder is water, also uses the ammonia spirit of 10 quality % to be adjusted into pH3.5.The matrix material metal impregnation in this plating solution, is used zine plate to electrode, at 30 ℃ with 5A/dm
2Current density carry out the catholyte in 10 seconds.Then wash, use electric furnace 80 ℃ of lower heat dryings 1 minute.
(2s: zinc is electroplated)
Made the following zinc electroplate liquid that amounts to 1000 parts, that is, 91.6 parts of ZINC SULFATE HEPTAHYDRATEs (in zinc), 200 parts, sodium sulphate, and remainder is water, also uses the ammonia spirit of 10 quality % to be adjusted into pH4.0.Then, the matrix material metal was at room temperature flooded 1 minute in nitric acid hydrofluoric acid aqueous solution (nitric acid 10 quality %, hydrofluoric acid 5 quality %), then wash., above-mentioned matrix material metal impregnation in above-mentioned zinc electroplate liquid, is used zine plate to electrode thereafter, at 30 ℃ with 5A/dm
2Current density carry out the catholyte in 10 seconds.Then wash, use electric furnace 80 ℃ of lower heat dryings 1 minute.
(2t: zinc is electroplated)
Made the following zinc electroplate liquid of 1000 parts altogether, that is, and 91.6 parts of ZINC SULFATE HEPTAHYDRATEs (in zinc), 27.5 parts of ferrous sulfate pentahydrates (in iron), 200 parts, sodium sulphate, and remainder is water, also uses the ammonia spirit of 10 quality % to be adjusted into pH4.0.Then, the matrix material metal was at room temperature flooded 1 minute in nitric acid hydrofluoric acid aqueous solution (nitric acid 10 quality %, hydrofluoric acid 5 quality %), then wash., above-mentioned matrix material metal impregnation in above-mentioned zinc electroplate liquid, is used zine plate to electrode thereafter, at 30 ℃ with 5A/dm
2Current density carry out the catholyte in 10 seconds.Then wash, use electric furnace 80 ℃ of lower heat dryings 1 minute.
(2u: the zinc oxide coating)
After being coated with machine coating zinc oxide colloidal sol (disperseing particle diameter 20nm, solid component concentration 1.5 quality %, pH9.0) with the #3 rod, spend heat drying 1 minute with 120 in electric furnace.
(2v: without the substrate tunicle)
For the matrix material metal, do not form the substrate tunicle, directly use electric furnace 80 ℃ of lower heat dryings 1 minute.
[the formation method of resin molding]
Utilize any one following method to form resin molding.
(3a: heat lamination)
Under 190 ℃ with surface heat crimping 10 seconds of 1MPa with the basad tunicle of maleic acid modified polypropylene film of thickness 50 μ m.
(3b: heat lamination)
10 seconds of surface heat crimping of the maleic acid modified polypropylene film layer side direction substrate tunicle of the resin molding of 2 layers of structure that with 1MPa, the copolymer layer lamination of the polypropylene of the maleic acid modified polypropene layer of thickness 20 μ m and thickness 30 μ m and ethene formed under 190 ℃.
(3c: heat lamination)
(Mitsui Chemicals, Inc makes at the dispersion liquid of the surface-coated acid modified polypropene of substrate tunicle to use #8SUS wheat rod, utilization rod to be coated with machine, trade name: R-120K, nonvolatile component concentration: 20 quality %), then in the heated air circulation type drying oven with 200 ℃ of dryings 1 minute, formed bond layer.Thereafter, under 190 ℃ with surface heat crimping 10 seconds of 1MPa with the bond layer on the basad tunicle of the polypropylene film of thickness 30 μ m (Tohcello Co., Ltd. make " CPPS ").
(3d: extrude lamination)
The molten resin layer that sour modified polypropene forms thickness 15 μ m is extruded on the surface of basad tunicle, and then the polypropylene film of coating thickness 30 μ m (Tohcello Co., Ltd. make " CPPS "), has implemented to extrude lamination.
(3e: dry lamination)
Use #8SUS wheat rod, utilize rod to be coated with machine in surface-coated polyurethanes dry lamination bonding agent (Japan Morton Co., Ltd. manufacturing of substrate tunicle, trade name: AD-503/CAT10, nonvolatile component concentration: 25 quality %), with 80 ℃ of dryings 1 minute, formed bond layer in electric furnace.Then, with the un-stretched polypropylene film of this bond layer and thickness 30 μ m (two village chemical industry Co., Ltd. make, trade name: Corona discharge Treatment face FCZX) under 100 ℃ with the 1MPa crimping after, 40 ℃ of lower slakings 4 days.
[for the making of test material]
With above-mentioned matrix material metal at Fine Cleaner 359E ((the NIHON PARKERIZING CO. of Nihon Parkerizing Co., Ltd., LTD.) make, alkali cleaner) carry out with 50 ℃ the degreasing of spraying for 10 seconds in 2% aqueous solution, then effects on surface is washed, and has prepared matrix material metal used in the embodiment 1 ~ 71 shown in table 1 ~ table 4 and comparative example 1 ~ 12.
Then, each shown in the matrix material metal application table 1 ~ table 4 that uses in the embodiment 1 ~ 71 shown in his-and-hers watches 1 ~ table 4 and comparative example 1 ~ 12 processed, and formed the substrate tunicle.Select any processing in 2a ~ 2t in embodiment 1 ~ embodiment 71 shown in table 1 ~ table 4, selected the processing of 2u or 2v in comparative example 1 ~ comparative example 12.
Here, due to matrix material metal generation etching when replacing plating, therefore measured its etch quantity (g/m
2).The mensuration of etch quantity is to utilize icp analysis (Shimadzu Scisakusho Ltd makes, and ICPE-9000) stripping has been carried out quantitatively to the matrix material metal in the displacement plating solution.To the results are shown in table 1 ~ table 4.In addition, to the adhesion amount (g/m of the metallic element (Zn, Fe, Ni, Co etc.) that consists of the substrate tunicle
2) also utilize icp analysis to carry out quantitatively.This adhesion amount is to dissolve in 60% nitric acid, this lysate is carried out icp analysis measure by the matrix material metal impregnation that will be provided with the substrate tunicle.Need to prove, if adhere to 1g/m
2Metallic element, the thickness of substrate tunicle just is about 0.5 μ m.To the results are shown in table 1 ~ table 4.In addition, for the surface of substrate tunicle, (Shimadzu Scisakusho Ltd makes, and ESCA-850M), identifies the chemical state of the zinc element in the substrate tunicle according to the peak position of ZnLMM auger spectrum to carry out XPS analysis.In the situation that the peak position of ZnLMM auger spectrum is set to 993.6eV, the zinc element is metallic state, in the situation that 988.6eV, the zinc element is the state of oxidation.To the results are shown in table 1 ~ table 4.
Then, for the matrix material metal with the substrate tunicle that uses in the embodiment 1 ~ 71 shown in table 1 ~ table 4 and comparative example 1 ~ 12, each lamination treatment shown in application table 1 ~ table 4 and formed resin molding.
Then, the embodiment 1 ~ 71 of gained and the metal-made exterior material with resin molding of comparative example 1 ~ 12 have been implemented deep-draw processing.At first, the metal-made exterior material with resin molding that is diameter 160mm to stamping-out carries out pull and stretch processing (for the first time), produces the cup of diameter 100mm.Next, with this cup again pull and stretch processing (for the second time) become diameter 75mm, further pull and stretch processing (for the third time) becomes diameter 65mm, has made as the tank for test material.Need to prove, the reduction (thin-walled property mark) in primary pull and stretch processing, the processing of secondary pull and stretch and the processing of pull and stretch for the third time is respectively 5%, 15% and 15%.
[performance evaluation]
For having implemented initial stage adaptation, durable adaptation, the electrolyte resistance driving fit retentivity of the tank (for test material) after deep-draw processing and liquid stabilising is following estimates with the metal-made exterior material of resin molding.The results are shown in table 1 ~ table 4.
(initial stage adaptation)
Conduct after deep-draw processing has been estimated the initial stage adaptation for the tank of test material.Can make tank, there is no the peeling off of resin molding, being made as of initial stage adaptation excellence " 3 minutes ", be made as " 2 minutes " with what the part of resin molding was peeled off, with resin molding whole peel off be made as " 1 minute ".
(electrolyte resistance driving fit retentivity)
The tank as for test material after deep-draw processing is immersed in the electrolyte solution for lithium ion secondary battery (LiPF6 of electrolyte: 1mol/L of the ion exchange water that is added with 1000ppm that is filled in closed container, the solvent volume ratio is EC:DMC:DEC=1:1:1) in, then put in the thermostat of 60 ℃ 7 days.Need to prove, " EC " is ethylene carbonate, and " DMC " is dimethyl carbonate, and " DEC " is diethyl carbonate.Then, take out for test material, dipping is 1 minute in ion exchange water, after shaking cleaning, in electric furnace with 100 ℃ of dryings 10 minutes.Then, tip with tweezers scratches the resin face, with do not occur fully resin molding peel off be made as " 4 minutes ", although will peel off but scratch the resistance eminence in be made as " 3 minutes " of realistic scale, to be made as " 2 minutes " with what very weak power can be peeled off, be made as " 1 minute " with what resin molding had been peeled off.
As shown in table 1 ~ table 4, embodiment 1 ~ 71 compares with the test material that supplies of comparative example 1 ~ 12 for test material (the metal-made exterior material with resin molding of the present invention), even in the situation that also can keep adaptation in impregnated in electrolyte, confirm that its electrolyte resistance driving fit retentivity is excellent.
Claims (8)
1. metal-made exterior material with resin molding, it has: the matrix material metal, be located at this matrix material metal one or both sides the substrate tunicle and be located at laminated film or resin coating film on this substrate tunicle, wherein, described substrate tunicle is metallic zinc tunicle or the tunicle that contains metallic zinc.
2. the metal-made exterior material with resin molding according to claim 1, wherein, described laminated film or resin coating film contain polyolefin or acid modified polyolefin.
3. the metal-made exterior material with resin molding according to claim 1 and 2, wherein, described matrix material metal is to be selected from any in aluminium or its alloy, stainless steel, copper or its alloy and nickel or its alloy.
4. the described metal-made exterior material with resin molding of any one according to claim 1 ~ 3, wherein, the described tunicle that contains metallic zinc comprises the one kind or two or more element in chosen from Fe, nickel and cobalt.
5. the described metal-made exterior material with resin molding of any one according to claim 1 ~ 4, it is implement deep-draw processing, attenuate processing or stretch-draw processing and form.
6. manufacture method with the metal-made exterior material of resin molding, the method has:
Utilize displacement plating method or galvanoplastic form as the metallic zinc tunicle of substrate tunicle or contain the operation of the tunicle of metallic zinc at the one or both sides of matrix material metal; And
Form the operation of laminated film or resin coating film on described substrate tunicle.
7. the manufacture method of the metal-made exterior material with resin molding according to claim 6, wherein, also have any manufacturing procedure more than 1 or 2 that is selected from deep-draw processing, attenuate processing and stretch-draw processing.
8. the manufacture method of according to claim 6 or 7 described metal-made exterior materials with resin molding wherein, before the formation operation of described substrate tunicle, also has the operation be used to the oxide tunicle of removing described matrix material metal surface.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-243944 | 2011-11-07 | ||
| JP2011243944A JP5980495B2 (en) | 2011-11-07 | 2011-11-07 | Metal exterior material with resin film and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103085384A true CN103085384A (en) | 2013-05-08 |
| CN103085384B CN103085384B (en) | 2016-08-10 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201210439629.7A Expired - Fee Related CN103085384B (en) | 2011-11-07 | 2012-11-06 | Metal exterior material and manufacture method thereof with resin molding |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5980495B2 (en) |
| KR (1) | KR101870455B1 (en) |
| CN (1) | CN103085384B (en) |
| TW (1) | TWI597161B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103847162A (en) * | 2014-02-21 | 2014-06-11 | 苏州米达思精密电子有限公司 | Surface gold-plated golden reinforcing piece and preparation process thereof |
| CN104953048A (en) * | 2014-03-24 | 2015-09-30 | 昭和电工包装株式会社 | Exterior material for electrochemical device and electrochemical device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP6626258B2 (en) | 2014-04-07 | 2019-12-25 | 昭和電工パッケージング株式会社 | Manufacturing method of laminate exterior material |
| KR102144161B1 (en) * | 2018-06-25 | 2020-08-12 | 현대제철 주식회사 | Plating solution for electro-galvanized steel sheet, manufacturing method for electro-galvanized steel sheet using the same, and electro-galvanized steel sheet prepared using the same |
| JP6733971B1 (en) * | 2019-04-23 | 2020-08-05 | 株式会社シミズ | Copper damage prevention film, method for producing copper member with copper damage prevention film, and copper damage prevention method |
| CN113381101A (en) * | 2021-05-07 | 2021-09-10 | 厦门大学 | Battery flexible packaging material with good heat dissipation performance and preparation method thereof |
| KR20230003964A (en) * | 2021-06-30 | 2023-01-06 | 삼성전자주식회사 | Electronic device comprising plate, plate, and manufacturing method of plate |
| KR20230100585A (en) | 2021-12-28 | 2023-07-05 | 주식회사 리베스트 | Apparatus and method for forming pattern on exterior material of battery |
| WO2023128234A1 (en) | 2021-12-28 | 2023-07-06 | 주식회사 리베스트 | Apparatus and method for forming pattern on exterior material of battery |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN103085384B (en) | 2016-08-10 |
| JP2013099869A (en) | 2013-05-23 |
| KR20130050255A (en) | 2013-05-15 |
| JP5980495B2 (en) | 2016-08-31 |
| TWI597161B (en) | 2017-09-01 |
| KR101870455B1 (en) | 2018-06-22 |
| TW201325891A (en) | 2013-07-01 |
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