CN112201389A - Conductive film replacing aluminum foil and preparation method thereof - Google Patents

Conductive film replacing aluminum foil and preparation method thereof Download PDF

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Publication number
CN112201389A
CN112201389A CN202011065257.7A CN202011065257A CN112201389A CN 112201389 A CN112201389 A CN 112201389A CN 202011065257 A CN202011065257 A CN 202011065257A CN 112201389 A CN112201389 A CN 112201389A
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layer
film
conductive film
aluminum foil
coating
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CN112201389B (en
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吴明忠
汪茹
黄云辉
伽龙
曾祥平
焦鑫鹏
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Zhejiang rouzhen Technology Co.,Ltd.
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Zhejiang Changyu New Materials Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0605—Carbon
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0635—Carbides
    • C—CHEMISTRY; METALLURGY
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641—Nitrides
    • C23C14/0652—Silicon nitride
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/081—Oxides of aluminium, magnesium or beryllium
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/20—Metallic material, boron or silicon on organic substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/20—Metallic material, boron or silicon on organic substrates
    • C23C14/205—Metallic material, boron or silicon on organic substrates by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/26—Vacuum evaporation by resistance or inductive heating of the source
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
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    • C23C14/30—Vacuum evaporation by wave energy or particle radiation by electron bombardment
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    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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Abstract

The invention discloses a conductive film for replacing aluminum foil and a preparation method thereof, the conductive film for replacing the aluminum foil comprises a metal layer, a middle reinforcement layer and a high polymer film layer, wherein the middle reinforcement layer is arranged at two sides of the high polymer film layer, the metal layer is arranged at the outer side of the middle reinforcement layer, the surface sheet resistance of the conductive film is 10-80m omega, the tensile strength is 150-350Mpa, the elongation at break is 75-150%, the elastic modulus is 3500-5500, the bonding force between the middle reinforcement layer and the metal layer is more than 2N/15mm, the bonding force between the high polymer film layer and the middle reinforcement layer is 2-4N/15mm, and the water vapor transmission rate is higher than<0.2g/(m224h), oxygen transmission rate<0.005cm3/(m224h). The conductive film replacing the aluminum foil can be made very light and thin, has the thickness of 3-20 microns, has strong coating binding force, is not easy to oxidize and fall off, has high barrier property and good conductivity, has the characteristics of light weight, thinness, high strength and good toughness, and effectively solves the problems of large hardness, large tensile strength, small tearing strength, high cost, heavy weight and the like of the pure aluminum foil. Can be used for replacing the application of the traditional aluminum foil in the fields of optical films, thermal protection coatings, shielding films, high-end food/medicine/cosmetic packaging with better barrier property requirements, electronic devices, batteries and the like.

Description

Conductive film replacing aluminum foil and preparation method thereof
Technical Field
The invention relates to the field of polymer films, in particular to a conductive film for replacing aluminum foil and a preparation method thereof
Background
Under the background that China has become the second largest aluminum foil consumer country after the United states, pure aluminum foils are widely applied to the fields of life, industry and the like, in particular to materials such as high-end packaging, electrolytic capacitors, heat insulation and the like. The surface of the aluminum foil is extremely clean and sanitary, so that bacteria are not easy to grow; it is used as a nontoxic packaging material, and can be directly contacted with food without causing the worry of harming human health; meanwhile, the aluminum foil is a tasteless and odorless packaging material, so that the packaged food does not have any peculiar smell; in addition, the aluminum foil is not volatile, and the aluminum foil and packaged food cannot be dried or shrunk; no grease penetration phenomenon occurs in the aluminum foil no matter at high temperature or low temperature; aluminum foil is an opaque packaging material, and therefore, a product having a high requirement for solar radiation is required to be applied in a large amount. However, pure aluminum foil has high hardness and high tensile strength, but has low tear strength, so that the pure aluminum foil is easy to tear and is not suitable for products with higher requirements on tensile strength or shielding films with higher requirements on flexibility. Pure aluminum foil has not been the best carrier for many reasons, including cost, weight and volume.
The traditional evaporation coating conductive film adopts a certain heating evaporation way to evaporate and gasify the coating material (or called coating material), and the particles fly to the surface of the substrate to condense and form the film. The physical process comprises the following steps: the deposition material is evaporated or sublimated into gaseous particles → the gaseous particles are rapidly transported from the evaporation source to the surface of the substrate → the gaseous particles are attached to the surface of the substrate to form nuclei, grow into a solid film → the atoms of the film are reconstructed or generate chemical bonding. The method has the advantages of simple film forming method, high film purity and compactness, and unique film structure and performance. Can be widely applied to the fields of optical films, thermal protection coatings and food/medicine packaging. The thickness of the coating can be controlled to be thinner, for example, the thickness of single evaporation coating by electron beam heating evaporation is 100-3000nm, for example, the thickness of single evaporation coating by resistance heating evaporation is 10-100 nm. If the conductive film is used for replacing the pure aluminum foil to achieve the metal conductivity, experience tests show that the resistance of the conductive film needs to meet certain conductivity requirements in a 50 +/-5 m omega direction, so that the conductive film replacing the aluminum foil can have stable conductivity only when a proper plating layer range is achieved. The metal coating directly deposited on the polymer film with a certain thickness is easy to fall off, so that the conductive effect of the conductive film is poor, and the barrier property is unstable.
Disclosure of Invention
Therefore, in order to overcome the problems, the invention provides a conductive film for replacing an aluminum foil, which is prepared by adopting one or a combination of two processes including but not limited to evaporation coating and magnetron sputtering coating, so that the conductive film with stability, stronger bonding force, better conductivity and better barrier property can be produced. Meanwhile, the conductive film which replaces the aluminum foil in the process has better weight advantages and volume space than the aluminum foil, and the cost of the aluminum foil can be greatly reduced.
The conductive film for replacing the aluminum foil comprises a metal layer, a middle enhancement layer and a high polymer film layer, wherein the middle enhancement layer is arranged on two sides of the high polymer film layer, the metal layer is arranged on the outer side of the middle enhancement layer, the surface sheet resistance of the conductive film is 10-80m omega, the tensile strength is 150-350Mpa, the elongation at break is 75-150%, the elastic modulus is 3500-5500, the bonding force between the middle enhancement layer and the metal layer is more than 2N/15mm, the bonding force between the high polymer film layer and the middle enhancement layer is 2-4N/15mm, and the water vapor transmission rate<0.2g/(m224h), oxygen transmission rate<0.005cm3/(m2.24h)。
Further, the polymer film layer includes a biaxially oriented polypropylene film (OPP), a cast polypropylene film (CPP), a polyethylene terephthalate film (PET), a polyimide film (PI), or a polyethylene naphthalate film (PEN).
Furthermore, the surface friction coefficient of the high polymer film layer is 0.5-1.
Furthermore, the thickness of the polymer film layer is 3-15 μm.
Further, the middle enhancement layer comprises a metal film layer and/or a non-metal film layer, the metal film layer comprises more than one of copper, nickel and nickel-chromium alloy, and the non-metal film layer comprises more than one of aluminum oxide, silicon carbide, silicon nitride, silicon oxide and graphite.
Further, the thickness of the middle enhancement layer is 10-100 nm.
Further, the metal layer comprises an aluminum metal layer, and the metal layer is made of a material different from that of the intermediate enhancement layer, and the thickness of the metal layer is 100-3000 nm.
Another object of the present invention is to provide a conductive film for replacing an aluminum foil, including the following steps:
1) coating the middle enhancement layers on the two sides of the high-molecular film layer in a magnetron sputtering coating or evaporation coating mode;
2) and coating the metal layer on the outer side of the middle enhancement layer in a vapor deposition coating or magnetron sputtering mode.
Further, the method also comprises the step of pretreating the surface of the high polymer film layer by at least one of surface plasma treatment, surface binder coating, surface particle adding, liquid honing, sand blasting, plasma etching, jet etching and chemical etching.
Further, the power of the surface plasma treatment is 1-10 kW.
Further, the evaporation coating in the step 1) adopts resistance heating, and the heating process parameters are as follows: the evaporation boat type wire feeding speed is 100-30-20 ℃, the film running speed is 2-15m/s, or the crucible type evaporation speed is 100-30-20 ℃, the film running speed is 2-15m/s, and the evaporation raw material is 3-10% of high boiling point metal with specific gravity.
Further, the evaporation coating film of the middle enhancement layer in the step 1) adopts resistance heating evaporation coating, and the single evaporation coating thickness is 10-100 nm.
Further, the magnetron sputtering process parameters of the middle enhancement layer in the step 1) are as follows: the power is less than or equal to 150kW, the transmission speed of the substrate is less than or equal to 15m/min, the argon introducing speed is 20-30L/min, and the ion source voltage is 200-250V.
Further, the thickness of the magnetron sputtering coating in the step 1) is 10-100nm
Further, the vapor deposition coating of the surface metal layer in the step 2) adopts electron beam heating vapor deposition with a single vapor deposition thickness of 100-3000nm, and adopts resistance heating vapor deposition with a single vapor deposition thickness of 10-100nm, so that the total thickness of the surface metal coating reaches 100-3000 nm.
Further, the thickness of the magnetron sputtering coating of the surface metal layer in the step 2) is 100-3000 nm.
Further, the evaporation coating film in the step 2) is heated by resistance heating or electron beams, wherein the resistance heating process parameters are as follows: evaporation boat wire feed speed: 100-1200mm/min cooling temperature: -30-20 ℃, membrane run speed: 5-15m/s or crucible type evaporation speed of 100-1200mm/min, cooling system temperature of-30-20 ℃, film running speed of 5-15m/s, evaporation of high boiling point metal with 3-10% of specific gravity of raw material; the electron beam heating process parameters are as follows: the high-voltage power supply provides acceleration voltage which is more than or equal to-30 kV for the electron beam, the film running speed is 10-20m/min, and the surface evaporation and gasification temperature reaches 1500-.
Further, the magnetron sputtering process parameters of the step 2) are as follows: the power is less than or equal to 150kW, the transmission speed of the substrate is less than or equal to 15m/min, the argon introducing speed is 20-30L/min, and the ion source voltage is 200-250V.
Further, the coating machine cavity for vapor plating is vacuumized to 10 DEG-7mbar～10-4mbar, and vacuum time of 5-30 min.
According to the technical scheme, when the surface of the high-molecular film layer is subjected to plasma impact on the surface of the material, the surface roughness of the material is effectively increased, active groups can be formed on the surface of the material, the bonding force between the high-molecular film material and the middle layer is provided, the material is easy to break down due to overlarge power, and after the plasma surface treatment is carried out by adopting the power of 1-10kW, the bonding force of an EAA test method is 2-4N/15 mm.
The invention has the beneficial effects that:
1. the polymer substrate biaxially oriented polypropylene film OPP, the casting polypropylene film CPP, the polyethylene terephthalate film PET, the polyimide film PI or the polyethylene naphthalate film PEN in the conductive film for replacing the aluminum foil can bear the radiation heat of an evaporation source and the condensation latent heat of an evaporant, and can maintain stable chemical performance and temperature resistance when being applied to various chemical systems, and can bear the temperature of-30 ℃ to 140 ℃; meanwhile, the composite material has good ductility and strength, the tensile strength reaches 150-350MPa, the elongation at break can reach 75-150%, and the elastic modulus can reach 3500-5500.
2. The selected base material has high density and light weight, the overall weight of the conductive film is effectively reduced, the aluminum-plated multilayer conductive film structure can reduce the weight by 40 percent, the thickness is reduced by 46 percent, and the cost reduction effect is obvious.
3. The amphiphilic characteristic (polymer-hydrophilic layer) of the middle enhancement layer is adopted to effectively solve the problems that the polymer material is not firmly combined with the metal layer and is easy to fall off, and the bonding force between the middle enhancement layer of the conductive film and the metal layer is more than 2N/15 mm.
4. The method adopts a combined form of processes such as vacuum evaporation, magnetron sputtering and the like, can improve the smoothness of the surface coating, simultaneously solves the problem that the surface coating is easy to fall off by repeated evaporation in a single process, and improves the yield of products.
5. The conductive film has excellent conductive performance, and the surface sheet resistance of the conductive film is 10-80m omega.
6. The conductive film has excellent barrier property and water vapor transmission rate
<0.2g/(m224h), oxygen transmission rate<0.005cm3/(m2.24h)。
Drawings
FIG. 1 is a schematic structural diagram of a conductive film replacing aluminum foil according to the present invention
1-metal layer, 2-intermediate reinforcing layer, 3-high molecular film layer
FIG. 2 is a scanning electron microscope microscopic image of the conductive film of the present invention instead of aluminum foil
Detailed Description
The technical solutions in the embodiments of the present invention will be specifically and clearly described below, but the present invention is not limited to the following embodiments, and all other embodiments obtained by a person of ordinary skill in the art without creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention.
Example 1
A conductive film for replacing aluminum foil comprises a 6 μm thick PET layer, 50nm thick aluminum oxide layers evaporated on both sides of the PET layer, and 500nm thick metal aluminum layers evaporated outside the aluminum oxide layers.
The preparation method of the conductive film comprises the following steps:
1) carrying out surface plasma treatment on the surface of the PET layer with the power of 5 kW;
2) preheating the evaporation boat, and vacuumizing the cavity of the evaporator to 10 DEG-5mbar, controlling the vacuumizing time to be 10min, then performing evaporation coating on the middle enhancement layer on two sides of the PET layer in the step 1), wherein the thickness of single aluminum oxide coating is 50nm, the evaporation boat type wire feeding speed is 500mm/min, the cooling temperature is-10 ℃, and the film running speed is 12 m/s;
3) and (3) evaporating and coating a metal aluminum layer on the outer side of the middle enhancement layer obtained in the step 2), wherein the heating mode is resistance heating, the speed of an aluminum wire is controlled in an evaporation boat mode to be 1000mm/min, the winding speed is 8m/s, the cooling temperature is-10 ℃, the single thickness is 100nm, and the evaporation frequency is 5 times.
The surface sheet resistance of the conductive film obtained based on the scheme is 50m omega, the EAA comparison method is used for detecting the products, the bonding force between the middle enhancement layer and the metal layer is 6N/15mm, the bonding force between the thin film layer and the middle layer is 4N/15mm, which is far larger than the bonding force of the metal aluminum directly plated on the high polymer film substrate by 0.7N/15mm, the bonding force of the conductive film replacing the aluminum foil is effectively enhanced under the condition of meeting the requirement of conductivity, and simultaneously, the water vapor permeability in the barrier property is 0.1g/(m omega)224h), oxygen transmission rate of 0.002cm3/(m224h), the water vapor transmission rate is 0.5 g/(m) better than that of pure aluminum foil224h), oxygen transmission rate of 0.4cm3/(m224h). The conductive film replacing the aluminum foil has the tensile strength of 280MPa, the elongation at break of 102 percent and the elastic modulus of 4500.
Example 2
A conductive film replacing an aluminum foil comprises an OPP layer with the thickness of 4.5 microns, nickel-chromium alloy middle reinforcing layers with the total thickness of 100nm are coated on two sides of the OPP layer through magnetron sputtering, and metal aluminum layers with the total thickness of 1000nm are formed on the outer side of the middle layer through vacuum evaporation.
The preparation method of the conductive film comprises the following steps:
1) carrying out surface plasma treatment on the surface of the OPP layer with the power of 7 kW;
2) coating a nickel-chromium alloy intermediate layer on two sides of the OPP layer in the step 1) by magnetron sputtering, wherein the magnetron sputtering process parameters are as follows: the power is 150kW, the transmission speed of the substrate is 8m/min, the argon introducing speed is 30L/min, and the ion source voltage is 250V;
3) evaporating the outer side of the middle enhancement layer obtained in the step 2) to form a coated metal aluminum layer, wherein the adopted evaporated coating is resistance heating, the crucible type evaporation speed is 1000mm/min, the cooling temperature is-20 ℃, the film running speed is 8m/s, and high-boiling point metal titanium powder with the specific gravity of 8% of the evaporation raw material is evaporated. The thickness of each time is 100nm, and the evaporation times are 10 times.
The surface sheet resistance of the conductive film obtained based on the scheme is 30m omega, an EAA test method is also adopted for the products, the bonding force of the film layer and the middle layer is 3.8N/15mm, the bonding force of the middle enhancement layer and the metal layer is 5N/15mm, the bonding force is far greater than the bonding force of metal copper directly plated on a high polymer film substrate by 0.7N/15mm, the bonding force of the conductive film under the preparation method is greatly improved when the conductive film meets the conductivity requirement, and meanwhile, the water vapor transmission rate in the barrier property is 0.05g/(m2.24h), the oxygen transmission rate is 0.0016cm 3/(. square meter.24 h), the water vapor transmission rate is 0.5g/(m2.24h), and the oxygen transmission rate is 0.4cm3The conductive film has the advantages of tensile strength of 285Mpa, elongation at break of 130% and elastic modulus of 4800 (square meter and 24h).
Example 3
A conductive film for replacing aluminum foil comprises a PET layer with the thickness of 12 mu m, aluminum oxide layers with the thickness of 80nm which are vacuum-evaporated on two sides of the PET layer, and metal aluminum layers with the thickness of 1000nm which are vacuum-evaporated on the outer sides of the aluminum oxide layers.
The preparation method of the conductive film comprises the following steps:
1) carrying out surface plasma treatment on the surface of the PET layer with the power of 6 kW;
2) preheating the evaporation boat, and vacuumizing the cavity of the evaporator to 10-5mbar, controlling the vacuumizing time to be 10min, then performing evaporation coating on the middle enhancement layer on two sides of the PET layer in the step 1), wherein the thickness of single aluminum oxide coating is 80nm, the evaporation boat type wire feeding speed is 500mm/min, the temperature of a cooling system is-10 ℃, and the film running speed is 8 m/s;
3) evaporating the outer side of the middle enhancement layer obtained in the step 2) to form a coated metal aluminum layer, wherein the evaporation coating is heated by adopting an electron beam, the accelerating voltage is-30 kV, the film running speed is 20m/min, the surface evaporation gasification temperature reaches 3000 ℃, and the cavity of a coating machine is vacuumized to 10 DEG C-7mbar. The thickness of each time is 1000nm, and the thickness requirement can be met by one-time vapor deposition.
The surface sheet resistance of the conductive film obtained based on the scheme is 40m omega, an EAA test method is also adopted for the products, the bonding force of the thin film layer and the middle layer is 2.5N/15mm, the bonding force of the middle enhancement layer and the metal layer is 2.8N/15mm, and the bonding force is far greater than the bonding force of metal copper directly plated on the high polymer film substrate by 0.7N/15mm, the bonding force of the conductive film replacing the aluminum foil under the same preparation method is greatly improved under the condition of meeting the conductivity requirement, and meanwhile, the water vapor transmission rate in the barrier property is 0.02g/(m omega)224h), oxygen transmission rate of 0.004cm3/(m224h), the water vapor transmission rate is 0.5 g/(m) better than that of pure aluminum foil224h), oxygen transmission rate of 0.4cm3/(m224h). The conductive film has a tensile strength of 210MPa, an elongation at break of 120% and an elastic modulus of 4200.
Comparative example 1
A conductive film for replacing aluminum foil comprises a 6 μm thick PET layer, 50nm thick aluminum oxide layers evaporated on both sides of the PET layer, and 500nm thick metal aluminum layers evaporated outside the aluminum oxide layers.
The preparation method of the conductive film comprises the following steps:
1) preheating the evaporation boat, and vacuumizing the cavity of the evaporator to 10-5mbar, controlling the vacuumizing time to be 10min, then performing evaporation coating on the middle enhancement layer on two sides of the PET layer, wherein the thickness of single-time aluminum oxide coating is 50nm, the evaporation boat type wire feeding speed is 500mm/min, the cooling temperature is-10 ℃, and the film running speed is 12 m/s;
2) and (2) evaporating and coating a metal aluminum layer on the outer side of the middle enhancement layer obtained in the step 1), controlling the speed of an evaporation boat type aluminum wire to be 1000mm/min, the winding speed to be 8m/s, the cooling temperature to be 10 ℃ below zero, the single thickness to be 100nm, and the evaporation times to be 5.
The surface sheet resistance of the conductive film obtained based on the scheme is 50m omega, the conductive film is detected by an EAA comparison method, the bonding force between the thin film layer and the middle layer is 2N/15mm, and the bonding force between the middle enhancement layer and the metal layer is 3N/15 mm. It can be seen that the plasma treatment has little influence on the sheet resistance of the surface metal plating layer, but has great influence on the binding force between the intermediate layer and the polymer substrate, which is less than the binding force of 4N/15mm after the surface plasma treatment, and the conductive film has the tensile strength of 140MPa, the elongation at break of 60% and the elastic modulus of 3406.

Claims (10)

1. A conductive film for replacing aluminum foil is characterized in that: the conductive film comprises a metal layer, a middle reinforcing layer and a high polymer film layer, wherein the middle reinforcing layer is arranged on two sides of the high polymer film layer, the metal layer is arranged on the outer side of the middle reinforcing layer, the surface sheet resistance of the conductive film is 10-80m omega, the tensile strength is 150-350Mpa, the elongation at break is 75-150%, the elastic modulus is 3500-5500, the bonding force between the middle reinforcing layer and the metal layer is more than 2N/15mm, the bonding force between the high polymer film layer and the middle reinforcing layer is 2-4N/15mm, and the water vapor transmission rate is 2-4N/15mm<0.2g/(m224h), oxygen transmission rate<0.005cm3/(m2.24h)。
2. The conductive film as claimed in claim 1, which replaces aluminum foil, wherein: the surface friction coefficient of the polymer film layer is 0.5-1.
3. The conductive film replacing an aluminum foil as set forth in claim 1 or 2, wherein: the middle enhancement layer comprises a metal film layer and/or a non-metal film layer, the metal film layer comprises more than one of copper, nickel and nickel-chromium alloy, and the non-metal film layer comprises more than one of aluminum oxide, silicon carbide, silicon nitride, silicon oxide and graphite.
4. The conductive film replacing an aluminum foil as set forth in claim 1 or 2, wherein: the thickness of the middle reinforcing layer is 10-100 nm.
5. The conductive film replacing an aluminum foil as set forth in claim 1 or 2, wherein: the high polymer film layer comprises a biaxially oriented polypropylene film (OPP), a casting polypropylene film (CPP), a polyethylene terephthalate film (PET), a polyimide film (PI) or a polyethylene naphthalate film (PEN), and the thickness of the high polymer film layer is 3-15 mu m.
6. The conductive film replacing an aluminum foil as set forth in claim 1 or 2, wherein: the metal layer comprises an aluminum metal layer, the material of the metal layer is different from that of the middle enhancement layer, and the thickness of the metal layer is 100-3000 nm.
7. A method for preparing the conductive film as claimed in any one of claims 1 to 6 instead of aluminum foil, comprising the steps of:
1) coating the middle enhancement layers on two sides of the high-molecular thin film layer in a magnetron sputtering coating or evaporation coating mode, wherein resistance heating is adopted for evaporation coating, and the resistance heating process parameters are as follows: the evaporation boat type parameter is wire feeding speed of 100-; the magnetron sputtering process parameters are as follows: the power is less than or equal to 150kW, the transmission speed of the substrate is less than or equal to 15m/min, the argon introducing speed is 20-30L/min, and the ion source voltage is 200-250V;
2) coating the metal layer on the outer side of the middle enhancement layer in a mode of vapor deposition coating or magnetron sputtering, wherein the vapor deposition coating adopts resistance heating or electron beam heating, and the resistance heating process parameters are as follows: evaporation boat wire feed speed: 100-1200mm/min cooling temperature: -30-20 ℃, membrane run speed: 5-15m/s or crucible type evaporation speed of 100-1200mm/min, cooling system temperature of-30-20 ℃, film running speed of 5-15m/s, evaporation of high boiling point metal with 3-10% of specific gravity of raw material; the electron beam heating process parameters are as follows: the high-voltage power supply provides acceleration voltage which is more than or equal to-30 kV for the electron beam, the film running speed is 10-20m/min, and the surface evaporation and gasification temperature reaches 1500-; the magnetron sputtering process parameters are as follows: the power is less than or equal to 150kW, the transmission speed of the substrate is less than or equal to 15m/min, the argon introducing speed is 20-30L/min, and the ion source voltage is 200-250V.
8. The method of claim 7, wherein: the method also comprises the step of pretreating the surface of the high-molecular film layer by at least one of surface plasma treatment, surface binder coating, surface particle adding, liquid honing, sand blasting, plasma etching, jet etching and chemical etching.
9. The method of claim 8, wherein: the power of the surface plasma treatment is 1-10 kW.
10. The method of any one of claims 7-9, wherein: the coating machine cavity for vapor plating is vacuumized to 10 DEG-7mbar～10-3mbar, and vacuum time of 5-30 min.
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