WO2022073309A1 - 一种用于电池封装的彩色铝塑膜、镀膜彩色铝合金及其制备方法 - Google Patents

一种用于电池封装的彩色铝塑膜、镀膜彩色铝合金及其制备方法 Download PDF

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WO2022073309A1
WO2022073309A1 PCT/CN2020/142400 CN2020142400W WO2022073309A1 WO 2022073309 A1 WO2022073309 A1 WO 2022073309A1 CN 2020142400 W CN2020142400 W CN 2020142400W WO 2022073309 A1 WO2022073309 A1 WO 2022073309A1
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layer
aluminum
color
aluminum alloy
plastic film
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French (fr)
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赵金保
代威明
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Xiamen University
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Xiamen University
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Priority claimed from CN202011079518.0A external-priority patent/CN112522757A/zh
Priority claimed from CN202011078024.0A external-priority patent/CN112389033A/zh
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the invention belongs to the technical field of aluminum-plastic films, and in particular relates to a color aluminum-plastic film for battery packaging, a color-coated aluminum alloy and a preparation method thereof.
  • the aluminum-plastic film is used as the outer packaging material of the battery to encapsulate the battery.
  • the battery encapsulated by the aluminum-plastic film has the advantages of high energy density, easy processing into various shapes, and the advantages of thinning and light weight.
  • the existing aluminum-plastic film endows the battery with many excellent properties
  • the existing aluminum-plastic film still has the following defects: the existing aluminum-plastic film product has a single appearance design and the prominence of the text is limited, and the existing aluminum-plastic film is mainly composed of transparent casting. It is composed of polypropylene film, transparent polyamide fiber, transparent adhesive and aluminum foil, so from the appearance, the aluminum-plastic film shows the color of the aluminum foil itself, so the color of the text printed on the surface of the aluminum-plastic film that characterizes the product information For example, when it is white and other light colors, its appearance is less prominent, which makes the appearance design of the aluminum-plastic film not rich enough.
  • the commonly used aluminum-plastic films for batteries are not printed, and the appearance looks like a monotonous metallic color. The reason is that most of them are difficult to color, difficult to reconcile the color and difficult to maintain the color. There are also problems that are easy to deform and difficult to process. And other issues. Some inks are added to the adhesive, mainly black, the color is monotonous, and the amount of carbon black added is too much, which is difficult to disperse and easy to settle. The molding performance of the plastic film is reduced, and delamination is particularly prone to occur, which affects the use and the final appearance of the aluminum plastic film. According to statistics, in the actual production process, the process of coating black matte oil will lead to the loss of about 30-40% of the aluminum-plastic film, which greatly increases the cost.
  • the single metallic color of the existing aluminum-plastic film packaging materials for batteries limits the design of the outer packaging pattern of the battery, and the use of inks easily leads to a decrease in the yield and performance of the aluminum-plastic film.
  • the purpose of the present invention is to overcome the deficiencies of the prior art, and to provide a colored aluminum-plastic film for battery packaging and a preparation method thereof.
  • the aluminum foil layer is endowed with a variety of colors, providing better character highlighting and color variability, and at the same time ensuring good adhesion between the substrate layer and the aluminum foil layer, solving the above-mentioned problems in the background art.
  • One of the technical solutions adopted by the present invention to solve the technical problem is to provide a colored aluminum-plastic film for battery packaging, which sequentially includes a base material layer, a first adhesive layer, and a metallized film layer from outside to inside. , aluminum foil layer, second adhesive layer and heat sealing layer;
  • the aluminum foil layer includes an intermediate layer and an anodized layer, and the anodized layer is arranged on one side or both sides of the intermediate layer; the metallized film layer is attached to the surface of the anodized layer by ion sputtering, for Showing a different color from the aluminum foil or the plated metal itself; the substrate layer is a transparent insulating material.
  • the thickness of the metal coating layer is 1-100 nm
  • the coating metal includes gold, platinum, and chromium
  • the particle size of the coating metal is 1-100 nm.
  • the thickness of the anodized layer is 10-2000 nm, and holes with a diameter of 30-140 nm are uniformly distributed on the anodized layer.
  • the second technical solution adopted by the present invention to solve the technical problem is: a preparation method of the above-mentioned colored aluminum-plastic film is provided, which comprises the following steps:
  • the aluminum foil is anodized on one or both sides to obtain an aluminum foil layer composed of an intermediate layer and an anodized layer;
  • the voltage of the anodization is 3-120V or the current density is 50-800mA/ dm 2 , the oxidation time is 5 ⁇ 60min, the electrolyte adopts at least one of 0.1 ⁇ 0.5mol/L phosphoric acid, sulfuric acid and oxalic acid, and the temperature of the electrolyte bath is 20 ⁇ 30°C;
  • Metal spray coating use an ion sputterer to spray metal on the surface of the aluminum foil layer of the anodic oxide layer, and the spray time is 15 to 60 s to obtain a colored laminate;
  • composite base material layer use the first adhesive layer to connect the base material layer on the surface of the colored laminated body in step (2) to obtain a laminated body compounded with a base material;
  • the aluminum foil in the step (1) is annealed, and is pretreated by alkali washing, degreasing, water washing, acid washing neutralization, and water washing before anodizing.
  • the step (3) and the step (4) use a dry lamination method or an extrusion molding method to realize the interlayer connection.
  • the invention also provides a method for preparing a coated color aluminum alloy.
  • the aluminum alloy is first subjected to anodizing treatment to obtain an aluminum alloy with an anodized film layer on the surface; and then the surface of the anodized layer is attached by ion sputtering for
  • the colored metal film layer is prepared by controlling the voltage or current, time and the type of coating metal of the anodizing treatment to obtain a color-coated color aluminum alloy with a controllable color; wherein, the voltage of the anodizing treatment is 3-120V or The current density is 50 ⁇ 800mA/dm 2 , and the oxidation time is 5 ⁇ 60min; the coating metal includes gold, platinum, and chromium with a particle size of 1 ⁇ 100nm; the color presented is in the visible light wavelength range except the color of aluminum and the coating metal itself s color.
  • This scheme uses constant voltage or constant current anodization combined with ion sputtering technology to make the aluminum-plastic film show different colors such as red, orange, yellow, purple, blue, etc., and control the color regularly by adjusting the parameters of anodization (especially through Change the type and concentration of anodized electrolyte, oxidation voltage, time and other process parameters, when the same metal is used for spray plating, the aluminum foil layer will produce different colors), give the aluminum foil layer a variety of colors, and provide better text highlighting Sex and color variability;
  • This solution replaces the ink to make the aluminum-plastic film appear colorful, ensures the good adhesion between the substrate layer and the aluminum foil layer, effectively avoids the degradation of the molding performance and delamination of the aluminum-plastic film caused by the ink, and obtains a color that meets the battery packaging requirements.
  • Aluminum plastic film
  • the present invention replaces the traditional dyeing and sealing process by anodizing combined with ion sputtering technology, so that the surface of the aluminum alloy presents different colors visible to the naked eye, and by controlling the voltage or current, time and type of coating metal of the anodizing process,
  • the control coating color aluminum alloy presents different colors such as red, orange, yellow, green, blue, purple, gray, etc., with simple operation, high production efficiency, bright and beautiful colors.
  • Fig. 1 is the layer structure diagram of the color aluminum-plastic film of Example 1.
  • FIG. 2 is a layer structure diagram of the color aluminum-plastic film of Example 2.
  • FIG. 2 is a layer structure diagram of the color aluminum-plastic film of Example 2.
  • FIG. 3 is a schematic diagram of a device for double-sided anodic oxidation.
  • Figure 4 is a schematic diagram of a device for single-sided anodizing.
  • Fig. 5 is the layer structure diagram of color aluminum alloy
  • Figure 6 is a photo of the actual aluminum alloy prepared under different parameters of the method.
  • 1- base material layer 2- first adhesive layer, 3- metallized film layer, 4- anodized layer (outer layer), 5- aluminum foil layer
  • the invention relates to a color aluminum plastic film for battery packaging, which sequentially comprises a base material layer, a first adhesive layer, a metallized film layer, an aluminum foil layer, a second adhesive layer and a heat-sealing layer from the outside to the inside;
  • the aluminum foil layer includes an intermediate layer and an anodized layer, and the anodized layer is arranged on one side or both sides of the intermediate layer; the metallized film layer is attached to the surface of the anodized layer by ion sputtering, for Showing a different color from the aluminum foil or the plated metal itself; the substrate layer is a transparent insulating material.
  • the thickness of the base material layer is not more than 30 ⁇ m, and the base material layer 1 is the layer on the outermost layer side.
  • the raw material for forming the base material layer 1 is not particularly limited as long as it has insulating properties. Examples of raw materials for forming the base material layer 1 include polyamide, polyester, epoxy resin, acrylic resin, fluororesin, polyurethane, silicone resin, phenolic resin, polyetherimide, polyimide, and polycarbonate. and their mixtures or copolymers.
  • polyamides include aliphatic polyamides such as nylon 6, nylon 66, nylon 610, nylon 12, nylon 46, and copolymers of nylon 6 and nylon 66; Hexamethylenediamine-isophthalic acid-terephthalic acid such as nylon 6I, nylon 6T, nylon 6IT, nylon 6I6T (I represents isophthalic acid, T represents terephthalic acid) as constituent units of phthalic acid
  • Aromatic-containing polyamides such as copolyamides and polymetaxylylene adipamide (MXD6); alicyclic polyamides such as polyaminomethylcyclohexyl adipamide (PACM6); and lactam components and/or or 4,4'-diphenylmethane-diisocyanate and other isocyanate components copolymerized polyamides, polyester amide copolymers that are copolymers of copolyamides, polyesters, and polyalkylene ether glycols, and polyethers Esteramide copoly
  • the stretched polyamide film is excellent in stretchability, can prevent whitening due to cracking of the resin of the base material layer 1 during molding, and is suitable for use as a material for forming the base material layer 1 .
  • polyester examples include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polymethylene terephthalate Ethylene terephthalate, copolyester mainly containing ethylene terephthalate as repeating unit, copolyester mainly containing isobutylene terephthalate as repeating unit, etc.
  • copolyester having ethylene terephthalate as the main body of the repeating unit specifically, ethylene terephthalate as the main body of the repeating unit and inter-ethylene terephthalate can be mentioned.
  • Polyester copolymers polymerized by phthalate hereinafter, abbreviated as polyethylene (terephthalate/isophthalate)), polyethylene (terephthalate/meta) phthalate), polyethylene (terephthalate/adipate), polyethylene (terephthalate/sodium sulfoisophthalate), polyethylene ( terephthalate/sodium isophthalate), polyethylene (terephthalate/phenyl-dicarboxylate), polyethylene (terephthalate/sebacic acid) ester) etc.
  • polyethylene (terephthalate/isophthalate) polyethylene (terephthalate/meta) phthalate), polyethylene (terephthalate/adipate), polyethylene (terephthalate/sodium sulfoisophthalate), polyethylene ( terephthalate/sodium isophthalate), polyethylene (terephthalate/phenyl-dicarboxylate), polyethylene (terephthalate/sebacic acid) ester) etc.
  • polyesters are used individually by 1 type, or may be used in combination of 2 or more types. Polyester has the advantages of being excellent in resistance to an electrolyte solution, and hardly causing whitening to adhere to an electrolyte solution, and is suitable for use as a material for forming the base material layer 1 .
  • the base material layer 1 may be formed of a monoaxially or biaxially stretched resin film, or may be formed of an unstretched resin film.
  • the resin film after uniaxial or biaxial stretching, especially the resin film after biaxial stretching is suitable for use as the base material layer 1 because heat resistance is improved by orientation crystallization.
  • the resin film forming 1 from the viewpoint of exhibiting high formability, nylon and polyester are preferable, biaxially stretched nylon and biaxially stretched polyester are more preferable, and biaxially stretched polyester is particularly preferable. stretch nylon.
  • the thickness of the polyamide film layer is not particularly limited, but from the viewpoint of reducing the thickness of the aluminum plastic film and exhibiting excellent moldability, it is preferably 30 ⁇ m or less, more preferably about 1 to 25 ⁇ m, and even more preferably about 10 to 25 ⁇ m .
  • the thickness of the polyester film layer is not particularly limited, but from the viewpoint of reducing the thickness of the aluminum plastic film and exhibiting excellent moldability, it is preferably about 20 ⁇ m or less, more preferably about 1 to 15 ⁇ m, and still more preferably 3 to 12 ⁇ m about.
  • the 1st adhesive bond layer 2 is a layer provided in between the base material layer 1 and the metal plating film layer 3 as needed in order to adhere firmly.
  • the 1st adhesive bond layer is formed of the adhesive agent which can bond a base material layer and a metal plating film layer.
  • the adhesive for forming the first adhesive layer may be a two-liquid curing type adhesive or a one-liquid curing type adhesive.
  • the adhesion mechanism of the adhesive used to form the first adhesive layer is not particularly limited, and any type such as chemical reaction type, solvent evaporation type, hot melt type, and hot pressing type may be used.
  • adhesive components that can be used to form the first adhesive layer include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene terephthalate, and polyethylene terephthalate.
  • Polyester resins such as butylene naphthalate, polyethylene isophthalate, and copolyester; polyether adhesives; polyurethane adhesives; epoxy resins; phenolic resins; Polyamide-based resins such as nylon 6, nylon 66, nylon 12, and copolyamides; polyolefin-based resins such as polyolefins, carboxylic acid-modified polyolefins, and metal-modified polyolefins; polyvinyl acetate-based resins; cellulose (meth)acrylic resin; polyimide resin; polycarbonate; amino resin such as urea resin and melamine resin; chloroprene rubber, nitrile rubber, styrene-butadiene Rubber such as rubber; Silicone resin, etc
  • the urethane-based adhesive examples include a urethane-based adhesive containing a main agent having a polyol component (A) and a curing agent having a polyisocyanate component (B), and the polyol component (A) includes a polyester polyol Alcohol (A1), polyester polyol (A1) is a polyester polyol with a number average molecular weight of 5,000 to 50,000 composed of a polybasic acid component and a polyol component, and contains an aromatic polybasic acid component in 100 mol% of the polybasic acid component 45 to 95 mol %, and the tensile stress at the time of 100% stretching of the adhesive bond layer is 100 kg/cm 2 or more and 500 kg/cm 2 or less.
  • polyester polyol (A1) is a polyester polyol with a number average molecular weight of 5,000 to 50,000 composed of a polybasic acid component and a polyol component, and contains an aromatic polybasic acid component in 100 mol% of the polybasic acid
  • a polyurethane-based adhesive containing a main agent and a polyisocyanate curing agent can also be mentioned.
  • the main agent contains a polyol component (A) and a silane coupling agent (B), and the polyol component (A) contains a glass transition temperature of 40 5 to 50 mass % of polyester polyol (A1) above °C and 95 to 50 mass % of polyester polyol (A2) with glass transition temperature lower than 40 °C, relative to the hydroxyl group derived from polyol component (A) and
  • the equivalence ratio [NCO]/([OH]+[COOH]) of the isocyanate groups contained in the curing agent is 1 to 30 in total of the carboxyl groups.
  • the thickness of the first adhesive layer is not particularly limited as long as it can function as an adhesive layer. From the viewpoint of thinning and weight reduction of the aluminum plastic film, the thickness of the first adhesive layer is For example, it is preferably about 1 to 10 ⁇ m, more preferably about 1 to 5 ⁇ m, and still more preferably about 1 to 3 ⁇ m.
  • the metallized film layer is sprayed on the anodized layer by ion sputtering technology, which can form the appearance of various colors, provide better text highlighting and color variability, and achieve the effect of color aluminum plastic film. It should be pointed out that by changing the type and concentration of the electrolyte in the anodizing process of the aluminum foil layer, as well as the oxidation voltage, time and other process parameters, when the same metal is used for spray plating, the aluminum foil layer will produce different colors. For example, sputtering aluminum foils treated with different anodizing conditions with gold will produce different colors such as red, orange, yellow, purple, and blue.
  • the coating metal selected for the metal coating film layer is one or more metals such as gold, platinum, silver, titanium, and chromium, preferably gold, platinum, and chromium metals.
  • the plating thickness of the metal plating is not particularly limited, but from the viewpoint of economy and aesthetics, the plating thickness is, for example, about 1 to 100 nm, preferably about 2 to 30 nm.
  • the anodized layer is obtained by anodizing the aluminum foil layer, which is mainly used as the base of the metallized layer. At the same time, the pores formed by anodization have good corrosion resistance and adsorption, which is beneficial to improve the adhesion with the adhesive layer 1. Adhesion.
  • the anodic oxide layer is obtained by constant voltage or constant current anodic oxidation process, and the temperature of the anodic oxidation bath is controlled at 20-30°C.
  • the aluminum foil layer is obtained by alkali washing, degreasing, water washing, acid washing neutralization, water washing, anodizing, water washing and drying.
  • the thickness of the oxide layer is 10-2000 nm, preferably 20-1500 nm, more preferably 50-1000 nm.
  • the oxide layer is observed by scanning electron microscope (SEM) as uniformly distributed pores, and the diameter of the pores is 30-140 nm, preferably 30-120 nm, more preferably 30-100 nm.
  • the voltage range of anodic oxidation is 3 ⁇ 120V, the current density is 50 ⁇ 300mA/dm 2 , and the oxidation time is 5 ⁇ 60min.
  • the electrolyte for anodic oxidation can be at least one of 0.1-0.5mol/L phosphoric acid, sulfuric acid, and oxalic acid; or,
  • the electrolyte for anodic oxidation can be at least one of phosphoric acid, sulfuric acid, and oxalic acid, and at least one of acid salt or fluoride corresponding to the acid group.
  • the aluminum foil layer is a layer that has the function of preventing water vapor, oxygen, light, etc. from entering the inside of the battery in addition to improving the strength of the aluminum plastic film. From the viewpoint of preventing the occurrence of wrinkles or pinholes in the aluminum foil layer, it is more preferable to use, for example, annealed aluminum (JIS H4160: 1994A8021H-O, JIS H4160: 1994A8079H-O, JIS H4000: 2014A8021P-O, JIS H4000: 2014A8079P- O) and other soft aluminum alloy foils are formed.
  • the thickness of the aluminum foil layer is not particularly limited as long as it can function as a barrier layer for water vapor or the like.
  • the upper limit is about 100 ⁇ m. or less, preferably about 80 ⁇ m or less, more preferably about 50 ⁇ m or less, still more preferably about 40 ⁇ m or less
  • the lower limit is preferably about 10 ⁇ m or more
  • the range of the thickness can be about 10 to 100 ⁇ m, about 10 to 80 ⁇ m, preferably 10 ⁇ 50 ⁇ m or so, 10 ⁇ 40 ⁇ m.
  • the 2nd adhesive bond layer is a layer provided between these layers as needed in order to make an aluminum foil layer and a heat-sealing layer adhere firmly.
  • the second adhesive layer is formed of an adhesive capable of bonding the aluminum foil layer and the heat-sealing layer.
  • the adhesive used for the formation of the second adhesive layer 6 the adhesion mechanism, the types of adhesive components, and the like are the same as in the case of the above-described adhesive layer 2 .
  • the adhesive component used in the second adhesive layer 6 a polyolefin-based adhesive with little swelling due to an electrolyte solution is preferably used, and a polyolefin-based resin is preferably used.
  • the second adhesive bond layer may be a cured product of a resin composition containing an acid-modified polyolefin and a curing agent from the viewpoint of thinning and forming an aluminum plastic film for a battery having excellent shape stability after molding.
  • the acid-modified polyolefin compounds similar to carboxylic acid-modified polyolefin and carboxylic acid-modified cyclic polyolefin are preferable.
  • curing agent if it can harden an acid-modified polyolefin, it will not specifically limit.
  • the curing agent include epoxy-based curing agents, polyfunctional isocyanate-based curing agents, carbodiimide-based curing agents, and oxazoline-based curing agents.
  • the epoxy-based curing agent is not particularly limited as long as it is a compound having at least one epoxy group.
  • epoxy-based curing agents include epoxy resins such as bisphenol A diglycidyl ether, modified bisphenol A diglycidyl ether, novolak glycidyl ether, glycerol polyglycidyl ether, and polyglycerol polyglycidyl ether. .
  • the polyfunctional isocyanate-based curing agent is not particularly limited as long as it is a compound having two or more isocyanate groups.
  • Specific examples of the polyfunctional isocyanate-based curing agent include isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), Products obtained by polymerizing or nurateing them, their mixtures, or copolymers with other polymers, and the like.
  • a polycarbodiimide compound having at least two or more carbodiimide groups is preferable.
  • the oxazoline-based curing agent is not particularly limited as long as it is a compound having an oxazoline skeleton.
  • Specific examples of the oxazoline-based curing agent include Epocros series manufactured by Nippon Shokubai Co., Ltd., and the like.
  • the curing agent may be composed of two or more kinds of compounds.
  • the content of the curing agent in the resin composition forming the second adhesive layer is preferably in a range of about 0.1 to 50 mass %, more preferably in a range of about 0.1 to 30 mass %, and still more preferably in a range of about 0.1 to 10 mass % around the range.
  • the thickness of the second adhesive layer is not particularly limited as long as it can function as an adhesive layer. From the viewpoint of thinning and weight reduction of the aluminum plastic film, the thickness of the second adhesive layer is For example, it is preferably about 1 to 10 ⁇ m, more preferably about 1 to 5 ⁇ m, and still more preferably about 1 to 3 ⁇ m.
  • the role of the heat seal layer is to provide excellent chemical resistance against highly corrosive electrolytes used in batteries, and to impart heat sealability to the aluminum plastic film.
  • the resin component used for the heat seal layer is not particularly limited, and examples thereof include polyolefin, cyclic polyolefin, acid-modified polyolefin, and acid-modified cyclic polyolefin. That is, the heat seal layer may contain a polyolefin skeleton, and preferably contains a polyolefin skeleton. For example, it can be analyzed by Fourier transform infrared spectroscopy, gas chromatography-mass spectrometry, or the like, and the analysis method is not particularly limited.
  • peaks derived from maleic anhydride are detected in the vicinity of the wavenumber of 1760 cm-1 and the vicinity of the wavenumber of 1780 cm-1.
  • the analysis can be performed by nuclear magnetic resonance spectroscopy.
  • polystyrene resins examples include polyethylenes such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene; homopolypropylene and block copolymers of polypropylene (for example, propylene and ethylene) Block copolymers), polypropylene random copolymers (for example, random copolymers of propylene and ethylene) and other polypropylenes; terpolymers of ethylene-butene-propylene, etc.
  • polyethylene and polypropylene are preferably cited.
  • the cyclic polyolefin is a copolymer of an olefin and a cyclic monomer
  • examples of the olefin constituting the monomer of the cyclic polyolefin include ethylene, propylene, 4-methyl-1-pentene, butadiene, Isoprene, etc.
  • examples of the cyclic monomer constituting the above-mentioned cyclic polyolefin include cyclic olefins such as norbornene, and specific examples include cyclopentadiene, dicyclopentadiene, cyclohexadiene, and norbornene. Cyclic dienes such as dienes, etc.
  • these polyolefins cyclic olefins are preferred, and norbornene is more preferred.
  • the above-mentioned acid-modified polyolefin is a polymer obtained by block-polymerizing or graft-polymerizing the above-mentioned polyolefin with an acid component such as carboxylic acid.
  • an acid component such as carboxylic acid.
  • the acid component used for modification include carboxylic acids such as maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, and itaconic anhydride, or their acid anhydrides.
  • the above acid-modified cyclic polyolefin is copolymerized by substituting a part of the monomers constituting the cyclic polyolefin with ⁇ , ⁇ -unsaturated carboxylic acid or its anhydride, or by copolymerizing ⁇ , ⁇ -unsaturated carboxylic acid or its acid anhydride.
  • the cyclic polyolefin modified with carboxylic acid is the same as above.
  • the carboxylic acid used for the modification is the same as the acid component used for the modification of the above-mentioned polyolefin.
  • polyolefins such as polypropylene and carboxylic acid-modified polyolefins are preferred, and polypropylene and acid-modified polypropylene are more preferred.
  • the heat-sealing layer may be formed from one resin component alone, or may be formed from a blended polymer in which two or more resin components are combined.
  • the heat seal layer may be formed of only one layer, or may be formed of two or more layers using the same or different resin components.
  • the thickness of the heat seal layer is not particularly limited, but from the viewpoint of reducing the thickness of the aluminum plastic film for batteries and exhibiting excellent moldability, the upper limit is preferably about 80 ⁇ m or less, the amount of resin used can be reduced, and cost reduction can be achieved.
  • the lower limit about 10 ⁇ m or more is preferable, since generation of pinholes can be sufficiently prevented, so about 10 ⁇ m to 80 ⁇ m is preferable, and about 10 to 40 ⁇ m is more preferable.
  • Lamination of the first adhesive layer and the base material layer on the metallized film layer of the colored laminate can be carried out by the following dry lamination methods: extrusion method, gravure coating method, A coating method such as a roll coating method coats the adhesive for forming the first adhesive layer on the base material layer or the metal-plated film layer and dries it, and then laminates the metal-plated film layer or the base material layer and laminates the metal-plated film layer or base material layer. The first adhesive layer is cured.
  • the second adhesive layer and the heat seal layer are laminated on the aluminum foil layer of the colored laminate.
  • the second adhesive layer and the heat-sealing layer are laminated on the aluminum foil layer, for example, by the following method: (1) On the aluminum foil layer of the colored laminate, the second adhesive layer and the heat-sealing layer are co-extruded. (2) A laminate obtained by forming a second adhesive layer and a heat-sealed lamination layer, and laminating the laminate on a colored surface by a thermal lamination method. (3) Coating the above-mentioned resin composition for forming the second adhesive layer on the aluminum foil of the colored laminate by coating methods such as gravure coating, roll coating, etc.
  • Dry lamination method in which the heat-sealing layer is laminated and the second adhesive layer is cured; (4) the molten second adhesive layer is poured into the aluminum foil layer of the colored laminate A method (sandwich lamination method), etc., in which the colored laminate and the heat seal layer are pasted together with the second adhesive bond layer interposed therebetween.
  • method (3) is preferable.
  • the heat-sealing layer is a multilayer, it is preferable that the innermost layer of the heat-sealing layer is a layer formed by a dry lamination method or extrusion molding.
  • the color aluminum plastic film of the present invention is used to encapsulate the battery, and the battery element having at least a positive electrode, a negative electrode and an electrolyte is formed on the edge of the battery element in a state where the metal terminals connected to the positive electrode and the negative electrode respectively protrude to the outside.
  • the heat-sealing layers of the flange portion are heat-sealed to each other to seal, thereby providing a battery using a colored aluminum-plastic film for batteries.
  • the heat-sealing layer resin portion of the colored aluminum-plastic film for batteries of the present invention as the inner side (surface in contact with the battery element).
  • the colored aluminum-plastic film for batteries of the present invention can be used for either a primary battery or a secondary battery, and is preferably a secondary battery.
  • the type of secondary battery to which the colored aluminum plastic film for batteries of the present invention is applied is not particularly limited, and examples include lithium ion batteries, lithium ion polymer batteries, lead storage batteries, nickel-hydrogen storage batteries, nickel-cadmium storage batteries, nickel storage batteries -Iron batteries, nickel-zinc batteries, silver oxide-zinc batteries, metal-air batteries, polyvalent cation batteries, capacitors, etc.
  • lithium ion batteries and lithium ion polymer batteries are exemplified as preferable application objects of the colored aluminum-plastic film for batteries of the present invention.
  • a method for preparing a colored aluminum-plastic film for battery packaging includes the following steps:
  • the aluminum foil layer (thickness of 40 ⁇ m) is washed with alkali to remove oil, washed with water, neutralized by acid washing, and washed with water to obtain a clean aluminum foil layer.
  • the aluminum foil layer is anodized on both sides to obtain an anodized layer 4 (see Figure 3 for the anodization device), including an ammeter 10, an anodizing power supply 11, a voltmeter 12, graphite plate electrodes 13 and 16, an anodizing tank 14 and the electrolysis in the tank Liquid 15.
  • the electrolyte formula of the anodization is 0.1mol/L phosphoric acid, the constant voltage is 5V, the anodization time is 10min, and the temperature is 25°C to obtain the anodized layer 4 (thickness 1 ⁇ m) and the anodized layer (inner layer) 9 (thickness 1 ⁇ m) .
  • the anodized aluminum foil layer exhibits the original color of the aluminum foil to the naked eye.
  • Gold (element symbol Au) was sprayed on the anodic oxide layer 4 with an ion sputtering time for 30 s to obtain a gold-plated film layer 3 (thickness 20 nm), and a laminate A was formed.
  • the time parameters of the anodizing process are different, the color displayed by the coating metal at this time is not the color of the gold body, but purple, forming a purple stack A.
  • biaxially stretched nylon was dry-laminated via a 2-liquid-curable urethane-based adhesive (first adhesive layer 2, thickness 3 ⁇ m).
  • the film (substrate layer 1, thickness 25 ⁇ m) was press-bonded by being sandwiched between a rubber nip roll and a lamination roll heated to 100°C.
  • a 2-liquid curing type maleic anhydride-modified polypropylene adhesive (second adhesive layer 6 , the thickness of 3 ⁇ m) is superimposed on the other side of the aluminum foil layer after dry lamination.
  • a purple aluminum plastic film for a battery formed by a laminate of the intermediate layer 5, the aluminum foil anodized layer (inner layer) 9, the second adhesive layer 6, and the hot-melt resin layer 7.
  • the aluminum foil layer (thickness of 40 ⁇ m) is washed with alkali to remove oil, washed with water, neutralized by acid washing, and washed with water to obtain a clean aluminum foil layer.
  • a 2-liquid curing type maleic anhydride-modified polypropylene adhesive (second adhesive layer 6 , a thickness of 3 ⁇ m) and one side of the aluminum foil layer is laminated to form a laminated body B.
  • a single-sided anodic oxidation process includes an ammeter 10, an anodizing power supply 11, a voltmeter 12, a graphite plate electrode 13, and an anodizing tank. 14 and the electrolyte 15 in the tank.
  • the electrolyte formula of the anodization is 0.1mol/L phosphoric acid, the constant voltage is 5V, the anodization time is 50min, and the temperature is 25°C to obtain an anodized layer 4 (thickness 1 ⁇ m).
  • a biaxially stretched nylon film (substrate Layer 1, thickness 25 ⁇ m), was crimped by being sandwiched between a rubber nip roll and a lamination roll that had been heated to 100°C.
  • a yellow aluminum plastic film for batteries formed by a laminate of the intermediate layer, the second adhesive layer 6, and the hot-melt resin layer 7.
  • the aluminum foil layer (thickness of 40 ⁇ m) is washed with alkali to remove oil, washed with water, neutralized by acid washing, and washed with water to obtain a clean aluminum foil layer.
  • the aluminum foil layer is anodized on both sides to obtain an anodic oxide layer 4 (see Figure 3 for the anodic oxidation device).
  • the electrolyte formula of the anodization is 0.1mol/L phosphoric acid, the constant current is 800mA/dm 2 , the anodization time is 5min, and the temperature is 25°C to obtain the anodized layer 4 (thickness 1 ⁇ m) and the aluminum foil anodized layer (inner layer) 9 (thickness 1 ⁇ m).
  • Gold (element symbol Au) was sprayed on the anodic oxide layer 4 with an ion sputtering time for 30 s to obtain a gold-plated film layer 3 (thickness 20 nm), and a laminate A was formed.
  • the color displayed by the coating metal at this time is not the color of the gold body, but blue, forming a blue color.
  • biaxially stretched nylon was dry-laminated via a 2-liquid-curable urethane-based adhesive (first adhesive layer 2, thickness 3 ⁇ m).
  • the film (substrate layer 1, thickness 25 ⁇ m) was press-bonded by being sandwiched between a rubber nip roll and a lamination roll heated to 100°C.
  • a 2-liquid curing type maleic anhydride-modified polypropylene adhesive (second adhesive layer 6 , the thickness of 3 ⁇ m) is superimposed on the other side of the aluminum foil layer after dry lamination.
  • a blue aluminum-plastic film for a battery formed by a laminate of the intermediate layer, the aluminum foil anodized layer (inner layer) 9, the second adhesive layer 6, and the hot-melt resin layer 7.
  • the aluminum foil layer (thickness of 40 ⁇ m) is washed with alkali to remove oil, washed with water, neutralized by acid washing, and washed with water to obtain a clean aluminum foil layer.
  • a 2-liquid curing type maleic anhydride-modified polypropylene adhesive (second adhesive layer 6 , a thickness of 3 ⁇ m) and one side of the aluminum foil layer is laminated to form a laminated body B.
  • the electrolyte formula of the anodization is 0.1mol/L phosphoric acid, the constant current is 150mA/dm 2 , the anodization time is 30min, and the temperature is 25°C to obtain an anodized layer 4 (thickness 1 ⁇ m).
  • platinum (element symbol Pt) was sprayed on the anodic oxide layer 4 with an ion sputtering time, and the platinum spraying time was 30s to obtain a gold-plated film layer 3 (thickness 20nm).
  • the color displayed by the coating metal is not the color of the platinum body , instead, it shows purple, and a purple laminate C is formed.
  • a biaxially stretched nylon film (substrate Layer 1, thickness 25 ⁇ m), was crimped by being sandwiched between a rubber nip roll and a lamination roll that had been heated to 100°C.
  • a purple aluminum plastic film for batteries formed by a laminate of the intermediate layer, the second adhesive layer 6, and the hot-melt resin layer 7.
  • the electrolyte formula for anodic oxidation is 0.1 mol/L phosphoric acid, the constant current is 130 mA/dm 2 , and the anodic oxidation time is 30 min. Except that, it is the same as in Example 1 to obtain a green aluminum-plastic film for batteries. .
  • the electrolyte formula for anodization is 0.1mol/L phosphoric acid, a constant voltage of 120V is used, and an anodization time is 10min.
  • a red aluminum-plastic film for batteries was obtained.
  • the electrolyte formula for anodization is 0.1mol/L phosphoric acid, a constant current of 250mA/dm 2 is used, and an anodization time is 10min. Other than that, in the same manner as in Example 1, an orange aluminum-plastic film for batteries was obtained.
  • the electrolyte formula of anodization is 0.1mol/L phosphoric acid, a constant current of 250mA/dm 2 is used, and an anodization time is 20min.
  • a yellow aluminum-plastic film for batteries was obtained.
  • the electrolyte formula of anodization is 0.1mol/L phosphoric acid and 2g/L sodium fluoride, a constant current of 250mA/dm 2 is used, and the anodization time is 30min.
  • a gray aluminum-plastic film for batteries was obtained.
  • the electrolyte formula for anodization is 0.1mol/L phosphoric acid, a constant current of 150mA/dm 2 is used, and an anodization time is 40min.
  • a green aluminum-plastic film for batteries was obtained.
  • the following embodiment is a coating method of colored aluminum alloy, and the coating metal can be gold or platinum.
  • the anodic oxidation treatment device used in the anodic oxidation tank 14 is provided with a graphite plate electrode 13 and an electrode of the aluminum alloy layer 5 or 21, and the graphite plate electrode 13 and the electrode of the aluminum alloy layer 5 or 21 are immersed or partially Immerse in the electrolyte 15, one end of the two is connected to the power source 11 and a voltmeter 12 and/or an ammeter 10 are provided.
  • the aluminum alloy 1 with a thickness of 40 ⁇ m was alkali-washed with a 40 g/L sodium hydroxide solution for 30 s, and then washed with water. Then neutralize with 10% mass fraction of nitric acid solution for 30s and wash with water to obtain clean aluminum alloy.
  • the aluminum alloy 21 is anodized to obtain an anodized layer 22.
  • the anodized electrolyte formula is 0.1 mol/L phosphoric acid, the constant voltage is 5V, the anodization time is 10min, and the temperature is 25°C.
  • the aluminum alloy now displays the original color of the aluminum alloy.
  • the aluminum alloy 1 with a thickness of 40 ⁇ m was alkali-washed with a 40 g/L sodium hydroxide solution for 30 s, and then washed with water. Then neutralize with 10% mass fraction of nitric acid solution for 30s and wash with water to obtain clean aluminum alloy.
  • the aluminum alloy 21 is anodized to obtain an anodized layer 22.
  • the anodized electrolyte formula is 0.1mol/L phosphoric acid, a constant current of 75mA/dm 2 is used, the anodization time is 40min, the temperature is 25°C, and the anode
  • the oxidized aluminum alloy now shows the original color of the aluminum alloy.
  • the anodic oxide layer 22 is sprayed with platinum (element symbol Pt) with an ion sputtering time, and the platinum spray time is 30s to obtain a gold-plated film layer 23 (thickness 20nm).
  • the color displayed by the coating metal is not the color of the platinum body, Instead, it shows a purple color, resulting in a purple-coated aluminum alloy.
  • a method for preparing a coated yellow aluminum alloy can be realized by controlling constant voltage or constant current.
  • the aluminum alloy 21 with a thickness of 40 ⁇ m was alkali-washed with a 40 g/L sodium hydroxide solution for 30 s, and then washed with water. Then neutralize with 10% mass fraction of nitric acid solution for 30s and wash with water to obtain clean aluminum alloy.
  • the aluminum alloy 21 is anodized to obtain an anodized layer 22.
  • the anodized electrolyte formula is 0.1 mol/L phosphoric acid, a constant voltage of 5V is used, the anodization time is 50min, and the temperature is 25°C.
  • the aluminum alloy now displays the original color of the aluminum alloy.
  • the electrolyte formula of anodization is 0.1mol/L phosphoric acid, a constant current of 250mA/dm 2 is used, and an anodization time is 20min. Other than that, in the same manner as 1 in Example 1, a yellow plated aluminum alloy was obtained.
  • a method for preparing a coated blue aluminum alloy can be realized by controlling constant voltage or constant current.
  • the aluminum alloy 21 with a thickness of 40 ⁇ m was alkali-washed with a 40 g/L sodium hydroxide solution for 30 s, and then washed with water. Then neutralize with 10% mass fraction of nitric acid solution for 30s and wash with water to obtain clean aluminum alloy.
  • the aluminum alloy 21 is anodized to obtain an anodized layer 22.
  • the anodized electrolyte formula is 0.1 mol/L phosphoric acid, the constant voltage is 20V, the anodization time is 10min, and the temperature is 25°C.
  • the aluminum alloy now displays the original color of the aluminum alloy.
  • the electrolyte formula of anodization is 0.1mol/L phosphoric acid, a constant current of 800mA/dm 2 is used, and the anodization time is 5min. Other than that, in the same manner as 1 in Example 11, a blue plated aluminum alloy was obtained.
  • a method for preparing a coated red aluminum alloy can be realized by controlling a constant voltage or constant current.
  • the aluminum alloy 21 with a thickness of 40 ⁇ m was alkali-washed with a 40 g/L sodium hydroxide solution for 30 s, and then washed with water. Then neutralize with 10% mass fraction of nitric acid solution for 30s and wash with water to obtain clean aluminum alloy.
  • the aluminum alloy 21 is anodized to obtain an anodized layer 22.
  • the anodized electrolyte formula is 0.1 mol/L phosphoric acid, the constant voltage is 120V, the anodization time is 10min, and the temperature is 25°C.
  • the aluminum alloy now displays the original color of the aluminum alloy.
  • the electrolyte formula of anodization is 0.1mol/L phosphoric acid, a constant current of 400mA/dm 2 is used, and the anodization time is 15min. Other than that, in the same manner as 1 in Example 11, a red-coated aluminum alloy was obtained.
  • This embodiment is a preparation method of green aluminum alloy coating, which can be realized by controlling constant current and oxidation time.
  • the electrolyte formula of anodization is 0.1mol/L phosphoric acid, a constant current of 130mA/dm 2 is used, and the anodization time is 30min.
  • the electrolyte formula for anodization is 0.1mol/L phosphoric acid, a constant current of 150mA/dm 2 is used, and the anodization time is 40min.
  • a green plated aluminum alloy was obtained.
  • a method for preparing an orange-coated aluminum alloy includes the following steps: as an anodic oxidation process, the electrolyte formula for anodic oxidation is 0.1 mol/L phosphoric acid, a constant current of 250 mA/dm 2 is used, and the anodic oxidation time is 10 minutes. Other than that, in the same manner as 1 in Example 11, an orange-coated aluminum alloy was obtained.
  • a method for preparing a coated gray aluminum alloy includes the following steps: as an anodic oxidation process, the electrolyte formula of the anodic oxidation is 0.1mol/L phosphoric acid and 2g/L sodium fluoride, and a constant current of 250mA/dm 2 is used, Anodizing time 30min. Other than that, in the same manner as in Example 11, a gray plated aluminum alloy was obtained.
  • the invention discloses a color aluminum-plastic film, a color-coated aluminum alloy and a preparation method thereof.
  • the color aluminum-plastic film sequentially includes a base material layer, a first adhesive layer, a metallized film layer, an aluminum foil layer, The second adhesive layer and the heat-sealing layer; the aluminum foil layer or the aluminum alloy includes an anodized layer, and the metallized film layer is attached to the surface of the anodized layer by ion sputtering, and the same metal film layer can show red , orange, yellow, green, blue, purple, gray and other different colors; the substrate layer is made of transparent insulating material, which has industrial practicability.

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Abstract

一种彩色铝塑膜（8）、镀膜彩色铝合金及其制备方法，该彩色铝塑膜（8）由外至内依次包括基材层（1）、第一粘接剂层（2）、镀金属膜层（3）、铝箔层（5）、第二粘接剂层（6）和热封层（7）；铝箔层（5）或铝合金（21）包括阳极氧化层（4，22），将所述镀金属膜层（3）通过离子溅射的方法附着于阳极氧化层（4，22）的表面，同一金属膜层可以呈现出红、橙、黄、绿、蓝、紫、灰等不同颜色；所述基材层（1）采用透明的绝缘材料。

Description

一种用于电池封装的彩色铝塑膜、镀膜彩色铝合金及其制备方法 技术领域
本发明属于铝塑膜技术领域，具体涉及一种用于电池封装的彩色铝塑膜、镀膜彩色铝合金及其制备方法。
背景技术
近年来，伴随着电动汽车、混合动力电动汽车、个人电脑、照相机、便携电话等的高性能化，对电池不仅追求高能量密度，要求多种多样的形状，还要求薄型化和轻量化。但是，以往大多使用的金属制的电池用包装材料存在如下的缺点：难以追随形状的多样化，并且在轻量化方面也存在限度。
于是采用铝塑膜作为电池的外包装材料，对电池进行封装。铝塑膜封装的电池，与传统的金属壳电池相比，具有能量密度高，容易加工成多样的形状、且能够实现薄型化、轻量化的优势。
尽管铝塑膜赋予了电池诸多优良性能，但现有铝塑膜仍存在以下缺陷：现有铝塑膜产品外观设计单一且文字的突显性受限制，现有铝塑膜主要由透明的流延聚丙烯薄膜、透明的聚酰胺纤维、透明的胶黏剂和铝箔组成，因而从外观上，铝塑膜显现出来的是铝箔本身的颜色，故印刷在铝塑膜表面的表征产品信息的文字颜色如为白色及其他浅色系时，其外观突显性较差，使得铝塑膜的外观设计不够丰富。
常用的电池用铝塑膜都没有印刷，外表看上去都是单调的金属色，究其原因，大多存在着色难度大，颜色难以调和及色彩保持难度高的问题，还存在着易变形、难以加工等问题。一些采用胶粘剂里加入油墨，主要是黑色，颜色单调，而且炭黑加入量过多，难分散，易沉降，油墨降低了复合的层间强度，胶粘剂对聚酰胺的粘接力会下降，导致铝塑膜成型性能下降，特别容易发生脱层现象，影响使用和铝塑膜最终表观。 有统计，在实际生产过程中，涂布黑色哑光油工艺会导致30-40％左右的铝塑膜损耗，极大增加成本。
因此，现有的电池用铝塑膜包装材料单一的金属色限制了电池的外包装图案设计，油墨的使用又容易导致铝塑膜成品率和性能下降。
发明内容
本发明的目的在于克服现有技术的不足之处，提供了一种用于电池封装的彩色铝塑膜及其制备方法，通过阳极氧化结合离子溅射技术替代油墨使铝塑膜呈现彩色，使铝箔层赋予多种颜色，提供较好的文字凸显性和颜色多变性的同时，保证基材层和铝箔层良好粘接力，解决了上述背景技术中的问题。
本发明解决其技术问题所采用的技术方案之一是：提供了一种用于电池封装的彩色铝塑膜，由外至内依次包括基材层、第一粘接剂层、镀金属膜层、铝箔层、第二粘接剂层和热封层；
所述铝箔层包括中间层和阳极氧化层，所述阳极氧化层设置于中间层的单面或双面；所述镀金属膜层通过离子溅射的方法附着于阳极氧化层的表面，用于呈现与铝箔或所镀金属本身不同的颜色；所述基材层采用透明的绝缘材料。
在本发明一较佳实施例中，所述镀金属膜层的厚度为1～100nm，镀层金属包括金、铂、铬，所述镀层金属的粒径为1～100nm。
在本发明一较佳实施例中，所述阳极氧化层的厚度为10～2000nm，阳极氧化层上均匀分布有孔径为30～140nm的孔洞。
本发明解决其技术问题所采用的技术方案之二是：提供了上述彩色铝塑膜的制备方法，包括如下步骤：
(1)制备铝箔层：将铝箔经单面或双面的阳极氧化，得到由中间层和阳极氧化层 组成的铝箔层；所述阳极氧化的电压为3～120V或电流密度为50～800mA/dm 2，氧化时间为5～60min，电解液采用0.1～0.5mol/L磷酸、硫酸、草酸的至少一种，电解液槽温度为20～30℃；
(2)喷镀镀金属膜层：用离子溅射仪在阳极氧化层铝箔层的表面喷镀金属，喷镀时间15～60s，得到带颜色的层叠体；
(3)复合基材层：利用第一粘接剂层在步骤(2)带颜色的层叠体表面连接基材层，得到复合有基材的层叠体；
(4)制备热封层：利用第二粘接剂将热熔性树脂复合至步骤(3)层叠体远离基材层的一面，形成热封层，并于60～120℃下老化加热3～4天，得到所述彩色铝塑膜。
在本发明一较佳实施例中，所述步骤(1)的铝箔经退火处理，且在阳极氧化前经过碱洗除油、水洗、酸洗中和、水洗的预处理。
在本发明一较佳实施例中，所述步骤(3)和步骤(4)采用干式层压法或挤出成型的方法实现层间连接。
本发明还提供了一种镀膜彩色铝合金的制备方法，将铝合金先进行阳极氧化处理，得到表面具有阳极氧化膜层的铝合金；再阳极氧化层的表面通过离子溅射的方法附着用于呈色的金属膜层，通过控制阳极氧化处理的电压或电流、时间以及镀层金属的种类，制备得到呈现颜色可控的镀膜彩色铝合金；其中，所述阳极氧化处理的电压为3～120V或电流密度为50～800mA/dm 2，氧化时间为5～60min；镀层金属包括粒径为1～100nm的金、铂、铬；呈现的颜色为除铝和镀层金属本身颜色外的可见光波长范围内的颜色。
本技术方案与背景技术相比，它具有如下优点：
1、本方案通过恒电压或恒电流阳极氧化结合离子溅射技术使铝塑膜呈现显示出红、橙、黄、紫、蓝等不同颜色，通过调节阳极氧化的参数实现规律控制颜色(特别通过改变阳极氧化的电解液种类、浓度以及氧化电压、时间等工艺参数，用同一种金属进行喷镀时，使铝箔层产生不同的颜色)，给予铝箔层赋予多种颜色，提供较好的文字凸显性和颜色多变性；
2、本方案替代油墨使铝塑膜呈现彩色，保证基材层和铝箔层良好粘接力，有效避免了铝塑膜因油墨导致的成型性能下降和脱层现象，得到满足电池封装要求的彩色铝塑膜。
3、本发明通过阳极氧化结合离子溅射技术替代传统染色和封孔处理工艺，使铝合金表面呈现肉眼可见的不同颜色，且通过控制阳极氧化处理的电压或电流、时间以及镀层金属的种类，控制镀膜彩色铝合金呈现出红、橙、黄、绿、蓝、紫、灰等不同颜色，操作简单、生产效率高、颜色鲜亮美观。
附图说明
图1为实施例1彩色铝塑膜的层结构图。
图2为实施例2彩色铝塑膜的层结构图。
图3为双面阳极氧化的装置示意图。
图4为单面阳极氧化的装置示意图。
图5为彩色铝合金的层结构图；
图6为本方法不同参数下制备的铝合金实物照片。
其中，1-基材层，2-第一粘接剂层、3-镀金属膜层、4-阳极氧化层(外层)、5-铝箔层
4-中间层、6-第二粘接剂层、7-热封层、8-彩色铝塑膜、9-阳极氧化层(内层)、10-电流表、11-阳极氧化电源、12-电压表、13-石墨板、14-阳极氧化槽、15-阳极氧化电 解液、16-石墨板(双面阳极氧化)；21-铝合金层，22-阳极氧化层，23-镀金属膜层。
具体实施方式
本发明一种用于电池封装的彩色铝塑膜，由外至内依次包括基材层、第一粘接剂层、镀金属膜层、铝箔层、第二粘接剂层和热封层；
所述铝箔层包括中间层和阳极氧化层，所述阳极氧化层设置于中间层的单面或双面；所述镀金属膜层通过离子溅射的方法附着于阳极氧化层的表面，用于呈现与铝箔或所镀金属本身不同的颜色；所述基材层采用透明的绝缘材料。
1、基材层
所述基材层的厚度不大于30μm，基材层1是位于最外层侧的层。关于形成基材层1的原材料，只要具有绝缘性即可，没有特别限制。作为形成基材层1的原材料，例如可以列举聚酰胺、聚酯、环氧树脂、丙烯酸树脂、氟树脂、聚氨酯、硅树脂、酚醛树脂、聚醚酰亚胺、聚酰亚胺、聚碳酸酯和它们的混合物或共聚物等。
作为聚酰胺，具体而言，可以列举尼龙6、尼龙66、尼龙610、尼龙12、尼龙46、尼龙6与尼龙66的共聚物等脂肪族系聚酰胺；包含来自对苯二甲酸和/或间苯二甲酸的构成单元的尼龙6I、尼龙6T、尼龙6IT、尼龙6I6T(I表示间苯二甲酸，T表示对苯二甲酸)等六亚甲基二胺－间苯二甲酸－对苯二甲酸共聚聚酰胺、聚己二酰间苯二甲胺(MXD6)等含有芳香族的聚酰胺；聚氨基甲基环己基己二酰胺(PACM6)等脂环系聚酰胺；以及使内酰胺成分和/或4,4′－二苯基甲烷－二异氰酸酯等异氰酸酯成分共聚而成的聚酰胺、作为共聚聚酰胺与聚酯、聚亚烷基醚二醇的共聚物的聚酯酰胺共聚物、聚醚酯酰胺共聚物；它们的共聚物等。这些聚酰胺既可以单独使用1种，或者也可以组合使用2种以上。拉伸聚酰胺膜的拉伸性优异，能够防止成型时因基材层1的树脂 破裂而发生白化，适合作为基材层1的形成原材料使用。
作为聚酯，具体而言，可以列举聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚萘二甲酸乙二醇酯、聚萘二甲酸丁二醇酯、聚间苯二甲酸乙二醇酯、以亚乙基对苯二甲酸酯为重复单元的主体的共聚聚酯、异亚丁基对苯二甲酸酯为重复单元的主体的共聚聚酯等。另外，作为以亚乙基对苯二甲酸酯为重复单元的主体的共聚聚酯，具体而言，可以列举以亚乙基对苯二甲酸酯为重复单元的主体并与亚乙基间苯二甲酸酯聚合的共聚物聚酯(以下，省略为聚亚乙基(对苯二甲酸酯/间苯二甲酸酯))、聚亚乙基(对苯二甲酸酯/间苯二甲酸酯)、聚亚乙基(对苯二甲酸酯/己二酸酯)、聚亚乙基(对苯二甲酸酯/磺基间苯二甲酸钠)、聚亚乙基(对苯二甲酸酯/间苯二甲酸钠)、聚亚乙基(对苯二甲酸酯/苯基－二羧酸酯)、聚亚乙基(对苯二甲酸酯/癸二羧酸酯)等。另外，作为以亚丁基对苯二甲酸酯为重复单元的主体的共聚聚酯，具体而言，可以列举以亚丁基对苯二甲酸酯为重复单元的主体并与亚丁基间苯二甲酸酯聚合的共聚物聚酯(以下，省略为聚亚丁基(对苯二甲酸酯/间苯二甲酸酯))、聚亚丁基(对苯二甲酸酯/己二酸酯)、聚亚丁基(对苯二甲酸酯/癸二酸酯)、聚亚丁基(对苯二甲酸酯/癸二羧酸酯)、聚萘二甲酸丁二醇酯等。这些聚酯既可以单独使用1种，或者也可以组合使用2种以上。聚酯具有耐电解液性优异、对于电解液的附着难以发生白化等的优点，适合作为基材层1的形成原材料使用。
基材层1可以由1轴或2轴拉伸后的树脂膜形成，还可以由未拉伸的树脂膜形成。其中，1轴或2轴拉伸后的树脂膜、特别是2轴拉伸后的树脂膜通过取向结晶化而耐热性提高，因此适合作为基材层1使用。这些之中，作为形成1的树脂膜，从发挥高的成型性的观点出发，优选列举尼龙、聚酯，更加优选列举2轴拉伸尼龙、2轴拉伸聚酯， 特别优选列举2轴拉伸尼龙。
作为聚酰胺膜层的厚度，没有特别限制，从使铝塑膜薄型化、并且发挥优异的成型性的观点出发，优选列举30μm以下、更优选列举1～25μm左右、进一步优选列举10～25μm左右。
作为聚酯膜层的厚度，没有特别限制，从使铝塑膜薄型化、并发挥优异的成型性的观点出发，优选列举约20μm以下，更优选列举1～15μm左右，进一步优选列举3～12μm左右。
2、第一粘接剂层
第一粘接剂层2是为了使基材层1与镀金属膜层3牢固地粘接而根据需要设置于它们之间的层。
第一粘接剂层由能够将基材层与镀金属膜层粘接的粘接剂形成。用于形成第一粘接剂层的粘接剂可以为双液固化型粘接剂，也可以为单液固化型粘接剂。另外，对于用于形成第一粘接剂层的粘接剂的粘接机理，也没有特别限制，化学反应型、溶剂挥发型、热熔融型、热压型等的任意类型均可。
作为能够用于形成第一粘接剂层的粘接成分，具体可以列举：聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚萘二甲酸乙二醇酯、聚萘二甲酸丁二醇酯、聚间苯二甲酸乙二醇酯、共聚聚酯等的聚酯系树脂；聚醚系粘接剂；聚氨酯系粘接剂；环氧系树脂；酚醛系树脂；尼龙6、尼龙66、尼龙12、共聚聚酰胺等的聚酰胺系树脂；聚烯烃、羧酸改性聚烯烃、金属改性聚烯烃等的聚烯烃系树脂、聚乙酸乙烯酯系树脂；纤维素系粘接剂；(甲基)丙烯酸系树脂；聚酰亚胺系树脂；聚碳酸酯；尿素树脂、三聚氰胺树脂等的氨基树脂；氯丁二烯橡胶、丁腈橡胶、苯乙烯－丁二烯橡胶等的橡胶； 有机硅系树脂等。这些粘接成分可以单独使用1种，也可以将2种以上组合使用。在这些粘接成分中，优选列举聚氨酯系粘接剂。
作为聚氨酯系粘接剂，例如可以列举包含具有多元醇成分(A)的主剂、和具有多异氰酸酯成分(B)的固化剂的聚氨酯系粘接剂，多元醇成分(A)含有聚酯多元醇(A1)，聚酯多元醇(A1)是由多元酸成分与多元醇成分构成的数均分子量为5000～50000的聚酯多元醇，多元酸成分100摩尔％中，含有芳香族多元酸成分45～95摩尔％，粘接剂层的100％拉伸时的拉伸应力在100kg/cm 2以上500kg/cm 2以下。例如还可以列举含有主剂和多异氰酸酯固化剂的聚氨酯系粘接剂，主剂含有多元醇成分(A)和硅烷偶联剂(B)，多元醇成分(A)包含玻璃化转变温度在40℃以上的聚酯多元醇(A1)5～50质量％和玻璃化转变温度低于40℃的聚酯多元醇(A2)95～50质量％，相对于来自多元醇成分(A)的羟基与羧基的合计，固化剂中所含的异氰酸酯基的当量比[NCO]/([OH]+[COOH])为1～30。
关于第一粘接剂层的厚度，只要能够发挥作为粘接层的功能即可，没有特别限制，从铝塑膜的薄膜化、轻质化的观点考虑，上述第一粘接剂层的厚度例如可以优选列举1～10μm左右、更优选列举1～5μm左右，进一步优选列举1-3μm左右。
3、镀金属膜层
镀金属膜层是通过离子溅射技术喷镀在阳极氧化层上，可以形成多种颜色的外观，提供较好的文字凸显性和颜色多变性，实现彩色铝塑膜的效果。需要指出的是，通过改变铝箔层的阳极氧化过程的电解液种类、浓度以及氧化电压、时间等工艺参数，用同一种金属进行喷镀时，铝箔层会产生不同的颜色。例如用金进行喷镀不同阳极氧化条件处理的铝箔，会产生红、橙、黄、紫、蓝等不同的颜色。
所述镀金属膜层所选的镀层金属为金、铂、银、钛、铬等金属的一种或多种，优选金、铂、铬金属。
关于镀金属的镀层厚度，没有特别的限制，从经济性和美观性考虑，例如可以列举镀层厚度1～100nm左右，优选镀层厚度为2～30nm左右。
4、阳极氧化层
阳极氧化层是铝箔层经过阳极氧化得到的，主要是用来作为镀金属层的基底，同时阳极氧化形成的孔洞，具有良好的耐腐蚀性和吸附性，有利于提高与粘接剂层1的粘接力。
阳极氧化层是通过恒电压或恒电流阳极氧化过程得到，阳极氧化槽液控制温度为20～30℃。将铝箔层经过碱洗除油，水洗，酸洗中和，水洗，阳极氧化，水洗，干燥过程得到。氧化层厚度在10～2000nm，优选厚度为20-1500nm，更优选厚度为50-1000nm。氧化层经扫描电子显微镜(SEM)观察为均匀分布的孔洞，孔洞直径为30～140nm，优选30-120nm，更优选30-100nm。
阳极氧化的电压范围是3～120V，电流密度为50～300mA/dm 2，氧化时间为5～60min。
阳极氧化的电解液可以采用0.1～0.5mol/L磷酸、硫酸、草酸的至少一种；或，
阳极氧化的电解液可以采用磷酸、硫酸、草酸的至少一种，以及该酸酸根对应的酸式盐或氟化物中的至少一种。
5、铝箔层
铝箔层是除了提高铝塑膜的强度以外、还具有防止水蒸气、氧、光等侵入电池内部的功能的层。从防止在铝箔层产生褶皱或针孔的观点考虑，更优选由例如经退火处理的铝(JIS H4160：1994A8021H-O、JIS H4160：1994A8079H-O、JIS H4000： 2014A8021P-O、JIS H4000：2014A8079P-O)等软质铝合金箔形成。
铝箔层的厚度，只要能够发挥作为水蒸气等的阻隔层的功能，就没有特别限制，从使电池用铝塑膜的薄膜化、轻质化的观点出发，例如，作为上限，可以列举约100μm以下、优选约80μm以下、更优选约50μm以下、更加优选约40μm以下，作为下限，可以列举优选约10μm以上，作为该厚度的范围，能够设为10～100μm左右、10～80μm左右、优选10～50μm左右、10～40μm左右。
6、第二粘接剂层
第二粘接剂层是为了使铝箔层与热封层牢固粘接而根据需要设置于这些层之间的层。
第二粘接剂层由能够粘接铝箔层与热封层的粘接剂形成。关于用于第二粘接剂层6的形成的粘接剂，其粘接机理、粘接剂成分的种类等与上述粘接层2的情况同样。作为第二粘接层6所使用的粘接剂成分，优选使用由电解液导致的溶胀少的聚烯烃系粘接剂，优选列举聚烯烃系树脂，进一步，从使电池用铝塑膜的厚度变薄、并且制成成型后的形状稳定性优异的电池用铝塑膜的观点考虑，第二粘接剂层也可以为含有酸改性聚烯烃和固化剂的树脂组合物的固化物。作为酸改性聚烯烃，优选羧酸改性聚烯烃、羧酸改性环状聚烯烃同样的化合物。
另外，作为固化剂，只要能够使酸改性聚烯烃固化即可，没有特别限定。作为固化剂，例如可以列举环氧系固化剂、多官能异氰酸酯系固化剂、碳化二亚胺系固化剂、噁唑啉系固化剂等。
环氧系固化剂只要是至少具有1个环氧基的化合物即可，没有特别限定。作为环氧系固化剂，例如可以列举双酚A二缩水甘油醚、改性双酚A二缩水甘油醚、酚醛清 漆缩水甘油醚、甘油聚缩水甘油醚、聚甘油聚缩水甘油醚等环氧树脂。
多官能异氰酸酯系固化剂只要是具有2个以上异氰酸酯基的化合物即可，没有特别限定。作为多官能异氰酸酯系固化剂的具体例，可以列举异佛尔酮二异氰酸酯(IPDI)、六亚甲基二异氰酸酯(HDI)、甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)、将它们聚合物化或脲酸酯(nurate)化而成的产物、它们的混合物或与其他聚合物的共聚物等。
碳化二亚胺系固化剂只要是至少具有1个碳化二亚胺基(－N＝C＝N－)的化合物即可，没有特别限定。作为碳化二亚胺系固化剂，优选至少具有2个以上碳化二亚胺基的多碳化二亚胺化合物。
噁唑啉系固化剂只要是具有噁唑啉骨架的化合物即可，没有特别限定。作为噁唑啉系固化剂，具体可以列举日本触媒株式会社生产的Epocros系列等。
从利用第二粘接剂层来提高铝箔层与热封层的密合性等观点考虑，固化剂也可以由2种以上化合物构成。
形成第二粘接剂层的树脂组合物中的固化剂的含量优选处于0.1～50质量％左右的范围内，更优选处于0.1～30质量％左右的范围内，进一步优选处于0.1～10质量％左右的范围内。
关于第二粘接剂层的厚度，只要能够发挥作为粘接层的功能即可，没有特别限制，从铝塑膜的薄膜化、轻质化的观点考虑，上述第二粘接剂层的厚度例如可以优选列举1～10μm左右、更优选列举1～5μm左右，进一步优选列举1-3μm左右。
7、热封层
热封层的作用是使得针对电池中使用的腐蚀性强的电解液等具备优异的耐化学药 品性，并且向对铝塑膜赋予热封性。
热封层使用的树脂成分，没有特别限制，可以列举例如聚烯烃、环状聚烯烃、酸改性聚烯烃、酸改性环状聚烯烃。即，热封层可以包含聚烯烃骨架，且优选包含聚烯烃骨架。如可以利用傅立叶红外光谱法、气相色谱-质谱法等进行分析，分析方法没有特别限定。例如在利用傅立叶红外光谱法测定马来酸酐改性聚烯烃时，在波数1760cm-1附近和波数1780cm-1附近检测出来自马来酸酐的峰。其中，在酸改性度低时，峰减小，有时检测不出来。此时，可以利用核磁共振光谱法进行分析。
作为上述聚烯烃，具体可以列举：低密度聚乙烯、中密度聚乙烯、高密度聚乙烯、线性低密度聚乙烯等聚乙烯；均聚丙烯、聚丙烯的嵌段共聚物(例如丙烯与乙烯的嵌段共聚物)、聚丙烯的无规共聚物(例如丙烯与乙烯的无规共聚物)等聚丙烯；乙烯－丁烯－丙烯的三元聚合物等。这些聚烯烃之中，优选列举聚乙烯和聚丙烯。
上述环状聚烯烃为烯烃与环状单体的共聚物，作为上述环状聚烯烃的构成单体的烯烃，可以列举例如乙烯、丙烯、4－甲基－1－戊烯、丁二烯、异戊二烯等。另外，作为上述环状聚烯烃的构成单体的环状单体，可以列举例如降冰片烯等环状烯，具体可以列举环戊二烯、二环戊二烯、环己二烯、降冰片二烯等环状二烯等。这些聚烯烃中，优选列举环状烯，进一步优选列举降冰片烯。
上述酸改性聚烯烃是通过利用羧酸等酸成分将上述聚烯烃嵌段聚合或接枝聚合而改性得到的聚合物。作为改性所使用的酸成分，可以列举例如马来酸、丙烯酸、衣康酸、巴豆酸、马来酸酐、衣康酸酐等的羧酸或其酸酐。
上述酸改性环状聚烯烃是通过将构成环状聚烯烃的单体的一部分替换成α,β－不饱和羧酸或其酸酐进行共聚、或者通过使α,β－不饱和羧酸或其酸酐与环状聚烯烃嵌段聚 合或接枝聚合而得到的聚合物。被羧酸改性的环状聚烯烃同上。另外，作为改性所使用的羧酸，与上述聚烯烃的改性所使用的酸成分同样。
这些树脂成分中，优选列举聚丙烯等聚烯烃、羧酸改性聚烯烃，进一步优选列举聚丙烯、酸改性聚丙烯。
热封层可以单独由1种树脂成分形成，还可以由将2种以上的树脂成分组合而成的掺混聚合物形成。另外，热封层可以仅由1层形成，还可以利用相同或不同的树脂成分由2层以上形成。
热封层的厚度，没有特别限制，从使电池用铝塑膜薄型化、并且发挥优异的成型性的观点出发，作为上限，优选列举约80μm以下，能够减少树脂使用量，可实现成本的降低，作为下限，优选列举约10μm以上，能够充分防止针孔的产生，因此优选列举为10μm～80μm左右，更优选10～40μm左右。
8、制备方法
在带颜色的层叠体的镀金属膜层上叠层第一粘接剂层和基材层，具体而言，可以通过如下的干式层压法进行：利用挤出法、凹版涂敷法、辊涂法等涂布方法将用于形成第一粘接剂层的粘接剂涂布在基材层或镀金属膜层上并进行干燥，之后将该镀金属膜层或基材层叠层并使第一粘接剂层固化。
接着，在带颜色的层叠体的铝箔层上叠层第二粘接剂层和热封层。在铝箔层上叠层第二粘接剂层和热封层，例如可以列举如下方法：(1)在带颜色的层叠体的铝箔层上，将第二粘接剂层和热封层共挤出而进行叠层的方法(共挤出层压法)；(2)形成第二粘接剂层和热封层叠层而得到的层叠体，利用热层压法将其叠层在带颜色的层叠体的铝箔层上的方法；(3)利用凹版涂敷法、辊涂法等涂布方法将用于形成第二粘接剂 层的上述树脂组合物涂布在带颜色的层叠体的铝箔层上并进行干燥，之后叠层该热封层并使第二粘接剂层固化的干式层压法；(4)使熔融的第二粘接剂层流入带颜色的层叠体的铝箔层与预先成膜为片状的热封层之间，并隔着第二粘接剂层将带颜色的层叠体与热封层贴合的方法(夹层层压法)等。这些方法之中，优选方法(3)。在采用方法(3)的情况下，优选将形成第二粘接剂层的上述树脂组合物叠层在铝箔层上，之后在60～120℃左右的温度进行干燥。在热封层为多层的情况下，优选该热封层的最内层为通过干式层压法或挤出成型形成的层。
此外，根据需要为了使制膜性、叠层化加工、最终制品2次加工(包装化、压花成型)适应性等提高或稳定化，对构成层叠体的各层实施电晕放电处理、喷砂处理、臭氧处理等表面活化处理。
9、用途
利用本发明的彩色铝塑膜进行电池的封装，将至少具有正极、负极和电解质的电池元件在与上述正极和负极各自连接的金属端子向外侧突出的状态下、以能够在电池元件的边缘形成凸缘部(热封层树脂彼此相接触的区域)的方式进行覆盖，将上述凸缘部的热封层彼此热封来进行密封，由此能够提供使用了彩色的电池用铝塑膜的电池。此外，在使用本发明的彩色的电池用铝塑膜收纳电池元件时，以本发明的彩色的电池用铝塑膜的热封层树脂部分成为内侧(与电池元件接触的面)的方式使用。
本发明的彩色的电池用铝塑膜可以使用于一次电池、二次电池的任意一种，优选为二次电池。关于应用本发明的彩色的电池用铝塑膜的二次电池的种类，没有特别限制，可以列举例如锂离子电池、锂离子聚合物电池、铅蓄电池、镍-氢蓄电池、镍-镉蓄电池、镍-铁蓄电池、镍-锌蓄电池、氧化银-锌蓄电池、金属空气电池、多价阳离子电 池、电容器等。这些二次电池中，作为本发明的彩色的电池用铝塑膜的优选应用对象，可以列举锂离子电池和锂离子聚合物电池。
实施例1
本实施例一种用于电池封装的彩色铝塑膜的制备方法，包括如下步骤：
铝箔层(厚度40μm)经过碱洗除油，水洗，酸洗中和，水洗，得到干净的铝箔层。
铝箔层经双面阳极氧化得到阳极氧化层4(阳极氧化装置见图3)，包括电流表10、阳极氧化电源11、电压表12、石墨板电极13和16、阳极氧化槽14以及槽内的电解液15。阳极氧化的电解液配方为0.1mol/L磷酸，采用恒电压5V，阳极氧化时间10min，温度为25℃，得到阳极氧化层4(厚度1μm)和阳极氧化层(内层)9(厚度1μm)。经阳极氧化后的铝箔层在肉眼下呈现铝箔原有的颜色。
用离子溅射仪在阳极氧化层4喷镀金(元素符号Au)，喷金时间为30s，得到镀金膜层3(厚度20nm)，形成层叠体A。此时镀层金属虽然只有金(元素符号Au)一种元素，但因为阳极氧化过程的时间参数不同，此时镀层金属显示的颜色不是金本体的颜色，而是显示出紫色，形成紫色的层叠体A。
接下来，在层叠体A的镀金属膜层3上，经由2液固化型的氨基甲酸酯类粘接剂(第一粘接剂层2，厚度3μm)而干式层压双轴拉伸尼龙膜(基材层1，厚度25μm)，通过夹入橡胶夹持辊与已加热至100℃的层压辊之间并进行压接。
接下来，在未拉伸聚丙烯膜(热熔性树脂层7，厚度80μm)的一个面上，经由2液固化型的马来酸酐改性聚丙烯粘接剂(第二粘接剂层6，厚度3μm)叠合上述干式 层压后的铝箔层的另一个面。
然后于75℃老化加热4天，由此得到图1所示的构成的总厚度153μm，包括依次层叠的基材层1，第一粘接剂层2，镀金属膜层3，铝箔阳极氧化层4，中间层5，铝箔阳极氧化层(内层)9，第二粘接剂层6，热熔性树脂层7的层叠体而形成的紫色的电池用铝塑膜。
实施例2
铝箔层(厚度40μm)经过碱洗除油，水洗，酸洗中和，水洗，得到干净的铝箔层。
接下来，在未拉伸聚丙烯膜(热熔性树脂层7，厚度80μm)的一个面上，经由2液固化型的马来酸酐改性聚丙烯粘接剂(第二粘接剂层6，厚度3μm)叠合铝箔层的一个面，形成叠层体B。
接下来，在叠层体B的铝箔层的另一面，进行单面阳极氧化过程(阳极氧化装置见图4)包括电流表10、阳极氧化电源11、电压表12、石墨板电极13、阳极氧化槽14以及槽内的电解液15。阳极氧化的电解液配方为0.1mol/L磷酸，采用恒电压5V，阳极氧化时间50min，温度为25℃，得到阳极氧化层4(厚度1μm)。
接下来，用离子溅射仪在阳极氧化层4喷镀金(元素符号Au)，喷金时间为30s，得到镀金膜层3(厚度20nm)，此时镀层金属显示的颜色不是金本体的颜色，而是显示出黄色，形成黄色的层叠体C。
接下来，在镀金属膜层3上，经由2液固化型的氨基甲酸酯类粘接剂(第一粘接剂层2，厚度3μm)而干式层压双轴拉伸尼龙膜(基材层1，厚度25μm)，通过夹入橡胶夹持辊与已加热至100℃的层压辊之间并进行压接。
然后于75℃老化加热4天，由此得到图2所示的构成的总厚度152μm，包括依次层叠的基材层1，第一粘接剂层2，镀金属膜层3，铝箔阳极氧化层4，中间层，第二粘接剂层6，热熔性树脂层7的层叠体而形成的黄色的电池用铝塑膜。
实施例3
铝箔层(厚度40μm)经过碱洗除油，水洗，酸洗中和，水洗，得到干净的铝箔层。
铝箔层经双面阳极氧化得到阳极氧化层4(阳极氧化装置见图3)。阳极氧化的电解液配方为0.1mol/L磷酸，采用恒电流800mA/dm 2，阳极氧化时间5min，温度为25℃，得到阳极氧化层4(厚度1μm)和铝箔阳极氧化层(内层)9(厚度1μm)。
用离子溅射仪在阳极氧化层4喷镀金(元素符号Au)，喷金时间为30s，得到镀金膜层3(厚度20nm)，形成层叠体A。此时镀层金属虽然只有金(元素符号Au)一种元素，但因为阳极氧化过程的时间参数不同，此时镀层金属显示的颜色不是金本体的颜色，而是显示出蓝色，形成蓝色的层叠体A。
接下来，在层叠体A的镀金属膜层3上，经由2液固化型的氨基甲酸酯类粘接剂(第一粘接剂层2，厚度3μm)而干式层压双轴拉伸尼龙膜(基材层1，厚度25μm)，通过夹入橡胶夹持辊与已加热至100℃的层压辊之间并进行压接。
接下来，在未拉伸聚丙烯膜(热熔性树脂层7，厚度40μm)的一个面上，经由2液固化型的马来酸酐改性聚丙烯粘接剂(第二粘接剂层6，厚度3μm)叠合上述干式层压后的铝箔层的另一个面。
然后于75℃老化加热4天，由此得到图1所示的构成的总厚度113μm，包括依次层叠的基材层1，第一粘接剂层2，镀金属膜层3，铝箔阳极氧化层4，中间层，铝箔阳极氧化层(内层)9，第二粘接剂层6，热熔性树脂层7的层叠体而形成的蓝色的电 池用铝塑膜。
实施例4
铝箔层(厚度40μm)经过碱洗除油，水洗，酸洗中和，水洗，得到干净的铝箔层。
接下来，在未拉伸聚丙烯膜(热熔性树脂层7，厚度40μm)的一个面上，经由2液固化型的马来酸酐改性聚丙烯粘接剂(第二粘接剂层6，厚度3μm)叠合铝箔层的一个面，形成叠层体B。
接下来，在叠层体B的铝箔层的另一面，进行单面阳极氧化过程(阳极氧化装置见图4)。阳极氧化的电解液配方为0.1mol/L磷酸，采用恒电流150mA/dm 2，阳极氧化时间30min，温度为25℃，得到阳极氧化层4(厚度1μm)。
接下来，用离子溅射仪在阳极氧化层4喷镀铂(元素符号Pt)，喷铂时间为30s，得到镀金膜层3(厚度20nm)，此时镀层金属显示的颜色不是铂本体的颜色，而是显示出紫色，形成紫色的层叠体C。
接下来，在镀金属膜层3上，经由2液固化型的氨基甲酸酯类粘接剂(第一粘接剂层2，厚度3μm)而干式层压双轴拉伸尼龙膜(基材层1，厚度25μm)，通过夹入橡胶夹持辊与已加热至100℃的层压辊之间并进行压接。
然后于75℃老化加热4天，由此得到图2所示的构成的总厚度112μm，包括依次层叠的基材层1，第一粘接剂层2，镀金属膜层3，铝箔阳极氧化层4，中间层，第二粘接剂层6，热熔性树脂层7的层叠体而形成的紫色的电池用铝塑膜。
实施例5
作为阳极氧化过程，阳极氧化的电解液配方为0.1mol/L磷酸，采用恒电流130mA/dm 2，阳极氧化时间30min，除此之外，与实施例1相同，得到绿色的电池用铝 塑膜。
实施例6
作为阳极氧化过程，阳极氧化的电解液配方为0.1mol/L磷酸，采用恒电压120V，阳极氧化时间10min。除此之外，与实施例1相同，得到红色的电池用铝塑膜。
实施例7
作为阳极氧化过程，阳极氧化的电解液配方为0.1mol/L磷酸，采用恒电流250mA/dm 2，阳极氧化时间10min。除此之外，与实施例1相同，得到橙色的电池用铝塑膜。
实施例8
作为阳极氧化过程，阳极氧化的电解液配方为0.1mol/L磷酸，采用恒电流250mA/dm 2，阳极氧化时间20min。除此之外，与实施例1相同，得到黄色的电池用铝塑膜。
实施例9
作为阳极氧化过程，阳极氧化的电解液配方为0.1mol/L磷酸和和2g/L氟化钠，采用恒电流250mA/dm 2，阳极氧化时间30min。除此之外，与实施例1相同，得到灰色的电池用铝塑膜。
实施例10
作为阳极氧化过程，阳极氧化的电解液配方为0.1mol/L磷酸，采用恒电流150mA/dm 2，阳极氧化时间40min。除此之外，与实施例4相同，得到绿色的电池用铝塑膜。
下述实施例为彩色铝合金的镀膜方法，镀层金属可采用金或铂。中采用的阳极氧 化处理装置包括阳极氧化槽14，阳极氧化槽14内设置有石墨板电极13和铝合金层5或21的电极，石墨板电极13和铝合金层5或21的电极浸入或部分浸入电解液15中，二者的一端连通电源11且设置有电压表12和/或电流表10。
实施例11
①当镀层金属为金时，包括如下步骤：
将厚度为40μm的铝合金1，经过40g/L氢氧化钠溶液碱洗30s，水洗。然后用10％质量分数的硝酸溶液中和30s，水洗，得到干净的铝合金。
接下来，对铝合金21进行阳极氧化处理，得到阳极氧化层22，阳极氧化的电解液配方为0.1mol/L磷酸，采用恒电压5V，阳极氧化时间10min，温度为25℃，阳极氧化后的铝合金此时显示的是铝合金原有的颜色。
接下来用离子溅射仪在阳极氧化层22喷镀金(元素符号Au)，喷金时间为30s，得到镀金膜层23(厚度20nm)，此时镀层金属显示的颜色不是金本体的颜色，而是显示出紫色，得到紫色的镀膜铝合金。
②当镀层金属为铂时，包括如下步骤：
将厚度为40μm的铝合金1，经过40g/L氢氧化钠溶液碱洗30s，水洗。然后用10％质量分数的硝酸溶液中和30s，水洗，得到干净的铝合金。
接下来，对铝合金21进行阳极氧化处理，得到阳极氧化层22，阳极氧化的电解液配方为0.1mol/L磷酸，采用恒电流75mA/dm 2，阳极氧化时间40min，温度为25℃，阳极氧化后的铝合金此时显示的是铝合金原有的颜色。
接下来用离子溅射仪在阳极氧化层22喷镀铂(元素符号Pt)，喷铂时间为30s，得到镀金膜层23(厚度20nm)，此时镀层金属显示的颜色不是铂本体的颜色，而是显示 出紫色，得到紫色的镀膜铝合金。
实施例12
本实施例一种镀膜黄色铝合金的制备方法，可以通过控制恒电压或恒电流实现。
①制恒电压，包括如下步骤：
将厚度为40μm的铝合金21，经过40g/L氢氧化钠溶液碱洗30s，水洗。然后用10％质量分数的硝酸溶液中和30s，水洗，得到干净的铝合金。
接下来，对铝合金21进行阳极氧化处理，得到阳极氧化层22，阳极氧化的电解液配方为0.1mol/L磷酸，采用恒电压5V，阳极氧化时间50min，温度为25℃，阳极氧化后的铝合金此时显示的是铝合金原有的颜色。
接下来用离子溅射仪在阳极氧化层22喷镀金(元素符号Au)，喷金时间为30s，得到镀金膜层23(厚度20nm)，此时镀层金属显示的颜色不是金本体的颜色，而是显示出黄色，得到黄色的镀膜铝合金。
②控制恒电流，包括如下步骤：
作为阳极氧化过程，阳极氧化的电解液配方为0.1mol/L磷酸，采用恒电流250mA/dm 2，阳极氧化时间20min。除此之外，与实施例1中①相同，得到黄色的镀膜铝合金。
实施例13
本实施例一种镀膜蓝色铝合金的制备方法，可以通过控制恒电压或恒电流实现。
①控制恒电压，包括如下步骤：
将厚度为40μm的铝合金21，经过40g/L氢氧化钠溶液碱洗30s，水洗。然后用10％质量分数的硝酸溶液中和30s，水洗，得到干净的铝合金。
接下来，对铝合金21进行阳极氧化处理，得到阳极氧化层22，阳极氧化的电解液配方为0.1mol/L磷酸，采用恒电压20V，阳极氧化时间10min，温度为25℃，阳极氧化后的铝合金此时显示的是铝合金原有的颜色。
接下来用离子溅射仪在阳极氧化层22喷镀金(元素符号Au)，喷金时间为30s，得到镀金膜层23(厚度20nm)，此时镀层金属显示的颜色不是金本体的颜色，而是显示出蓝色，得到蓝色的镀膜铝合金。
②制恒电流，包括如下步骤：
作为阳极氧化过程，阳极氧化的电解液配方为0.1mol/L磷酸，采用恒电流800mA/dm 2，阳极氧化时间5min，。除此之外，与实施例11中①相同，得到蓝色的镀膜铝合金。
实施例14
本实施例一种镀膜红色铝合金的制备方法，可以通过控制恒电压或恒电流实现。
①控制恒电压，包括如下步骤：
将厚度为40μm的铝合金21，经过40g/L氢氧化钠溶液碱洗30s，水洗。然后用10％质量分数的硝酸溶液中和30s，水洗，得到干净的铝合金。
接下来，对铝合金21进行阳极氧化处理，得到阳极氧化层22，阳极氧化的电解液配方为0.1mol/L磷酸，采用恒电压120V，阳极氧化时间10min，温度为25℃，阳极氧化后的铝合金此时显示的是铝合金原有的颜色。
接下来用离子溅射仪在阳极氧化层22喷镀金(元素符号Au)，喷金时间为30s，得到镀金膜层23(厚度20nm)，此时镀层金属显示的颜色不是金本体的颜色，而是显 示出红色，得到红色的镀膜铝合金。
②制恒电流，包括如下步骤：
作为阳极氧化过程，阳极氧化的电解液配方为0.1mol/L磷酸，采用恒电流400mA/dm 2，阳极氧化时间15min，。除此之外，与实施例11中①相同，得到红色的镀膜铝合金。
实施例15
本实施例一种镀膜绿色铝合金的制备方法，可以通过控制恒电流和氧化时间实现。
①作为阳极氧化过程，阳极氧化的电解液配方为0.1mol/L磷酸，采用恒电流130mA/dm 2，阳极氧化时间30min，除此之外，与实施例1中①相同，得到绿色的镀膜铝合金。
②作为阳极氧化过程，阳极氧化的电解液配方为0.1mol/L磷酸，采用恒电流150mA/dm 2，阳极氧化时间40min。除此之外，与实施例14相同，得到绿色的镀膜铝合金。
实施例16
本实施例一种镀膜橙色铝合金的制备方法，包括如下步骤：作为阳极氧化过程，阳极氧化的电解液配方为0.1mol/L磷酸，采用恒电流250mA/dm 2，阳极氧化时间10min。除此之外，与实施例11中①相同，得到橙色的镀膜铝合金。
实施例17
本实施例一种镀膜灰色铝合金的制备方法，包括如下步骤：作为阳极氧化过程，阳极氧化的电解液配方为0.1mol/L磷酸和2g/L氟化钠，采用恒电流250mA/dm 2，阳极氧化时间30min。除此之外，与实施例11相同，得到灰色的镀膜铝合金。
以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实 施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。
工业实用性
本发明公开了一种彩色铝塑膜、镀膜彩色铝合金及其制备方法，该彩色铝塑膜由外至内依次包括基材层、第一粘接剂层、镀金属膜层、铝箔层、第二粘接剂层和热封层；铝箔层或铝合金包括阳极氧化层，将所述镀金属膜层通过离子溅射的方法附着于阳极氧化层的表面，同一金属膜层可以呈现出红、橙、黄、绿、蓝、紫、灰等不同颜色；所述基材层采用透明的绝缘材料,具有工业实用性。

Claims (20)

  1. 一种用于电池封装的彩色铝塑膜，其特征在于：由外至内依次包括基材层、第一粘接剂层、镀金属膜层、铝箔层、第二粘接剂层和热封层；
    所述铝箔层包括中间层和阳极氧化层，所述阳极氧化层设置于中间层的单面或双面；所述镀金属膜层通过离子溅射的方法附着于阳极氧化层的表面，用于呈现与铝箔或所镀金属本身不同的颜色；所述基材层采用透明的绝缘材料。
  2. 根据权利要求1所述的一种用于电池封装的彩色铝塑膜，其特征在于：所述镀金属膜层的厚度为1～100nm，镀层金属包括金、铂、铬，所述镀层金属的粒径为1～100nm。
  3. 根据权利要求1所述的一种用于电池封装的彩色铝塑膜，其特征在于：所述阳极氧化层的厚度为10～2000nm，阳极氧化层上均匀分布有孔径为30～140nm的孔洞。
  4. 根据权利要求1所述的一种用于电池封装的彩色铝塑膜，其特征在于：所述中间层的厚度为10～100μm。
  5. 根据权利要求1所述的一种用于电池封装的彩色铝塑膜，其特征在于：所述基材层的厚度不大于30μm，基材层包括聚酰胺、聚酯、环氧树脂、丙烯酸树脂、氟树脂、聚氨酯、硅树脂、酚醛树脂、聚醚酰亚胺、聚酰亚胺、聚碳酸酯，或者上述材料的混合物或共聚物。
  6. 根据权利要求1所述的一种用于电池封装的彩色铝塑膜，其特征在于：所述第一粘接层的厚度为1～10μm，第二粘接层采用聚烯烃系粘接剂，且第二粘接层的厚度为1～10μm。
  7. 根据权利要求1所述的一种用于电池封装的彩色铝塑膜，其特征在于：所述热封层的厚度不大于80μm。
  8. 如权利要求1～7任一项所述一种用于电池封装的彩色铝塑膜的制备方法，其特征在于：包括如下步骤：
    (1)制备铝箔层：将铝箔经单面或双面的阳极氧化，得到由中间层和阳极氧化层组成的铝箔层；所述阳极氧化的电压为3～120V或电流密度为50～800mA/dm 2，氧化时间为5～60min，电解液包括0.1～0.5mol/L的磷酸、硫酸、草酸中的至少一种，电解液槽温度为20～30℃；
    (2)喷镀镀金属膜层：用离子溅射仪在阳极氧化层铝箔层的表面喷镀金属，喷镀时间15～60s，得到带颜色的层叠体；
    (3)复合基材层：利用第一粘接剂层在步骤(2)带颜色的层叠体表面连接基材层，得到复合有基材的层叠体；
    (4)制备热封层：利用第二粘接剂将热熔性树脂复合至步骤(3)层叠体远离基材层的一面，形成热封层，并于60～120℃下老化加热3～4天，得到所述彩色铝塑膜。
  9. 根据权利要求8所述一种用于电池封装的彩色铝塑膜的制备方法，其特征在于：所述步骤(1)的铝箔经退火处理，且在阳极氧化前经过碱洗除油、水洗、酸洗中和、水洗的预处理。
  10. 根据权利要求8所述一种用于电池封装的彩色铝塑膜的制备方法，其特征在于：所述步骤(3)和步骤(4)采用干式层压法或挤出成型的方法实现层间连接。
  11. 一种镀膜彩色铝合金的制备方法，其特征在于：将铝合金先进行阳极氧化处理，得到表面具有阳极氧化膜层的铝合金；再阳极氧化层的表面通过离子溅射的方法附着用于呈色的金属膜层，通过控制阳极氧化处理的电压或电流、时间以及镀层金属的种类，制备得到呈现颜色可控的镀膜彩色铝合金；其中，所述阳极氧化处理的电压 为3～120V或电流密度为50～800mA/dm 2，氧化时间为5～60min；镀层金属包括粒径为1～100nm的金、铂、铬；呈现的颜色为除铝和镀层金属本身颜色外的可见光波长范围内的颜色。
  12. 根据权利要求11所述的一种镀膜彩色铝合金的制备方法，其特征在于：所述阳极氧化膜层的厚度为10～2000nm，阳极氧化膜层上均匀分布有孔径为30～140nm的孔洞。
  13. 根据权利要求11所述的一种镀膜彩色铝合金的制备方法，其特征在于：所述阳极氧化处理的电解液槽温度为20～30℃，电解液浓度为0.1～0.5mol/L，电解液包括磷酸、硫酸、草酸中的至少一种。
  14. 根据权利要求13所述的一种镀膜彩色铝合金的制备方法，其特征在于：所述电解液还包括磷酸、硫酸、草酸酸根对应的酸式盐或氟化物中的至少一种。
  15. 根据权利要求11所述的一种镀膜彩色铝合金的制备方法，其特征在于：所述镀金属膜层的厚度为1～100nm。
  16. 根据权利要求1所述的一种镀膜彩色铝合金的制备方法，其特征在于：所述阳极氧化处理的电压采用恒电压，或电流采用恒流电流。
  17. 根据权利要求11所述的一种镀膜彩色铝合金的制备方法，其特征在于：所述彩色包括单色光颜色所述单色光颜色包括紫色、蓝色、绿色、黄色、橙色和红色。
  18. 根据权利要求11所述的一种镀膜彩色铝合金的制备方法，其特征在于：所述彩色还包括复色光颜色，所述复色光颜色为灰色。
  19. 根据权利要求11所述的一种镀膜彩色铝合金的制备方法，其特征在于：所述铝合金经过碱洗除油、水洗、酸洗中和、水洗的预处理工序后进行阳极氧化处理。
  20. 根据权利要求11所述的一种镀膜彩色铝合金的制备方法，其特征在于：所述阳极氧化处理的装置包括阳极氧化槽，阳极氧化槽内设置有石墨板电极和铝合金，石墨板电极和铝合金浸入或部分浸入电解液中，二者的一端相互连接且设置有电压表和/或电流表。
PCT/CN2020/142400 2020-10-10 2020-12-31 一种用于电池封装的彩色铝塑膜、镀膜彩色铝合金及其制备方法 Ceased WO2022073309A1 (zh)

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