JP2013099869A - Metal made exterior material with resin film and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metal made exterior material with resin film excellent in chemical resistance capable of providing high adhesiveness in which a laminated film or a resin coating film does not peel further capable of maintaining the high adhesiveness even in the case of contacting an acid or solvents even in the case the resin film is laminated or resin coating film is formed on a base material metal such as aluminum or stainless steel and thereafter severe shaping machining such as deep-draw machining, ironing machining, or stretch draw machining is applied.SOLUTION: The metal made exterior material with resin film has a base material metal 1, a substrate film 2 arranged one or both surfaces of the base material metal 1, a laminate film or the resin coating film 3 arranged on the substrate film 2 and is characterized in that the substrate film 2 is a metal zinc film or a metal zinc-containing film. Here, it is preferable that the metal zinc film or the metal zinc-containing film is formed in a substituting plating method or an electroplating method.

Description

  The present invention relates to a metal exterior material with a resin film and a method for producing the same. Specifically, the present invention relates to a metal exterior material with a resin film that can maintain the adhesion between a base metal and a laminate film or a resin coating film even when it comes into contact with an electrolytic solution, and a method for producing the same.

  More specifically, when a resin film is laminated or a resin coating film is formed on a base metal such as aluminum or stainless steel, and then severe molding processing such as deep drawing processing, ironing processing or stretch drawing processing is performed. The laminate film or resin coating film can be imparted with high adhesion such that it does not peel off, and it has excellent chemical resistance that can maintain high adhesion even if it is in contact with an acid or solvent for a long time. The present invention relates to a metal exterior material with a resin film.

  Lamination is a processing means for heat-pressing a resin film (hereinafter referred to as a resin film or a laminate film) to the surface of a metal material, and is intended to protect the surface or impart design properties. This is one of the methods for coating the surface of a metal material, and is used in various fields. Laminating process generates less waste gas such as solvent, carbon dioxide, etc. or warming gas generated during drying compared to a method of forming a resin coating by applying and drying a resin composition on the surface of a metal material. Therefore, it is preferably applied from the viewpoint of environmental protection, and its use is expanded. For example, a body or lid of a food can made of aluminum thin plate material, steel thin plate material, packaging aluminum foil, stainless steel foil, etc. It is used for containers or dry battery containers.

  Particularly recently, a metal plate such as a lightweight and high barrier metal plate such as an aluminum plate or a stainless steel plate is preferably used as the exterior material of a mobile lithium ion secondary battery used in a mobile phone, an electronic notebook, a notebook computer, a video camera, or the like. Lamination is applied to the surface of such a metal plate. In addition, lithium ion secondary batteries are being studied as driving energy for electric vehicles or hybrid vehicles, and laminated metal plates are also being examined as exterior materials.

  The laminate film used for such a lamination process is directly bonded to a metal material and then heat-pressed. Therefore, there are advantages such that the waste of the raw material can be suppressed, the number of pinholes (defects) is small, and the workability is excellent as compared with a general resin coating film formed by applying and drying a resin composition. As materials for the laminate film, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyolefins such as polyethylene and polypropylene, and polyamide resins such as nylon are generally used.

  When laminating a laminate film to a metal material surface (hereinafter also simply referred to as “metal surface”), the metal surface is degreased and washed to improve the adhesion between the laminate film and the metal surface and the corrosion resistance of the metal surface. Thereafter, chemical conversion treatment such as phosphoric acid chromate is usually performed. However, such a chemical conversion treatment requires a washing step for removing excess treatment liquid after the treatment, and costs for waste water treatment of washing water discharged from the washing step. In particular, chemical treatments such as phosphoric acid chromate tend to be avoided from environmental considerations in recent years because a treatment solution containing hexavalent chromium is used.

  On the other hand, when the lamination process is performed without performing a chemical conversion treatment or the like on the metal surface, there is a problem that the laminate film is peeled off from the metal surface or the metal material is corroded. For example, an exterior material of a lithium ion secondary battery is subjected to processing with a high degree of processing in the manufacturing process. As the electrolyte of the lithium ion secondary battery, an organic solvent such as ethyl carbonate or diethyl carbonate and a fluorine-based lithium complex salt such as lithium hexafluorophosphate or lithium tetrafluoroborate are used. Therefore, when such an exterior material is used for a long period of time, not only the organic solvent that is an electrolyte but also moisture in the atmosphere enters the container, which reacts with the electrolyte to produce hydrofluoric acid, There is a problem that hydrogen acid permeates the laminate film to cause peeling between the metal surface and the laminate film, and corrodes the metal surface. Moreover, there is a case where the metal material is preheated (200 to 300 ° C.) before laminating, and there is a problem that the film is deteriorated by heat and the adhesion is lowered.

  As packaging materials for packaging lithium secondary batteries, various laminates having resistance to organic solvents and hydrofluoric acid have been proposed. For example, in Patent Document 1, outermost layer / barrier layer / innermost layer, or In the laminate comprising the outermost layer / barrier layer / intermediate layer / innermost layer, the innermost layer surface side surface of the barrier layer is degreased or the surface oxide is removed, and the phosphate film, chromate, fluoride system A laminated body subjected to formation of an acid-resistant film composed of a compound or an organosilicon compound, an organotitanium compound, an organoaluminum compound and / or a coupling treatment composed of a silane, organotitanium, or organoaluminum material Proposed. According to this technology, as a laminated film used for a case for housing a polymer battery, it is excellent in water vapor and other gas barrier properties, is excellent in content resistance and adhesive strength between layers of the laminate, and has puncture resistance, etc. It is said that it has mechanical strength, can be used at high temperatures, and can provide a stable laminate structure with respect to an electrolytic solution.

  In Patent Document 2, at least an adhesive resin layer, a first chemical conversion treatment layer, an aluminum foil layer, a second chemical conversion treatment layer, an adhesive layer, and a base material layer are sequentially laminated on one surface of the sealant layer. In a lithium ion battery packaging material, a lithium ion battery packaging material is proposed in which the aluminum foil layer is made of an aluminum foil etched on both sides, and the first chemical conversion treatment layer and the second chemical conversion treatment layer are made of a zinc oxide coating. Has been. According to this technology, it is possible to obtain excellent electrolytic solution resistance and hydrofluoric acid resistance without using chromium, which may cause environmental impact, and high production that can easily form a chemical conversion treatment layer on both sides of an aluminum foil. It is said that a packaging material for a lithium ion battery can be provided.

  Further, in Patent Document 3, in a plastic laminate film in which a plastic base film, a metal foil, and a functional plastic layer are overlaid, the surface of the metal foil facing at least the functional plastic layer and the functional plastic layer Proposed technology for physical vapor deposition of at least one metallic protective layer, such as a chromium layer, on the surface facing the metal foil and / or inside the functional plastic layer Has been. According to this technique, it is said that the adhesion between individual layers can be improved and it can be preferably used as a plastic laminate film used for cladding of a lithium ion polymer battery or a lithium polymer battery.

JP 2001-35453 A JP 2011-76887 A Special table 2009-544492

  However, any of the techniques proposed in Patent Documents 1 to 3 is a laminate film for wrapping a lithium secondary battery, and does not receive processing with a high degree of processing as described above. Therefore, it is unclear whether or not the laminate film still has a high electrolytic solution resistance when used for a long time after being processed with a high degree of processing.

  An object of the present invention is to laminate a resin film or form a resin coating film (hereinafter also referred to as “resin film”) on a base metal such as aluminum or stainless steel, and then perform deep drawing, ironing or stretch drawing. Even when it is subjected to severe molding such as, it can provide high adhesion so that the laminate film or resin coating does not peel off, and it is high even if it is in contact with acid or solvent for a long time An object of the present invention is to provide a metal exterior material with a resin film excellent in chemical resistance capable of maintaining adhesion and a method for producing the same.

  A metal exterior material with a resin film according to the present invention for solving the above problems is provided with a base metal, a base film provided on one or both surfaces of the base metal, and the base film. The base film is a metal zinc film or a metal zinc-containing film.

  According to this invention, when a metal zinc film or a metal zinc-containing film is provided as a base film between the base metal and the resin film, the laminate film or the resin film exhibits high adhesion that does not peel off, and acid or The result was that high adhesion was maintained even after contact with a solvent or the like for a long time.

  In the metal exterior material with a resin film according to the present invention, the laminate film or the resin coating film preferably contains a polyolefin or an acid-modified polyolefin.

  In the metal exterior material with a resin film according to the present invention, the base metal is preferably selected from aluminum or an alloy thereof, stainless steel, copper or an alloy thereof, and nickel or an alloy thereof.

  In the metal exterior material with a resin film according to the present invention, the metal zinc-containing coating may be configured to include one or more elements selected from iron, nickel, and cobalt.

  According to the present invention, by providing a metal zinc-containing film containing one or more elements selected from iron, nickel and cobalt as a base film, for example, when forming a base film by displacement plating, The amount of metal replacement can be reduced, and the mechanical strength of the underlying film can be increased.

  In the metal exterior material with a resin film according to the present invention, deep drawing processing, ironing processing, or stretch drawing processing may be performed.

  According to this invention, even if it is a case where severe shaping | molding processes, such as deep drawing process, ironing process, or stretch draw process, are given with respect to the metal exterior material after providing the resin film, the resin film is high It has adhesiveness and chemical resistance that can maintain high adhesion even when it is in contact with acid or solvent for a long time.

  In order to solve the above-mentioned problems, a method for producing a metal exterior material with a resin film according to the present invention comprises a metal zinc film or a metal zinc-containing film on one or both surfaces of a base metal by a displacement plating method or an electroplating method. And a step of forming a laminate film or a resin coating film on the base coating.

  According to this invention, a metal zinc film or a metal zinc-containing film is formed as a base film on one or both surfaces of the base metal by a displacement plating method or an electroplating method, and then a laminate film or a resin coating is formed on the base film. When the film is formed, the manufactured metal exterior material with resin film shows high adhesion that the laminate film or resin coating does not peel off, and maintains high adhesion even if it is in contact with acids or solvents for a long time. The result of doing was obtained.

  In the manufacturing method of the metal exterior material with a resin film which concerns on this invention, you may comprise so that it may further have any 1 or 2 or more processing processes chosen from deep drawing processing, ironing processing, and stretch drawing processing.

  In the manufacturing method of the metal exterior material with a resin film according to the present invention, it may be configured to further include a step of removing the oxide film on the surface of the base metal before the base film forming step. .

  According to this invention, since it has further the process of removing the oxide film of the surface of a base metal before the formation process of a base film, the adhesiveness of a base metal and a base film can be improved more.

  According to the metal exterior material with a resin film and the method for producing the same according to the present invention, a laminate film or a resin coating is provided by providing a metal zinc film or a metal zinc-containing film as a base film between the base metal and the resin film. It was possible to obtain a result that the film showed high adhesion without peeling and maintained high adhesion even when contacted with an acid or a solvent for a long time. Even when severe molding processing such as deep drawing, ironing or stretch draw processing is applied to a metal exterior material with a resin film having such effects, the laminate film or the resin coating film is high enough not to peel off Adhesiveness can be imparted, and further, an effect of excellent chemical resistance capable of maintaining high adhesiveness even when contacted with an acid or a solvent for a long time was obtained.

It is typical sectional drawing which shows an example of the metal exterior material with a resin film which concerns on this invention.

  Hereafter, the metal exterior material with a resin film concerning the present invention and its manufacturing method are explained. The technical scope of the present invention is not limited by the following description and the form of the drawings.

[Metal exterior material with resin film]
As shown in FIG. 1, a metal exterior material 10 with a resin film according to the present invention includes a base metal 1, a base film 2 provided on one or both surfaces of the base metal 1, and the base film 2 has a laminate film or resin coating (hereinafter referred to as “resin film 3” unless otherwise specified). And the base film 2 is characterized in that it is a metal zinc film or a metal zinc-containing film. In FIG. 1, the base coating 2 and the resin film 3 are provided on one side of the base metal 1, but the base coating 2 and the resin film 3 may be provided on both sides of the base metal 1.

  Hereinafter, the configuration of the present invention will be described in detail.

(Base metal)
The base metal 1 is a metal thin plate material or foil that serves as a base (base material) of the metal exterior member 10 with a resin film according to the present invention. Examples of the material of the base metal 1 include any one selected from aluminum or an alloy thereof, stainless steel, copper or an alloy thereof, and nickel or an alloy thereof. Such a base metal 1 may be a purchased product or may be obtained by hot rolling or cold rolling a plate material having a predetermined thickness. Although the thickness of the base metal 1 is not specifically limited, For example, it is about 0.01 mm-2.0 mm. In addition, when providing the base film 2 by the displacement plating mentioned later, since the base metal 1 is etched, thickness is designed in consideration of the etching amount.

  Further, other metals or alloys may be provided on these metals or alloys. Examples of other metal or alloy forming means include plating (electroplating, electroless plating) means, vapor deposition means, and clad means. As an example, nickel plating copper etc. which carried out electro nickel plating on copper or a copper alloy can be mentioned.

(Undercoat)
The base film 2 is a metal zinc film or a metal zinc-containing film provided on one or both surfaces of the base metal 1. In the metal exterior material 10 with a resin film according to the present invention, by providing a metal zinc film or a metal zinc-containing film on the base metal 1 as the base film 2 of the resin film 3, the resin film 3 and the base metal 1 In addition, it was possible to obtain a result that the high adhesiveness can be maintained even if it is in contact with an acid or a solvent for a long time.

  The metal zinc film is a layer composed only of metal zinc, and the metal zinc-containing film is a layer made of a metal film containing metal zinc. “Contains” means that a metal element other than zinc is included. Examples of such a metal element include one or more iron group metals selected from iron, nickel, and cobalt. The metal zinc-containing coating containing these iron group metals has the advantage that the mechanical strength such as hardness can be increased and the etching amount of the base metal 1 can be suppressed during displacement plating described later. The content of the iron group metal in the metal zinc-containing film is preferably in the range of 0.5% by mass to 15% by mass. From the viewpoint that the metal zinc-containing film containing the iron group element in such a range can suppress the etching amount of the base metal 1, it is sufficiently resistant to electrolysis even if the thickness of the base film 2 is not excessively increased. There is an advantage that a base film having liquid adhesion maintaining property can be formed. In addition, the metal zinc containing film | membrane at this time is all metal zinc except an unavoidable impurity component (a trace amount oxide component is included).

  The metal zinc film or the metal zinc-containing film that is the base film 2 is formed by a displacement plating method or an electroplating method.

  The displacement plating method oxidizes and dissolves the base metal 1 and reduces and precipitates zinc ions depending on the size of the redox potential of the base metal 1 in contact with the displacement plating solution and the redox potential of the zinc ions contained in the plating solution. Are redox reactions that occur simultaneously by a chemical reaction, and the base film 2 is formed by the precipitation of zinc that occurs simultaneously with the dissolution (also referred to as etching) of the base metal 1. Therefore, the displacement plating method depends on the oxidation-reduction potential between the base metal 1 and the metal ions that can be deposited in the displacement plating solution, and a chemical reaction occurs in which the base metal 1 is oxidized and dissolved leaving an electron. This method is applied when a redox environment is prepared in which a chemical reaction occurs in which the electrons are received by metal ions in the liquid and reduced and deposited. The same applies when the plating solution contains one or more selected from iron, nickel, and cobalt, depending on the redox potential of the base metal 1 and the metal ions that can be deposited. , It may or may not be included in the undercoat 2. This displacement plating method is convenient because it can form the base coating 2 having a uniform thickness regardless of the shape of the base metal 1, and is harder than the base coating 2 formed by electroplating, and has a tensile strength. Excellent mechanical strength.

  Formation of the base film 2 by the displacement plating method is performed by bringing the base metal 1 into contact with an alkaline or acidic displacement plating solution. Whether alkaline or acidic substitution plating solution is used can be appropriately selected depending on whether or not substitution plating occurs depending on the redox potential of the base metal 1 and metal ions in the substitution plating solution. Examples of the means for “contacting” include immersion of the base metal 1 in the displacement plating solution, spray injection of the displacement plating solution onto the base metal 1, and the like.

  The displacement plating solution is not particularly limited. For example, an alkaline displacement plating solution (called a zincate bath, mainly composed of zinc sulfate and sodium hydroxide) and an acidic displacement plating solution (zinc sulfate and acidic fluoride) used in Examples described later. And ammonium fluoride or hydrofluoric acid as a main component). These substitution plating solutions may contain additives such as brighteners, complexing agents, reducing agents, pH adjusting agents, buffering agents, etc., if necessary, such as sodium gluconate, other Additives can be mentioned. In addition, when the undercoat 2 further contains one or more metals selected from iron, nickel and cobalt, for example, ferrous sulfate, nickel sulfate, cobalt sulfate, etc. are optionally blended in the replacement plating solution. To do.

  In addition, each above-mentioned salt is illustration, and if the target metal zinc film | membrane or a metal zinc containing film | membrane can be formed in the one or both surfaces of the base metal 1, zinc salts other than the above, various metal salts, etc. will be used. Also good. Moreover, the liquid composition of the displacement plating solution is not particularly limited. For example, in the case of a zincate bath, zinc sulfate 8 to 16 g / L and sodium hydroxide 90 to 150 g / L are common.

  In the electroplating method, an electric current is applied between the base metal 1 in contact with the electroplating solution and a counter electrode (also referred to as a counter electrode) that is also in contact with the electroplating solution, and electricity is applied on the base metal 1. This is a means for forcibly reducing and depositing metal ions in the plating solution.

  Formation of the base film 2 by electroplating is performed by applying a current or voltage in a state where the electrogalvanizing solution is in contact with the base metal 1 and the counter electrode. As the counter electrode, a zinc plate or an insoluble electrode (for example, a carbon electrode, a platinum-coated titanium electrode, etc.) can be used. Further, when the metal zinc-containing film is formed using an electroplating solution containing a metal component other than the zinc component, a counter electrode containing the same amount of the metal component other than zinc contained in the metal zinc-containing film is formed. It may be used. By carrying out like this, the quantity according to the reduction | decrease amount of the metal component in an electroplating liquid can be supplied from a counter electrode. Since such an electroplating method does not involve a chemical reaction unlike the displacement plating method, the base film 2 having a desired thickness can be easily formed only by controlling the current or voltage. Further, since the deposition rate is higher than that of the displacement plating method, formation at a high speed is possible.

  The electrogalvanizing solution is not particularly limited, and examples thereof include a zinc sulfate plating solution used in Examples described later. The electroplating solution may contain additives such as a brightener, a complexing agent, a pH adjuster, and a buffer as necessary. In addition, when the base film 2 further contains one or more metals selected from iron, nickel and cobalt, for example, ferrous sulfate, nickel sulfate, cobalt sulfate, etc. are arbitrarily blended in the electroplating solution. To do.

The thickness of the base film 2 formed by each of these means is usually 0.01 μm to 0.70 μm (corresponding to a total adhesion amount of about 0.10 g / m ² to about 5.0 g / m ² ), preferably Is 0.03 μm to 0.28 μm (corresponding to a total deposition amount of about 0.2 g / m ² to about 2.0 g / m ² ). If the thickness of the base film 2 is less than 0.01 μm, sufficient resistance to electrolyte solution adhesion may not be obtained. On the other hand, when the thickness of the base film 2 exceeds 0.70 μm, although the electrolytic solution adhesion maintaining property is excellent, it takes time to form the base film 2 and the productivity may be inferior. The total adhesion amount 1 g / m ² of the base film 2 corresponds to a thickness of the base film 2 of about 0.14 μm.

The reason why the adhesion resistance of the electrolytic solution is maintained when a metal zinc coating or a metal zinc-containing coating is provided as the base coating 2 is not clear at this time, but is probably in the electrolyte containing LiPF ₆ or the like as an electrolyte. When the metal outer packaging material 10 with a resin film according to the present invention was immersed, the concentrated phosphorus element was confirmed between the base film 2 and the resin film 3, and thus the hydrolysis product of LiPF ₆ when immersed. This is because the zinc component in the undercoat 2 is eluted by hydrofluoric acid, and the zinc component reacts with the phosphorus compound which is also a hydrolysis product of LiPF ₆ to form an insoluble salt. It may be a factor that maintains the electrolyte adhesion.

(Resin film)
The resin film 3 is provided as a laminate film obtained by laminating a resin film on the base film 2 or as a resin coating film obtained by applying a resin on the base film 2. The resin film 3 is formed of polyolefin, acid-modified polyolefin, or a resin composition containing them as a main component. Such a resin film 3 is provided in order to prevent the base metal 1 from being corroded or eroded even if it is in contact with an acid or a solvent for a long time.

  Polyolefins include polyethylenes such as high-density polyethylene and low-density polyethylene; copolymers of ethylene and α-olefins; polypropylenes based on homopolymers, random copolymers or block copolymers; copolymers of propylene and α-olefins And the like, and one or more selected from these can be used. The acid-modified polyolefin can be obtained by kraft modification of polyolefin with maleic anhydride or the like.

  The resin film 3 may be a single layer or a multilayer structure in which a plurality of layers are laminated. Further, if necessary, a resin such as a copolymer of ethylene and a cyclic olefin may be further laminated to provide moisture resistance. Moreover, the resin film 3 may contain additives, such as antioxidant, a flame retardant, and a tackifier, as needed. The thickness of the resin film 3 is usually 10 μm to 100 μm, and preferably 20 μm to 50 μm.

  Examples of the laminating process for providing the laminate film include a heat lamination method, a dry lamination method, an extrusion lamination method, and a coextrusion lamination method.

  Formation of the resin film 3 by the heat lamination method is performed by thermocompression bonding the resin film 3 to the surface of the base film 2. The temperature and pressure at the time of thermocompression bonding are arbitrarily set according to the properties of the resin film 3. In addition, an adhesive layer may be provided on the surface of the resin film 3 as necessary, and the adhesive layer may be used as a thermocompression bonding layer. Examples of such an adhesive layer include a layer made of a resin composition such as an epoxy resin, a phenol resin, an acrylic resin, and a urethane resin, and such a resin can be provided by applying, drying, or the like.

  Formation of the resin film 3 by the dry lamination method is performed by forming an adhesive layer on the surface of the base film 2 and pressing the resin film 3 on the surface of the adhesive layer at room temperature. Adhesive layers include polyester adhesives, polyethylene adhesives, polyether adhesives, cyanoacrylate adhesives, urethane adhesives, organic titanium adhesives, polyether urethane adhesives, epoxy adhesives And resin compositions such as polyester urethane adhesives, isocyanate adhesives, polyolefin adhesives, and the like. The adhesive layer can be formed by applying and drying such a resin composition on the surface of the undercoat 2.

  Formation of the resin film 3 by the extrusion lamination method or the coextrusion lamination method is performed by directly extruding the molten resin onto the surface of the base coating 2 and then cooling. For extrusion and cooling of the resin, for example, equipment of a flat die method or a melt extrusion method can be used.

(Metal exterior material with resin film)
The metal exterior material 10 with a resin film thus configured is then subjected to deep drawing processing, ironing processing, or stretch drawing processing as necessary, and is formed into a predetermined shape and used for various applications. For example, it is used as an exterior material for mobile lithium-ion secondary batteries used in mobile phones, electronic notebooks, notebook computers, video cameras, and the like. Moreover, it can also be used as a frame of a portable device such as a smart phone or a tablet PC. Moreover, it can also be used as an exterior material of a lithium ion secondary battery as drive energy of an electric vehicle or a hybrid vehicle.

  As explained above, according to the metal exterior material 10 with a resin film according to the present invention, by providing a metal zinc film or a metal zinc-containing film as the base film 2 between the base metal 1 and the resin film 3. Moreover, the high adhesiveness which the resin film 3 does not peel was shown, and the result that high adhesiveness was maintained even if it contacted an acid, a solvent, etc. for a long time was able to be obtained. Even if the metal exterior material 10 with a resin film having such an effect is subjected to severe molding processing such as deep drawing processing, ironing processing or stretch drawing processing, the high adhesion that the resin film 3 does not peel off. In addition, an effect of being excellent in chemical resistance capable of maintaining high adhesion even when contacted with an acid or a solvent for a long time was obtained.

[Method for producing metal exterior material with resin film]
The manufacturing method of the metal exterior material 10 with a resin film which concerns on this invention is using the metal zinc film | membrane or a metal zinc containing film | membrane as the base film 2 by the displacement plating method or the electroplating method on the one or both surfaces of the base metal 1. It has the base film formation process to form, and the resin film formation process which forms a laminate film or a resin coating film on the base film 2. “Having” means that a step other than the base film forming step and the resin film forming step may be included. For example, you may have any 1 or 2 or more of the pre-processing process mentioned later, a process process, an oxide film removal process, etc.

  The details of each step are as described in the explanation section of the above-mentioned “metal exterior material with resin film”, and the preparation or formation step of the base metal 1, the formation step of the base film 2, and the formation step of the resin film 3 The description of processing steps such as deep drawing will be omitted below. In this manufacturing method, a step of removing the oxide film on the surface of the base metal 1 may be further provided before the base film 2 is formed. The oxide film can be removed by general acid cleaning using an acid such as sulfuric acid, nitric acid, hydrochloric acid, or hydrofluoric acid. Examples of the acid cleaning means include immersion cleaning or spray cleaning. Moreover, the degreasing process which is a general pretreatment can also be performed as needed. In addition, water washing is normally arrange | positioned between each process.

  Thereafter, the metal outer packaging material 10 with a resin film is processed by a processing step such as deep drawing, ironing, or stretch drawing as necessary. By such a processing step, it is formed into a predetermined shape and used for various applications.

  As mentioned above, according to the manufacturing method of the metal exterior material 10 with a resin film which concerns on this invention, the metal zinc film | membrane or a metal zinc containing film | membrane is grounded by the displacement plating method or the electroplating method to one or both surfaces of the base metal 1 When the resin film 3 (laminated film or resin coating film) was formed on the base film 2 after forming as the film 2, the resin-coated metal exterior material 10 with the resin film 3 was not peeled off. The result was that it showed adhesion and maintained high adhesion even when it was in contact with an acid or a solvent for a long time.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited by the following examples. In the following, “part” means “part by mass”, “mass%” is synonymous with “wt%”, and may be simply expressed as “%” below.

[Base metal]
The following metal plates or metal foils were used as the base metal.

1a: Aluminum plate (JIS symbol: A1100P, pure aluminum, thickness 0.3 mm)
1b: Aluminum alloy foil (JIS symbol: A8079, thickness 0.03 mm)
1c: Stainless steel foil (JIS symbol: SUS304, thickness 0.1 mm)
1d: Copper plate (JIS symbol: C1020P, oxygen-free copper, thickness 0.3 mm)
1e: Nickel plate (purity 99% by mass or more, thickness 0.3 mm)
1f: Ni plating Cu plate (electric Ni plating Cu, copper plate: oxygen free copper of C1020P, thickness 0.3 mm, Ni plating thickness 2 μm)

[Formation method of undercoat]
An undercoat was formed on the surface of the base metal by the following method.

(2a: Alkaline displacement plating)
A total of 1000 parts of alkaline displacement plating solution was produced, comprising 16.87 parts of zinc sulfate heptahydrate (as zinc), 116 parts of sodium hydroxide, 20 parts of sodium gluconate and the balance water. The base metal was immersed in this plating solution at 30 ° C. for 30 seconds, washed with water, and then heated and dried at 80 ° C. for 1 minute using an electric furnace.

(2b: Alkaline displacement plating)
A total of 16.87 parts zinc sulfate heptahydrate (as zinc), 1.16 parts ferrous sulfate pentahydrate (as iron), 116 parts sodium hydroxide, 20 parts sodium gluconate and the balance water. 1000 parts of alkaline displacement plating solution was prepared. The base metal was immersed in this plating solution at 30 ° C. for 30 seconds, washed with water, and then heated and dried at 80 ° C. for 1 minute using an electric furnace.

(2c: Alkaline displacement plating)
16.87 parts of zinc sulfate heptahydrate (as zinc), 2.0 parts of nickel sulfate hexahydrate (as nickel), 116 parts of sodium hydroxide, 20 parts of sodium gluconate, and the rest are water for a total of 1000 parts An alkaline displacement plating solution was prepared. The base metal was immersed in this plating solution at 30 ° C. for 30 seconds, washed with water, and then heated and dried at 80 ° C. for 1 minute using an electric furnace.

(2d: Alkaline displacement plating)
16.87 parts of zinc sulfate heptahydrate (as zinc), 3.0 parts of cobalt sulfate heptahydrate (as cobalt), 116 parts of sodium hydroxide, 20 parts of sodium gluconate, and the balance is water for a total of 1000 parts An alkaline displacement plating solution was prepared. The base metal was immersed in this plating solution at 30 ° C. for 30 seconds, washed with water, and then heated and dried at 80 ° C. for 1 minute using an electric furnace.

(2e: Alkaline displacement plating)
16.87 parts of zinc sulfate heptahydrate (as zinc), 1.16 parts of ferrous sulfate pentahydrate (as iron), 0.23 parts of nickel sulfate hexahydrate (as nickel), sodium hydroxide A total of 1000 parts of alkaline displacement plating solution was prepared with 116 parts, 20 parts of sodium gluconate and the balance water. The base metal was immersed in this plating solution at 30 ° C. for 30 seconds, washed with water, and then heated and dried at 80 ° C. for 1 minute using an electric furnace.

(2f: Alkaline displacement plating)
16.87 parts of zinc sulfate heptahydrate (as zinc), 1.16 parts of ferrous sulfate pentahydrate (as iron), 1.06 parts of cobalt sulfate heptahydrate (as cobalt), sodium hydroxide A total of 1000 parts of alkaline displacement plating solution was prepared with 116 parts, 20 parts of sodium gluconate and the balance water. The base metal was immersed in this plating solution at 30 ° C. for 30 seconds, washed with water, and then heated and dried at 80 ° C. for 1 minute using an electric furnace.

(2g: acidic displacement plating)
10 parts of zinc sulfate heptahydrate (as zinc), 7.65 parts of ammonium ammonium fluoride and the rest are water, and a total of 1000 parts adjusted to pH 3.0 using a 10% by weight aqueous sodium hydroxide solution. An acidic displacement plating solution was prepared. The base metal was immersed in this plating solution at 30 ° C. for 30 seconds, washed with water, and then heated and dried at 80 ° C. for 1 minute using an electric furnace.

(2h: acidic displacement plating)
13 parts of zinc sulfate heptahydrate (as zinc), 3.6 parts of ferrous sulfate pentahydrate (as iron), 12.1 parts of 55% by weight aqueous hydrofluoric acid solution and the rest are water, A total of 1000 parts of acidic displacement plating solution adjusted to pH 2.0 using a 10% by mass aqueous sodium hydroxide solution was prepared. The base metal was immersed in this plating solution at 30 ° C. for 30 seconds, washed with water, and then heated and dried at 80 ° C. for 1 minute using an electric furnace.

(2i: acidic displacement plating)
13 parts of zinc sulfate heptahydrate (as zinc), 0.8 part of nickel sulfate hexahydrate (as nickel), 12.1 parts of 55% by weight aqueous hydrofluoric acid solution and the rest are water, and further 10 parts by weight A total of 1000 parts of acidic displacement plating solution adjusted to pH 3.0 using an aqueous sodium hydroxide solution of 10% was prepared. The base metal was immersed in this plating solution at 30 ° C. for 30 seconds, washed with water, and then heated and dried at 80 ° C. for 1 minute using an electric furnace.

(2j: acidic displacement plating)
13 parts of zinc sulfate heptahydrate (as zinc), 2.1 parts of cobalt sulfate heptahydrate (as cobalt), 9.7 parts of 55% by weight hydrofluoric acid aqueous solution and the rest are water, and further 10% A total of 1000 parts of acidic displacement plating solution adjusted to pH 3.0 using an aqueous sodium hydroxide solution of 10% was prepared. The base metal was immersed in this plating solution at 30 ° C. for 30 seconds, washed with water, and then heated and dried at 80 ° C. for 1 minute using an electric furnace.

(2k: acidic displacement plating)
13 parts of zinc sulfate heptahydrate (as zinc), 2.5 parts of ferrous sulfate pentahydrate (as iron), 0.3 part of nickel sulfate hexahydrate (as nickel), 55% by mass fluoride A total of 1000 parts of an acidic displacement plating solution was prepared in which 12.1 parts of aqueous hydrogen acid solution and the remainder were water, and further adjusted to pH 2.5 using a 10% by mass aqueous ammonia solution. The base metal was immersed in this plating solution at 30 ° C. for 30 seconds, washed with water, and then heated and dried at 80 ° C. for 1 minute using an electric furnace.

(2l: acidic displacement plating)
Zinc sulfate heptahydrate 13 parts (as zinc), ferrous sulfate pentahydrate 1.5 parts (as iron), cobalt sulfate heptahydrate 0.4 parts (as cobalt), 55% by mass fluoride A total of 1000 parts of acidic displacement plating solution was prepared in which 12.1 parts of aqueous hydrogen acid solution and the remainder were water, and further adjusted to pH 3.0 using a 10% by mass aqueous ammonia solution. The base metal was immersed in this plating solution at 30 ° C. for 30 seconds, washed with water, and then heated and dried at 80 ° C. for 1 minute using an electric furnace.

(2m: electrogalvanizing)
91.6 parts of zinc sulfate heptahydrate (as zinc), 200 parts of sodium sulfate and the rest are water, and 1000 parts of an electrogalvanizing solution adjusted to pH 4.0 using a 10% by mass aqueous ammonia solution. Produced. The base metal was immersed in this plating solution, a zinc plate was used as a counter electrode, and cathode electrolysis was performed at 30 ° C. and a current density of 5 A / dm ^{2 for} 10 seconds. Then, it washed with water and heat-dried at 80 degreeC for 1 minute using the electric furnace.

(2n: Electrogalvanizing)
32.7 parts of zinc sulfate heptahydrate (as zinc), 27.5 parts of ferrous sulfate pentahydrate (as iron), 200 parts of sodium sulfate and the rest are water, and a 10% by mass aqueous ammonia solution A total of 1000 parts of electrogalvanizing solution adjusted to pH 3.5 using was prepared. The base metal was immersed in this plating solution, a zinc plate was used as a counter electrode, and cathode electrolysis was performed at 30 ° C. and a current density of 5 A / dm ^{2 for} 10 seconds. Then, it washed with water and heat-dried at 80 degreeC for 1 minute using the electric furnace.

(2o: Electrogalvanizing)
32.7 parts of zinc sulfate heptahydrate (as zinc), 25 parts of nickel sulfate hexahydrate (as nickel), 200 parts of sodium sulfate and the rest are water, and pH 3 using a 10% by mass aqueous ammonia solution. A total of 1000 parts of electrogalvanizing solution adjusted to .5 was prepared. The base metal was immersed in this plating solution, a zinc plate was used as a counter electrode, and cathode electrolysis was performed at 30 ° C. and a current density of 5 A / dm ^{2 for} 10 seconds. Then, it washed with water and heat-dried at 80 degreeC for 1 minute using the electric furnace.

(2p: electrogalvanization)
32.7 parts of zinc sulfate heptahydrate (as zinc), 25 parts of cobalt sulfate heptahydrate (as cobalt), 200 parts of sodium sulfate and the remainder are water, and pH 4 using a 10% by mass aqueous ammonia solution. A total of 1000 parts of electrogalvanizing solution adjusted to 0.0 was prepared. The base metal was immersed in this plating solution, a zinc plate was used as a counter electrode, and cathode electrolysis was performed at 30 ° C. and a current density of 5 A / dm ^{2 for} 10 seconds. Then, it washed with water and heat-dried at 80 degreeC for 1 minute using the electric furnace.

(2q: electrogalvanizing)
32.7 parts of zinc sulfate heptahydrate (as zinc), 27.5 parts of ferrous sulfate pentahydrate (as iron), 25 parts of nickel sulfate hexahydrate (as nickel), 200 parts of sodium sulfate and The balance was water, and a total of 1000 parts of an electrogalvanizing solution adjusted to pH 3.5 using a 10% by mass aqueous ammonia solution was prepared. The base metal was immersed in this plating solution, a zinc plate was used as a counter electrode, and cathode electrolysis was performed at 30 ° C. and a current density of 5 A / dm ^{2 for} 10 seconds. Then, it washed with water and heat-dried at 0 degreeC for 1 minute using the electric furnace.

(2r: electrogalvanizing)
32.7 parts of zinc sulfate heptahydrate (as zinc), 27.5 parts of ferrous sulfate pentahydrate (as iron), 25 parts of cobalt sulfate heptahydrate (as cobalt), 200 parts of sodium sulfate and The balance was water, and a total of 1000 parts of an electrogalvanizing solution adjusted to pH 3.5 using a 10% by mass aqueous ammonia solution was prepared. The base metal was immersed in this plating solution, a zinc plate was used as a counter electrode, and cathode electrolysis was performed at 30 ° C. and a current density of 5 A / dm ^{2 for} 10 seconds. Then, it washed with water and heat-dried at 80 degreeC for 1 minute using the electric furnace.

(2s: electrogalvanizing)
91.6 parts of zinc sulfate heptahydrate (as zinc), 200 parts of sodium sulfate and the rest are water, and a total of 1000 parts of electrogalvanizing solution adjusted to pH 4.0 using 10% by mass aqueous ammonia solution Was made. Thereafter, the base metal was immersed in a hydrofluoric acid aqueous solution (nitric acid 10 mass%, hydrofluoric acid 5 mass%) at room temperature for 1 minute, and then washed with water. Thereafter, the base metal was immersed in the electrogalvanizing solution, a zinc plate was used as a counter electrode, and cathode electrolysis was performed at 30 ° C. and a current density of 5 A / dm ^{2 for} 10 seconds. Then, it washed with water and heat-dried at 80 degreeC for 1 minute using the electric furnace.

(2t: Electrogalvanizing)
91.6 parts of zinc sulfate heptahydrate (as zinc), 27.5 parts of ferrous sulfate pentahydrate (as iron), 200 parts of sodium sulfate and the rest are water, and a 10% by mass aqueous ammonia solution A total of 1000 parts of electrogalvanizing solution adjusted to pH 4.0 by using was prepared. Thereafter, the base metal was immersed in a hydrofluoric acid aqueous solution (nitric acid 10 mass%, hydrofluoric acid 5 mass%) for 1 minute at room temperature, and then washed with water. Thereafter, the base metal was immersed in the electrogalvanizing solution, a zinc plate was used as a counter electrode, and cathode electrolysis was performed at 30 ° C. and a current density of 5 A / dm ^{2 for} 10 seconds. Then, it washed with water and heat-dried at 80 degreeC for 1 minute using the electric furnace.

(2u: Zinc oxide coating)
Zinc oxide sol (dispersed particle size 20 nm, solid content concentration 1.5 mass%, pH 9.0) was applied with a # 3 bar coater, and then heated and dried at 120 ° C. for 1 minute in an electric furnace.

(2v: No undercoat)
The base metal was heat-dried at 80 ° C. for 1 minute using an electric furnace as it was without forming a base film.

[Method for forming resin film]
A resin film was formed by any of the following methods.

(3a: Heat lamination)
A maleic acid-modified polypropylene film having a thickness of 50 μm was thermocompression bonded to the surface of the base film at 190 ° C. and 1 MPa for 10 seconds.

(3b: Heat lamination)
The maleic acid-modified polypropylene film layer side of a two-layer resin film in which a maleic acid-modified polypropylene layer having a thickness of 20 μm and a copolymer layer of propylene and ethylene having a thickness of 30 μm are laminated on the surface of the base film, Thermocompression bonding was performed at 190 ° C. and 1 MPa for 10 seconds.

(3c: Heat lamination)
After applying a dispersion of acid-modified polypropylene (trade name: R-120K, non-volatile content: 20% by mass, manufactured by Mitsui Chemicals, Inc.) to the surface of the undercoat using a # 8SUS Meyer bar, An adhesive layer was formed by drying at 200 ° C. for 1 minute in a hot air circulating drying oven. Thereafter, a 30 μm-thick polypropylene film (manufactured by Tosero Co., Ltd., “CPPS”) was thermocompression bonded at 190 ° C. and 1 MPa for 10 seconds to the surface of the adhesive layer on the base film.

(3d: extrusion lamination)
Extrusion lamination was performed by extruding acid-modified polypropylene as a molten resin layer having a thickness of 15 μm on the surface of the base film, and then bonding a polypropylene film having a thickness of 30 μm (manufactured by Tosero Co., Ltd., “CPPS”).

(3e: Dry lamination)
A urethane-based dry laminate adhesive (manufactured by Toyo Morton Co., Ltd., trade name: AD-503 / CAT10, non-volatile content: 25% by mass) was applied to the surface of the base film by bar coating using a # 8SUS Meyer bar. Then, it dried at 80 degreeC and 1 minute with the electric furnace, and formed the adhesive bond layer. Thereafter, the adhesive layer and a corona discharge-treated surface of a 30 μm-thick unstretched polypropylene film (trade name: FCZX, manufactured by Nimura Chemical Industry Co., Ltd.) were pressure-bonded at 100 ° C. and 1 MPa, and then heated at 40 ° C. Cured for days.

[Production of test materials]
The above-described base metal was spray-degreased with a 2% aqueous solution of fine cleaner 359E (manufactured by Nihon Parkerizing Co., Ltd., alkaline degreasing agent) at 50 ° C. for 10 seconds, and the surface was washed with water. It prepared as a base metal used by 1-71 and Comparative Examples 1-12.

  Next, each treatment shown in Tables 1 to 4 was applied to the base metal used in Examples 1 to 71 and Comparative Examples 1 to 12 shown in Tables 1 to 4 to form a base film. In Examples 1 to 71 shown in Tables 1 to 4, any one of 2a to 2t was selected, and in Comparative Examples 1 to 12, 2u or 2v was selected.

Here, since the base metal is etched in the case of displacement plating, the etching amount (g / m ² ) was measured. The amount of etching was determined by ICP analysis (ICPE-9000, manufactured by Shimadzu Corporation) for the base metal eluted in the displacement plating solution. The results are shown in Tables 1 to 4. Further, the adhesion amount (g / m ² ) of metal elements (Zn, Fe, Ni, Co, etc.) constituting the undercoat was also quantified by ICP analysis. The amount of adhesion was measured by immersing and dissolving the base metal provided with the base film in 60% nitric acid, and analyzing the solution by ICP analysis. When 1 g / m ² of metal element is attached, the thickness of the base film is about 0.5 μm. The results are shown in Tables 1 to 4. Further, the surface of the undercoat was subjected to XPS analysis (manufactured by Shimadzu Corporation, ESCA-850M), and the chemical state of the zinc element in the undercoat was identified from the peak position of the ZnLMM Auger spectrum. When the peak position of the ZnLMM Auger spectrum is 993.6 eV, the zinc element is in a metallic state, and when it is 988.6 eV, the zinc element is in an oxidized state. The results are shown in Tables 1 to 4.

  Next, each treatment laminating process shown in Tables 1 to 4 was applied to the base metal with base film used in Examples 1 to 71 and Comparative Examples 1 to 12 shown in Tables 1 to 4, and resin. A film was formed.

  Next, the obtained metal exterior materials with resin films of Examples 1 to 71 and Comparative Examples 1 to 12 were subjected to deep drawing. First, the metal exterior material with a resin film punched out to a diameter of 160 mm was drawn (first time) to produce a cup having a diameter of 100 mm. Subsequently, the cup was again drawn to a diameter of 75 mm (second time), and further drawn to a diameter of 65 mm (third time) to prepare a can as a test material. The ironing ratio (thinning ratio) in the first drawing process, the second drawing process, and the third drawing process was 5%, 15%, and 15%, respectively.

[Performance evaluation]
The initial adhesion, durability adhesion, electrolyte solution adhesion maintenance, and liquid stability of the can (test material) after deep drawing the metal exterior material with a resin film were evaluated as follows. The results are shown in Tables 1 to 4.

(Initial adhesion)
The initial adhesion was evaluated for the can, which is a test material after deep drawing. Cans can be prepared, and there is no peeling of the resin film and excellent initial adhesion is designated as “3 points”, a part of the resin film is peeled off as “2 points”, and the resin film is peeled off as “ 1 point ".

(Electrolytic solution adhesion resistance)
A can, which is a test material after deep drawing, is an electrolyte for a lithium ion secondary battery to which 1000 ppm of ion-exchanged water filled in an airtight container is added (electrolyte: 1 mol / L LiPF ₆ , solvent volume ratio; After being immersed in EC: DMC: DEC = 1: 1: 1), it was put into a constant temperature bath at 60 ° C. for 7 days. “EC” refers to ethylene carbonate, “DMC” refers to dimethyl carbonate, and “DEC” refers to diethyl carbonate. Thereafter, the specimen was taken out, immersed in ion-exchanged water for 1 minute, swung and washed, and then dried at 100 ° C. for 10 minutes in an electric furnace. Then, the surface of the resin film is scratched with the tip of tweezers, and “4 points” indicates that the resin film does not peel at all, and “3 points” indicates that it is peeled but has high scratch resistance and is at a practical level. What peeled off by force was made into "2 points", and what has already peeled the resin film was made into "1 point."

  As shown in Tables 1 to 4, the test materials of Examples 1 to 71 (metal exterior materials with a resin film according to the present invention) were used as electrolytes compared to the test materials of Comparative Examples 1 to 12. Even when immersed, it was possible to maintain the adhesion, and it was confirmed that the electrolyte solution adhesion retention was excellent.

1 Base metal 2 Base film (metal zinc film or metal zinc-containing film)
3 Resin film (laminate film or resin coating)
10 Metal exterior with resin film

Claims (8)

  A base metal, a base coating provided on one or both surfaces of the base metal, and a laminate film or a resin coating provided on the base coating, wherein the base coating is a metal zinc coating or A metal exterior material with a resin film, which is a metal zinc-containing film.   The metal exterior material with a resin film according to claim 1, wherein the laminate film or the resin coating film contains polyolefin or acid-modified polyolefin.   The metal exterior material with a resin film according to claim 1 or 2, wherein the base metal is any one selected from aluminum or an alloy thereof, stainless steel, copper or an alloy thereof, and nickel or an alloy thereof.   The metal exterior material with a resin film of any one of Claims 1-3 in which the said metal zinc containing film | membrane contains 1 type, or 2 or more types of elements chosen from iron, nickel, and cobalt.   The metal exterior material with a resin film according to any one of claims 1 to 4, which is subjected to deep drawing processing, ironing processing, or stretch drawing processing. Forming a metal zinc film or a metal zinc-containing film as a base film by displacement plating or electroplating on one or both surfaces of the base metal; and
And a step of forming a laminate film or a resin coating film on the undercoat. The method for producing a metal exterior material with a resin film, comprising:   The manufacturing method of the metal exterior material with a resin film of Claim 6 which further has any 1 or 2 or more processing process chosen from deep drawing processing, ironing processing, and stretch drawing processing.   The manufacturing method of the metal exterior material with a resin film of Claim 6 or 7 which further has the process of removing the oxide film on the surface of the said base metal before the formation process of the said base film.

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