WO2019206058A1 - 一种金属化薄膜 - Google Patents

一种金属化薄膜 Download PDF

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Publication number
WO2019206058A1
WO2019206058A1 PCT/CN2019/083601 CN2019083601W WO2019206058A1 WO 2019206058 A1 WO2019206058 A1 WO 2019206058A1 CN 2019083601 W CN2019083601 W CN 2019083601W WO 2019206058 A1 WO2019206058 A1 WO 2019206058A1
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metallized film
film according
metal
silicon
metal layer
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PCT/CN2019/083601
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English (en)
French (fr)
Inventor
桂宗彦
阮晓白
王儒旭
荒井崇
长田俊一
Original Assignee
东丽先端材料研究开发（中国）有限公司
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Priority to JP2020532931A priority Critical patent/JP7465805B2/ja
Priority to CN201980004289.5A priority patent/CN111225994B/zh
Publication of WO2019206058A1 publication Critical patent/WO2019206058A1/zh

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    • 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
    • C23C14/22—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
    • 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
    • C23C14/58—After-treatment

Definitions

  • the present invention relates to the field of metallized film capacitors, and more particularly to a metallized film having a special structure, a method for preparing the same, and a capacitor comprising the metalized film.
  • the present invention relates to a technique for improving the heat and humidity resistance of a metallized film.
  • Safety capacitors have been widely adopted in this context. Safety capacitors refer to safety capacitors that do not cause electric shock after the capacitor fails, and do not endanger personal safety. Safety capacitors are typically only used for filtering in anti-jamming circuits. They are used in the power supply filter to filter the power supply and filter the common mode and differential mode interference respectively.
  • a metallized film capacitor is generally roughly classified into a metallized film capacitor using a metal foil as an electrode, and a metallized film capacitor using an evaporated metal provided on a dielectric film as an electrode.
  • the metalized film capacitor using the vapor-deposited metal as an electrode (hereinafter referred to as a metal vapor-deposited electrode) has a small volume in the metalized film capacitor using the metal foil as an electrode, and can be made small. Lightweight.
  • the metal vapor-deposited electrode has a unique function of evaporating the metal vapor-deposited electrode around the defect portion and recovering the function of the capacitor after the splash, which is generally called a self-recovery function.
  • Metallized film capacitors using vapor-deposited metal as an electrode are widely used because of their high reliability against dielectric breakdown due to the self-recovery function.
  • Metallized films often use aluminum or zinc aluminum alloys as their electrode layer materials. Capacitors can be used in high temperature and high humidity environments, especially in the presence of voltage, zinc and aluminum are easily oxidized in a hot and humid environment to form non-conductive substances such as metal oxides, hydroxides and salts. Poor heat and humidity resistance of the metallized film results in rapid attenuation of the capacitor capacity in a hot and humid environment.
  • the heat and humidity resistance of capacitors is related to many factors, including potting resin, capacitor housing, wire soldering, gold spray treatment and heat and humidity resistance of capacitor film.
  • the heat and humidity resistance of capacitor film directly affects the heat and humidity resistance of capacitors. Performance is of great significance for the heat and humidity resistance of capacitors.
  • the improvement of the moist heat resistance of the capacitor film can be performed by using an oxide, an oil or the like as a protective layer to protect the metal layer.
  • an oxide, an oil or the like used as a protective layer to protect the metal layer.
  • CN97114365.X uses silicon oxide as a protective layer for the zinc-aluminum layer
  • CN95120817.9 uses aluminum oxide as a protective layer for the zinc-aluminum layer.
  • the oxide coating needs to be formed under high vacuum and high temperature, which increases the difficulty of production; and the oxide has brittleness, and the protective layer is easy to be brittle, thereby reducing the protective property, and the low-thickness oxide is insufficient to form. Sufficient protection. Therefore, the method of using an oxide as a protective layer of a metallized film is not practical.
  • CN95191020.5 uses at least one of a silicone-based oil, a fluorine-based oil, an alkylnaphthalene, a polydiphenyl ether, a fatty acid, a fatty acid salt, and a paraffin as a protective layer, but the actual protective effect is unsatisfactory. With the increase of the humidity and heat resistance requirements of the capacitor, the protection effect cannot be achieved under the conditions of high temperature and high humidity.
  • the present invention provides a metallized film excellent in moisture and heat resistance.
  • the metallized film has a metal layer on at least one side of both faces of the substrate film.
  • the metal layer refers to a layer containing a metal element or a metal compound. Specifically, the metal layer contains a metal element, but it also covers a case where a metal compound is contained.
  • the metallized film provided by the invention can have the above properties after high temperature and high humidity treatment, that is, after the metallized film provided by the invention is subjected to high temperature and high humidity treatment, a certain proportion of the metal zinc remains in the metal elemental substance. status.
  • Such a metallized film is excellent in its resistance to moist heat after being prepared into a capacitor, and even after the moisture and oxidizing gas intrude into the capacitor, the metallized film can remain in the elemental state for a long period of time, thereby The capacitor can maintain capacity and other performance stability for a long period of time, so that the capacitor has excellent heat and humidity resistance.
  • the specific method of the above XPS test is as follows: the metal surface of the metallized film is subjected to surface analysis using XPS (Thermo scientific K-Alpha).
  • the analysis conditions were as follows: Monochromatic Al K ⁇ 1, 2 lines (1486.6 eV) was used, the diameter of the X-ray was 400 ⁇ m, and the angle of photoelectron extraction was 90°.
  • the resulting XPS lines were smoothed using Savitzky and Golay smoothing, and C1s were calibrated at 284.6 eV.
  • the intensity values at 490 eV and 498 eV were obtained on the line, the ratio of which is the required data.
  • the zinc-aluminum alloy metallized film provided by the present invention preferably has a ratio of the intensity at 490 eV measured by XPS to the intensity at 498 eV of more than 0.2 after being treated at 105 ° C and 100% RH for 3 hr. That is, more metal zinc remains in the elemental state of the metal.
  • a metallized film that is more resistant to heat and humidity provides better heat and humidity resistance to the capacitor.
  • oxygen may be introduced into the metallized film.
  • an oxide can be deposited on the base film of the metallized film, but a method such as processing the metallized film in an aerobic environment is preferred.
  • the metalized film contains oxygen, which has the following effects: improving the adhesion of the base film and the metal layer, inhibiting the metal layer from being oxidized on the base film side; forming an oxygen content of the metal on the surface of the metal layer at the interface between the base film and the metal layer
  • the compound has the effect of blocking an oxidizing gas (such as oxygen, water vapor, etc.), and can improve the moist heat resistance of the metalized film.
  • the distribution of oxygen elements affects the heat and humidity resistance of the metal layer. It is preferable that oxygen is present on the surface of the substrate of the metallized film, and at least two oxygen elements are concentrated in the cross-sectional direction of the metal layer.
  • the specific test method for the enrichment of oxygen is as follows: The metallized film was subjected to cross-sectional analysis using STEM-EDX (JEOL JEM-ARM200F Dual-X, detector: JEOL JED2300).
  • the analysis conditions were as follows: a section of the metallized film was prepared by a method of resin-embedded-FIB (SIINT SMI3200SE, Hitachi FB-2000A-2, and FEI company Strata 400S), and the obtained sample section was subjected to STEM-EDX at 200 kV. Analysis shows that the distribution state of oxygen element in the cross-sectional direction is determined according to the number of points of the maximum value of the oxygen element content on the distribution curve of the metal layer of the metallized film and the cross-section of the protective layer, and each maximum value corresponds to An enrichment of oxygen.
  • the metallized film one or more of aluminum, zinc, magnesium, tin, copper, or the like may be used as the material of the metal layer.
  • zinc aluminum alloy is preferably used as the material of the metal layer of the metalized film.
  • Aluminum and zinc have better stability than other commonly used metals, among which aluminum has relatively good moist heat resistance, but aluminum has poor corona resistance. In the heat and humidity resistance test, under the condition of loading voltage, the capacitor is traced. The air will be broken down, causing a corona phenomenon, causing the metal to scatter, resulting in a decrease in capacitor capacity. Zinc is better in corona resistance.
  • zinc aluminum alloy as the electrode material of the metallized film in the present invention, and further preferably aluminum and zinc in the metallized film.
  • the weight ratio is from 1:99 to 10:90.
  • the enrichment of aluminum in the thickness direction of the metal layer further enhances the heat and humidity resistance of the metallized film.
  • the heat and humidity resistance of aluminum is better than that of zinc.
  • the enrichment in the cross-section of the metallized film can effectively prevent the oxidation of metal zinc by moisture and oxidizing gas, and the aluminum will be oxidized into aluminum oxide and hydroxide. And carbonates, etc., such substances have better performance in blocking oxidizing gases, thereby improving the heat and humidity resistance of the capacitor film.
  • At least two aluminum elements are enriched in the cross-sectional direction of the metallized film, and the intrusion of the oxidizing gas mainly from the outer surface of the metal layer and the interface between the base film and the metal layer, so that the aluminum element Enrichment at these two locations provides better protection of the metal layer, i.e., it is further preferred that the aluminum enrichment is located on both surfaces of the metal layer.
  • the determination of the enrichment state of the aluminum element can be determined by referring to the method of determining the oxygen element enrichment state, that is, using the same cross-sectional sample as that for judging the oxygen element enrichment state, and obtaining the aluminum element on the metallized film section by STEM-EDX test.
  • the distribution of the aluminum element determines the number of aluminum-rich enrichment positions based on the number of maximum values of the aluminum element content in the direction from the metal layer to the protective layer.
  • the metal layer is added with a protective layer to better insulate the contact between the metal layer and the oxidizing gas.
  • a substance containing a silicon element and/or a fluorine element has a better protection effect on the metal layer. Therefore, the present invention further preferably contains a silicon element and/or a fluorine element on the outer surface of the metal layer or the metal layer.
  • the silicon-containing compound is preferably a polysiloxane, and the polysiloxane forms a protective layer on the surface of the metal layer, which can effectively prevent the metal from being oxidized.
  • Polysiloxane is a kind of polymer which has a repeating Si-O bond as a main chain and directly connects an organic group on a silicon atom.
  • a liquid polysiloxane is generally called a silicone oil.
  • Polysiloxane has excellent heat resistance and cold resistance, electrical insulation, weather resistance and water repellency, and is very suitable as a metal protective layer for a metallized film used as a capacitor.
  • methyl silicone oil, ethyl silicone oil, phenyl silicone oil, methyl phenyl silicone oil, etc. can be used as a protective layer material for the metallized film.
  • the polysiloxane can also be modified.
  • the modified polysiloxane refers to a silicon hydride group, an epoxy group, a hydroxyl group, a carboxyl group, an amine group, a vinyl group, a fluorenyl group, and a carbon number of 4 or more.
  • the modified polysiloxane provides better resistance to moist heat than the unmodified polysiloxane.
  • the modified silicone oil has higher reactivity than the functional group, and it is easier to form a cross-linking and inorganic reaction when the protective layer is modified such as plasma treatment, and at the same time, the modified polysiloxane is more easily associated with the metal.
  • the reaction occurs to increase the binding force of the polysiloxane to the metal, and the barrier effect against the oxidizing gas is better.
  • the fluorine-containing compound is preferably a perfluoropolyether, and the perfluoropolyether has excellent heat resistance and oxidation stability, is chemically stable, cannot be water, and is common. The solvent is dissolved, and the surface tension of the perfluoropolyether is very low.
  • the oxidizing gas hardly corrodes the metal layer through the oil film, so the perfluoropolyether is As an excellent choice for metallized film protective layer materials.
  • the perfluoropolyether in this viscosity range can provide better heat and humidity resistance. performance.
  • the viscosity is too low, and the perfluoropolyether has a low molecular weight and easily enters the metal layer, and the protection effect on the metal layer is relatively poor.
  • the perfluoropolyether with too high viscosity has a high molecular weight and a high boiling point, which is not suitable for the spraying process.
  • the thickness of the metal layer is very thin, only a few to several tens of nanometers, and the metal layer under the microstructure is not completely dense.
  • the liquid protective layer material enters the metal layer and is dispersed in the metal layer, so that an effective protective layer cannot be formed on the surface of the metal, and the ability to insulate the oxidizing gas is greatly impaired.
  • a silicon-containing compound is used as the protective layer of the metal layer in the present invention, it is preferred that at least one silicon element is enriched in the cross-sectional direction of the metallized film, and the enriched silicon element forms a protective film, which can effectively block the metal layer and the air. The contact thus protects the metallized film.
  • the method for determining the enrichment state of silicon element is the same as the method for determining the oxygen element, that is, the distribution of silicon element on the cross section of the metallized film is obtained by the same cross-section STEM-EDX test method using the oxygen element enrichment state, according to
  • the number of silicon element enrichment positions is determined by the number of maximum values of the silicon element content in the cross-sectional direction of the metal layer and the protective layer.
  • the protective layer material used is a silicon-containing compound
  • the effect is that the inorganic silicon-containing compound is more dense, can provide better barrier ability, and also enhance the bonding ability between the protective layer and the metal layer, and the bonding ability between the protective layer and the metal layer is improved, and the protection is provided.
  • the layer is better attached to the metal layer for longer lasting protection.
  • Inorganized silicon can be obtained by plasma treatment of an organic silicon compound. Since the inorganic silicon element is dispersed in the organosilicon compound, the thermal resistance of the protective layer is not caused by the brittleness of the inorganic silicon compound. Decline.
  • the test method for determining the presence of a peak representing a mineralized silicon element in the metallized film by XPS analysis is as follows: XPS (Thermo scientific K-Alpha) is used for surface analysis of the metallized region of the metallized film, and the analysis conditions are as follows: Using Monochromatic Al K ⁇ 1, 2 lines (1486.6 eV), the X-ray has a diameter of 400 ⁇ m, and the photoelectron extraction angle is 90°. The resulting XPS lines were smoothed using Savitzky and Golay smoothing and the C1s were calibrated at 284.6 eV. Check if there is a peak at 104eV, and the presence of a peak indicates the presence of inorganic silicon.
  • XPS Thermo scientific K-Alpha
  • Time-of-flight secondary ion mass spectrometry can also determine whether the metallized film contains inorganic silicon and quantitatively characterize the degree of mineralization of silicon.
  • the protective layer material used is a silicon-containing compound, it is further preferred that the degree of mineralization of silicon is 0.1 or more by time-of-flight secondary ion mass spectrometry (TOF-SIMS) analysis for the metalized film.
  • TOF-SIMS is an extremely high-resolution measurement technique for measuring the ion mass by exciting the surface of the sample with a single ion and depending on the time at which the generated secondary ions fly to the detector due to the difference in mass.
  • the test method is as follows: Surface analysis is performed on the metallized area of the metallized film using TOF-SIMS, and the analysis conditions are as follows: TOF. SIMS 5 type flight time secondary ion mass spectrometer manufactured by ION-TOF, 1 time electron For Bi3 ++ , the intensity ratio of [ 76 SiO 3 - ] and [ 75 SiO 2 CH 3 - ] was measured as the degree of mineralization of silicon. More preferably, the degree of mineralization of silicon is 0.15 or more.
  • a preferred silicon element content is from 0.005 to 0.3 ⁇ g/cm 2 . If the amount of the silicon-containing substance is too small, a sufficient protective layer may not be formed, and the metal layer may not be well protected. Excessive silicon-containing material, vapor deposited film rolls may form slippage between the metallized films during storage, which may cause processing difficulties when winding the capacitor core. Slippage may occur between the film and the film in the coiled capacitor core, and a larger slip may occur in the hot pressing process, so that the gold spray layer may not be in good contact with the metal on the metallized film. The resulting capacitor performance may be degraded or even fail. Experiments have shown that when the content of silicon element is 0.005 to 0.3 ⁇ g/cm 2 , the silicon-containing substance can form an effective protective layer without affecting the processing performance of the capacitor.
  • the content of the fluorine element is preferably 5 ⁇ g/cm 2 to 40 ⁇ g/cm 2 . Similar to the silicon-containing compound as a protective layer material, if the content of the fluorine-containing substance is too small, a sufficient protective layer may not be formed, and the metal layer may not be well protected. Excessive fluorine-containing substances may cause slippage between the metallized films, and when the capacitor core is wound, slippage may occur between the film and the film, and the workability is affected.
  • the content of the fluorine element is from 5 ⁇ g/cm 2 to 40 ⁇ g/cm 2 .
  • the fluorine-containing substance can form an effective protective layer without affecting the production performance of the capacitor.
  • a commonly used film can be used as a base film of the metallized film of the present invention, preferably polypropylene, polyethylene, polyethylene terephthalate or polynaphthalene dicarboxylic acid.
  • a film such as ethylene glycol ester, polyphenylene sulfide, polycarbonate, polystyrene or polyvinylidene fluoride is used as the base film.
  • the outer surface of the metal layer of the present invention has a protective layer, and the protective layer contains one or more of polysiloxane or perfluoropolyether.
  • the polysiloxane is a modified polysiloxane, that is, an alkyl group or an acid anhydride having a silicon hydrogen group, an epoxy group, a hydroxyl group, a carboxyl group, an amine group, a vinyl group, a fluorenyl group, and a carbon number of 4 or more.
  • the polysiloxane is preferably a polysiloxane having one or more of an epoxy group and a hydroxyl group.
  • the capacitor is made of the above metalized film, and the heat and humidity resistance is excellent. In a high temperature and high humidity environment, the speed of the capacitor capacity is lowered, and the service life of the capacitor is greatly prolonged.
  • test methods used in the examples and comparative examples are as follows.
  • the ratio of the intensity at 490 eV to the intensity at 498 eV is simply referred to as "Zn ratio” (referred to as “pre-Zn ratio” before moisture-resistant heat treatment and "post-Zn ratio” after moisture-resistant heat treatment).
  • Zn ratio The surface of the metallized film after the moisture-resistant heat treatment was measured by XPS (Thermo scientific K-Alpha), and the peak of Zn LMM was obtained between 485eV and 505 eV, and processed by XPS software to distinguish 0-valent zinc (490 eV) and + The peak of divalent zinc (498 eV) calculates the intensity ratio of zero-valent zinc to +2-valent zinc by the ratio of peak intensities.
  • the specific method of the test was as follows: the metallized films before and after treatment at 105 ° C and 100% RH for 3 hr were subjected to surface analysis using XPS.
  • the analysis conditions were as follows: Monochromatic Al K ⁇ 1, 2 lines (1486.6 eV) was used, the diameter of the X-ray was 400 ⁇ m, and the angle of photoelectron extraction was 90°.
  • the resulting XPS lines were smoothed using Savitzky and Golay smoothing, and C1s were calibrated at 284.6 eV.
  • the intensity values at 490 eV and 498 eV were obtained on the line, the ratio of which is the required data.
  • Degree of mineralization of silicon The metal surface of the metallized film was tested using a TOF.SIMS 5 time-of-flight secondary ion mass spectrometer manufactured by ION-TOF. The first electron was Bi3 ++ to measure [ The intensity ratio of 76 SiO 3 - ⁇ and [ 75 SiO 2 CH 3 - ⁇ is used as the degree of mineralization of silicon.
  • Test for element enrichment state in metallized film The metallized film was subjected to cross-sectional analysis using STEM-EDX (JEOL JEM-ARM200F Dual-X, detector: JEOL JED2300).
  • the analysis conditions were as follows: a section of the metallized film was prepared by a method of resin-embedded-FIB (SIINT SMI3200SE, Hitachi FB-2000A-2, and FEI company Strata 400S), and the obtained sample section was subjected to STEM-EDX at 200 kV. Analysis shows the distribution of each element in the cross-sectional direction.
  • the enrichment state determination method is as follows: in the range from the metal layer to the protective layer, it is determined that there is a number n of maximum points on the respective content distribution curves of oxygen, aluminum, and silicon elements, and it is determined that there are n points where the element is enriched.
  • Metallized film moisture resistance test The metallized film was suspended in a high temperature and high humidity tester (Espec, EHS-221MD) using a clip, and the conditions were set at 105 ° C, 100% RH, and the treatment time was 3 h.
  • Espec high temperature and high humidity tester
  • Capacitor heat and humidity evaluation The capacity attenuation ratio, that is, " ⁇ C/C", is determined based on the following method.
  • the metallized film of the present invention (metal surface width 14.0 mm ⁇ white side width 2.0 mm) was wound into a capacitor core using a core having a diameter of 3.0 mm, and the wrong side was 0.6 mm. According to the different base film, the hot pressing is carried out under the corresponding conditions.
  • the two end faces of the capacitor core are sprayed with gold and then the wire with a diameter of 0.8 mm is welded into the 14 mm capacitor box, and the epoxy resin is potted and cured.
  • the prepared capacitor was treated at 310 VAc, 85 ° C, 85% RH for 1000 h, and the capacitor capacity C before and after the test was calculated and calculated.
  • Al% (amount of aluminum as a percentage of zinc-aluminum alloy) is measured by the proportion of zinc-aluminum content: XRF (X-ray fluorescence spectrometer: ZSX Primus III+) is used to test the areal density of zinc and aluminum AD Zn and AD Al . It is ⁇ g/cm 2 . The ratio of aluminum in the metallized film was calculated using the obtained areal density.
  • XRF X-ray fluorescence spectrometer: ZSX Primus III+
  • Silicon content AD Si The surface density of the silicon element was measured using XRF (X-ray fluorescence spectrometer: Science ZSX Primus III+) in units of ⁇ g/cm 2 .
  • Fluorine content AD F The metallized film was tested for fluorine content C F in a metallized film using oxygen bomb-ion chromatography (DIONEX, ICS-1600) in units of %.
  • the film sample is cut into an oxygen bomb containing an absorbing liquid, ignited with oxygen, and shaken, and then allowed to stand, so that the fluorine-containing substance obtained after the combustion is completely absorbed, and the absorbing liquid is taken out to make a constant volume.
  • the well-adsorbed absorption liquid was further measured by ion chromatography.
  • the surface density converted to fluorine is then expressed in ⁇ g/cm 2 .
  • the calculation method is as follows,
  • AD F C F ⁇ (D base film ⁇ 10 -4 ⁇ ⁇ base film ) ⁇ 10 6
  • the D base film and the p base film are respectively the thickness and density of the base film, and the units are ⁇ m and g/cm 3 , respectively.
  • the amount of the metal layer is very low relative to the base film during the calculation, and is neglected.
  • Judgment of the presence of inorganic silicon element The surface of the metallized film was measured by XPS (Thermo scientific K-Alpha), and if a significant peak was present at 104 eV, it was determined that inorganic silicon was present.
  • the specific method of the test was as follows: the metallized films before and after treatment at 105 ° C and 100% RH for 3 hr were subjected to surface analysis using XPS.
  • the analysis conditions were as follows: Monochromatic Al K ⁇ 1, 2 lines (1486.6 eV) was used, the diameter of the X-ray was 400 ⁇ m, and the angle of photoelectron extraction was 90°.
  • the resulting XPS lines were smoothed using Savitzky and Golay smoothing, and C1s were calibrated at 284.6 eV. Observe whether there is a distinct peak at 104 eV on the line.
  • Viscosity The kinematic viscosity of the sample at 25 ° C was measured in mm 2 /s.
  • Polypropylene PP (produced by Toray Industries, Inc.)
  • polyester PET produced by Toray Industries, Inc.
  • a metallized film is produced as a base film.
  • the base film is subjected to plasma treatment to remove foreign matter such as dust on the surface, and the surface tension of the base film is increased to enhance the adhesion of the metal to the base film, and an oxygen-rich layer can be formed on the base film.
  • the surface tension of a polypropylene film is about 31 mN/m. Under such surface tension, the adhesion between the metal and the polypropylene film is very weak, and a slight rubbing causes the metal to fall off.
  • the surface tension of the polypropylene-based film reaches 37-43 mN/m, and the adhesion of the metal on the base film is remarkably enhanced.
  • the atmosphere of the plasma treatment is preferably oxygen, nitrogen or a mixed gas of oxygen and nitrogen, and the plasma treatment power is preferably 0.2 kW or more, preferably 0.5 kW or more.
  • the plasma-treated atmosphere was a mixed gas of oxygen and nitrogen, and the power was 1 kW unless otherwise specified.
  • the portion of the oil-sprayed material is not deposited on the oily substance when the metal is vapor-deposited, thereby forming a blank-free side without metal.
  • the blank margin provides insulation between the two layers of metal for the fabrication of the capacitor, and capacitors cannot be made without blank margins.
  • the base film is subjected to metal evaporation to form a metal layer.
  • the appropriate amount of zinc and aluminum vapor deposition is adjusted as needed to obtain a metallized film of rated resistance.
  • it can be obtained by first aluminizing, re-galvanizing, and then aluminizing; or by first aluminizing and then galvanizing an aluminum alloy.
  • the latter utilizes the difference between the melting point and the boiling point of zinc and aluminum in the zinc-aluminum alloy.
  • the aluminum is evaporated, and as the zinc-aluminum alloy wire is continuously fed into the evaporation source, the process in which zinc and aluminum are successively vapor-deposited onto the base film is cycled, thereby forming aluminum in another position on the metallized film. Enrichment.
  • the film coated with the metal layer is sprayed with a protective layer by means of a fuel injection device, and the content of silicon element on the metallized film when the silicon-containing compound is sprayed is 0.005-0.3 ⁇ g/cm 2 , preferably 0.01-0.08 ⁇ g/cm. 2 .
  • the content of the fluorine element on the metallized film when the fluorine-containing compound is sprayed is 5 to 40 ⁇ g/cm 2 , preferably 8 to 30 ⁇ g/cm 2 .
  • the protective layer is further subjected to plasma treatment to form a crosslinked structure and a mineralized structure.
  • the crosslinked structure makes the protective layer denser and has better insulation ability; the crosslinked structure and the inorganicized structure enable the protective layer to adhere more closely to the surface of the metal layer. Thereby achieving long-lasting protection.
  • the atmosphere of the plasma treatment is preferably oxygen, nitrogen or a mixed gas of oxygen and nitrogen, and the plasma treatment power is preferably 2 kW or more, preferably 3 kW or more. In each of the examples and comparative examples, the plasma-treated atmosphere was oxygen and the power was 5 kW unless otherwise specified.
  • the single-sided vapor-deposited film is again subjected to the above steps to form a metallized film having a protective layer on the other side of the base film.
  • Metallization films of different metal ratios and protective layer materials were prepared according to the above method, and the chemical composition of the metallized film was analyzed by XPS, TOF-SIMS, XRF and oxygen bomb-ion chromatography using a metallized film before and after moisture resistance heat treatment. State and structure.
  • the metallized film was formed into a capacitor in accordance with the above method, and then subjected to moisture heat resistance evaluation, and the capacity change before and after the moisture resistance heat treatment was evaluated.
  • Examples 1-4 use Toray's PP film ( a thickness of 6 ⁇ m) as a substrate, after plasma treatment of one surface of the substrate in a mixed gas of oxygen and nitrogen (2 Pa), Fomblin Y04 forms a white edge on the partial sputtering of this surface, and then on this surface
  • the aluminum, zinc and aluminum are sequentially plated, and then the protective layer is sprayed, and then subjected to plasma treatment in an oxygen (2 Pa) environment, and the obtained metallized film is wound and slit.
  • a rolled metallized film having a metal surface width of 14.0 mm in the width direction and a white side width of 2.0 mm was obtained.
  • the ratio of zinc to aluminum and the type of protective layer are shown in Table 2, and the coating amount of the protective layer was the same.
  • the metallized film is then formed into a capacitor.
  • the metallized film and capacitor were tested and analyzed respectively, and the results obtained are shown in Table 2.
  • Examples 5 and 6 were slightly adjusted in the embodiment of Example 2.
  • the metal evaporation was performed by sequentially coating aluminum and zinc, and adjusting the protective layer to modify the type of the silicon-containing compound, respectively, using a low coating amount and a high coating amount.
  • the other implementation methods are the same as those in the second embodiment, and the implementation conditions and test results are shown in Table 3.
  • Examples 7 and 8 were slightly adjusted in the embodiment of Example 2, using a ratio of aluminum to zinc in the metal evaporation, respectively, using a high aluminum content formulation and a low aluminum content formulation to adjust the modified silicon containing the protective layer.
  • the other methods were the same as those in Example 2, and the implementation conditions and test results are shown in Table 3.
  • the method of the second embodiment was slightly adjusted, and the substance of the protective layer was changed to a fluorine-containing compound, and the coating amount of the fluorine-containing compound was also adjusted.
  • the other embodiment was carried out in the same manner as in the example 2, and the conditions were implemented. And the test results are listed in Table 4.
  • Examples 11 and 12 were adjusted in the method of Example 2 to change the base film to Toray PET ( The thickness and the coating amount of the modified silicon-containing compound used for the protective layer were adjusted to have a thickness of 6 ⁇ m.
  • the other methods were the same as those in Example 2.
  • the implementation conditions and test results are shown in Table 4.
  • Examples 13 and 14 were adjusted in the same manner as in Example 2, and the coating layer materials used in Examples 1 and 3 were used to adjust the coating amount of the protective layer material.
  • Other embodiments were the same as in Example 2, and the conditions were implemented. And the test results are listed in Table 5.
  • Examples 15 and 16 were adjusted on the basis of Example 2, and plasma treatment, blank edging, metal evaporation, and protective layer spraying were performed on both sides of the base film, and the substance of the protective layer and the coating amount thereof were adjusted.
  • the mode was the same as that of Example 2, and the implementation conditions and test results are shown in Table 5.
  • Examples 17 to 20 were adjusted in accordance with Example 2, and the protective material was changed to an unmodified silicon-containing compound, and the coating amount of the protective layer material was adjusted.
  • Other embodiments were the same as in Example 2, and the implementation conditions and test results were obtained. Listed in Table 6.
  • Comparative Example 1-6 was adjusted on the basis of Example 2, and the adjustment parts were as follows: Comparative Example 1 adjusted the ratio of aluminum to zinc, and the protective layer was not sprayed; Comparative Example 2 did not spray the protective layer; Comparative Example 3 did not apply to the base film.
  • the plasma treatment is carried out, and the protective layer material is an unmodified silicon-containing compound, and the plasma protective layer is not subjected to plasma treatment; the metal deposited in Comparative Example 4 is pure aluminum, and the sprayed protective layer material is unmodified.
  • Comparative Example 5 adjusts the ratio of evaporated aluminum and zinc, and the metal layer is prepared by first aluminizing and then galvanizing, and the protective layer of the spray is unmodified.
  • the silicon-containing compound is not plasma-treated after the protective layer is sprayed.
  • Comparative Example 6 was prepared by first aluminizing and then galvanizing, and the sprayed protective layer was an unmodified silicon-containing compound.
  • Other embodiments are the same as in Embodiment 2, and the implementation conditions and test results are shown in Tables 7 and 8. Table 2
  • Example 2 Example 3
  • Example 4 Base film PP PP PP PP PP The protective layer DY-E701 PMX-0156 KF-6000 X-22-163C metal Single side Single side Single side Single side Pre-Zn ratio 0.72 0.72 0.72 0.72 Post Zn ratio 0.42 0.35 0.33 0.38
  • Oxygen enrichment 2 places 2 places 2 places Al% (%) 1 3 7
  • Example 5 Example 6
  • Example 7 Base film PP PP PP PP
  • the protective layer KF-6003 X-22-162C X-21-5841 KF-9701 metal Single side Single side Single side Single side Pre-Zn ratio 0.72 0.72 0.75 0.57 Post Zn ratio 0.21 0.27 0.23 0.21
  • Example 10 Example 11
  • Example 12 Base film PP PP PET PET The protective layer
  • Fomblin Y06/6 Fomblin Y04 X-22-161A X-22-163C metal Single side Single side Single side Single side Pre-Zn ratio 0.72 0.72 0.72 0.72 Post Zn ratio 0.32 0.28 0.27 0.26
  • Example 16 Base film PP PP PP PP The protective layer DY-E701 KF-6000 X-21-5841 SH702 metal Single side Single side Double sided Double sided Pre-Zn ratio 0.72 0.72 0.72 0.72 Post Zn ratio 0.29 0.24 0.24 0.18 Oxygen enrichment 2 places 2 places 4 places 4 places Al% (%) 3 3 3 3 3 Al enrichment status 2 places 2 places 4 places 4 places Si enrichment state 1 place 1 place 2 places no Inorganic silicon Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have
  • Example 19 Base film PP PP PP PP PP The protective layer SH704 HIVAC F4 KF-96 KF-99 metal Single side Single side Single side Single side Pre-Zn ratio 0.72 0.72 0.72 0.72 Post Zn ratio 0.17 0.12 0.15 0.16 Oxygen enrichment 2 places 2 places 2 places Al% (%) 3 3 3 3 3 Al enrichment status 2 places 2 places 2 places Si enrichment state no no no no no Inorganic silicon Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have Have
  • Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Base film PP PP PP PP PP The protective layer - - SH702 SH702 metal Single side Single side Single side Single side Pre-Zn ratio 0.76 0.72 0.72 0.001 Post Zn ratio 0.01 0.01 0.07 0.001 Oxygen enrichment 1 place 1 place no 1 place Al% (%) 40 3 3 100 Al enrichment status no 2 places 2 places no Si enrichment state no no no no no Inorganic silicon Have Have no no Degree of silicon mineralization Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not determined Not

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Abstract

本发明提供了一种具有优异的耐湿热性的用于电容器的金属化薄膜。该金属化薄膜经105℃、100％RH处理3hr后，经XPS测定的490eV处的强度与498eV处的强度的比大于0.1，使用该金属化薄膜制备得到的电容器耐湿热性优良，在高温高湿的环境下，电容器容量的下降速度会明显下降，电容器的使用寿命大大延长。

Description

一种金属化薄膜 技术领域
本发明涉及金属化薄膜电容器领域，特别涉及一种具有特殊结构的金属化薄膜及其制备方法和包含该金属化薄膜的电容器，本发明涉及改进金属化薄膜的耐湿热性的技术。
背景技术
随着我国经济的高速发展，人们的生活水平不断提高，电子产品大量进入家庭，由于这些设备存在触电、火灾、有害辐射、化学、爆炸及机械伤人的危险，为了保护用户的生命财产安全，维护消费者利益，促进企业提高产品质量，国家相继制定了有关产品的安全标准，将上述危险减到最小，并通过立法保证安全标准的贯彻执行。被国家认可的国家认证机构，对通过有关检验的电子产品，予以认可，承认这些产品符合有关安全标准。安规电容器就在这种背景下被大量采用。安规电容是指电容器失效后，不会导致电击，不危及人身安全的安全电容器。安规电容通常只用于抗干扰电路中的滤波作用。它们用在电源滤波器里，起到电源滤波作用，分别对共模、差模干扰起滤波作用。
对于安规电容器的要求越来越高，耐湿热性的要求也变得更加严苛。采用寿命极长的金属化薄膜电容器的趋势也较为显著。金属化薄膜电容器一般大致划分为：将金属箔用作电极的金属化薄膜电容器；和将设置在电介质薄膜上的蒸镀金属用作电极的金属化薄膜电容器。其中，较之将金属箔用作电极的金属化薄膜电容器而言，将蒸镀金属用作电极(以下称作金属蒸镀电极)的金属化薄膜电容器中电极所占的体积小，可谋求小型轻便化。此外，金属蒸镀电极具有缺陷部周边的金属蒸镀电极蒸发、飞溅后电容器的功能能够得到恢复的特有功能，这一般被称作自我恢复功能。由于自恢复功能而使得其 针对绝缘破坏的可靠性高，因此以蒸镀金属用作电极的金属化薄膜电容器被广泛使用。
金属化薄膜经常采用铝或锌铝合金作为其电极层材料。电容器会在高温高湿的环境中使用，尤其是在带电压的状态下，锌和铝在湿热环境下容易被氧化，形成金属氧化物、氢氧化物和盐类等不导电的物质。金属化薄膜的耐湿热性不良会导致在湿热环境下，电容器容量的快速衰减。
电容器的耐湿热性与很多因素有关，包括灌封的树脂、电容器壳体、导线的焊接、喷金的处理以及电容器薄膜的耐湿热性能，其中电容器薄膜的耐湿热性能直接影响了电容器的耐湿热性能，对于电容器的耐湿热性具有重要的意义。
电容器薄膜的耐湿热性能的改进可以采用氧化物、油类等作为保护层来保护金属层。如CN97114365.X采用氧化硅作为锌铝层的保护层；CN95120817.9采用氧化铝作为锌铝层的保护层。但是氧化物的镀层需要在高真空和高温度下形成，增加了生产的难度；而且氧化物具有脆性，厚度较高保护层容易出现脆裂，从而降低保护性能，低厚度的氧化物不足以形成足够的保护作用。因此氧化物作为金属化薄膜的保护层的方法并不实用。CN95191020.5采用硅基油类、氟基油类、烷基萘、聚二苯醚、脂肪酸类、脂肪酸盐类和石蜡中的至少一种作为保护层，但是实际的保护效果不能令人满意，随着电容器耐湿热要求的提高，在高温高湿条件下，保护效果不能达到要求。
发明内容
基于以上情况，本发明提供了一种耐湿热性优秀的金属化薄膜。该金属化薄膜在基材薄膜的两个面的至少一侧具有金属层。金属层是指含有金属单质或金属化合物的层，具体来说，金属层含有金属单质，但也涵盖含有金属化合物的情况。本发明的金属化薄膜经105℃、100％RH处理3hr后，经XPS (X射线光电子能谱仪)测定的490eV处的强度与498eV处的强度的比大于0.1。需要说明，490eV对应Zn金属单质，498eV对应+2价形态的Zn。本发明所提供的金属化薄膜，经过高温高湿处理后，能够具备上述性能，即，本发明所提供的金属化薄膜经过高温高湿处理后，仍然有一定比例以上的金属锌保持在金属单质状态。这样的金属化薄膜在制备成电容器后，因为其自身耐湿热性能优良，即使在水气和氧化性气体侵入电容器后，金属化薄膜在较长的时间内金属部分仍然能保持在单质状态，从而使电容器在长时间内可以保持容量及其他性能的稳定，从而使电容器具有优良的耐湿热性能。
上述的XPS测试的具体方法如下：金属化薄膜的金属面使用XPS(Thermo scientific K-Alpha)进行表面分析。分析条件如下：使用Monochromatic Al Kα 1，2线(1486.6eV)，X射线的直径为400μm，光电子脱出的角度为90°。得到的XPS谱线采用Savitzky and Golay smoothing进行平滑处理，C1s在284.6eV进行校准。在谱线上得到490eV和498eV处的强度值，其比值即为所需数据。
进一步的，本发明提供的锌铝合金金属化薄膜，优选为经105℃、100％RH处理3hr后，经XPS测定的490eV处的强度与498eV处的强度的比大于0.2。即有更多的金属锌保持在金属单质状态。耐湿热性更佳的金属化薄膜，可以给电容器提供更好的耐湿热性能。
进一步的，为了提高金属化薄膜的耐湿热性能，可以在金属化薄膜中引入氧。如可以在金属化薄膜的基膜上蒸镀氧化物，但优选诸如将金属化薄膜在有氧的环境中进行加工的方法。金属化薄膜中含有氧，具有以下效果：提高基膜和金属层的附着力，抑制金属层在基膜侧被氧化；在基膜和金属层的界面上，于金属层表面形成金属的含氧化合物具有阻隔氧化性气体(如氧气、水蒸气等)效果，可以提高金属化薄膜的耐湿热性能。
基于以上效果，可以认为氧元素的分布会影响金属层的耐湿热性能。优选金属化薄膜的基材表面存在氧元素，且金属层断面方向至少有两处氧元素 富集。氧元素的富集情况的具体测试方法如下：将金属化薄膜使用STEM-EDX(JEOL公司JEM-ARM200F Dual-X，检出器：JEOL公司JED2300)进行断面分析。分析条件如下：使用树脂包埋-FIB(SIINT公司SMI3200SE、日立公司FB-2000A-2和FEI公司Strata 400S)的方法制备金属化薄膜的断面，对得到的样品断面在200kV下进行STEM-EDX的分析，得到氧元素在断面方向上的分布状态，根据金属化薄膜的金属层和保护层断面方向上的分布曲线上的氧元素含量极大值的点的数目来确定，每个极大值对应一处氧元素的富集。
进一步的，金属化薄膜可以使用铝、锌、镁、锡、铜等中的一种或多种作为其金属层的材料，本发明优选使用锌铝合金作为金属化薄膜的金属层的材料。铝和锌相对于其他常用的金属稳定性较好，其中铝的耐湿热性能又相对较好，但是铝的耐电晕性能较差，在耐湿热测试中，加载电压的条件下，电容器内微量的空气会被击穿，出现电晕现象，导致金属的飞散，从而导致电容器容量的下降。锌则耐电晕性较好，为了平衡耐湿热性和抗电晕性，所以本发明中优选使用锌铝合金作为金属化薄膜的电极材料，进一步的优选为金属化薄膜中铝元素和锌元素的重量比为1∶99-10∶90。
与氧元素的富集类似的，铝元素在金属层厚度方向上的富集更进一步提高了金属化薄膜的耐湿热性。铝的耐湿热性能优于锌，其在金属化薄膜断面方向上的富集可以有效地阻止湿气和氧化性气体对于金属锌的氧化，而且铝会被氧化成铝的氧化物、氢氧化物和碳酸盐等，这类物质的阻隔氧化性气体的性能比较好，从而提高了电容器薄膜的耐湿热性能。因此，本发明进一步优选所述的金属化薄膜断面方向至少有两处铝元素富集，由于氧化性气体的侵入主要是从金属层的外表面以及基膜和金属层的界面侵入，于是铝元素在这两个位置的富集能够更好的保护金属层，即进一步优选为铝富集位置在金属层的两个表面。铝元素的富集状态的判定可以参照氧元素富集状态判定的方法，即使用与用于判断氧元素富集状态相同的断面样品，通过STEM-EDX 测试得到铝元素在金属化薄膜断面上的铝元素的分布，根据在金属层到保护层断面方向上的铝元素含量的极大值的数目来判定铝元素富集位置的数量。
仅仅改变金属层的结构和金属层的元素富集状态虽然能够提高金属化薄膜的耐湿热性能，但是考虑到进一步提高电容器耐湿热性，为了达到更佳的耐湿热性能，还可进一步优选地给金属层增加保护层，以更好的隔绝金属层和氧化性气体的接触。含有硅元素和/或氟元素的物质对于金属层的保护效果较好。因此，本发明进一步优选在所述的金属层或金属层的外表面含有硅元素和/或氟元素。
其中，金属层或金属层的外表面含有硅元素时，含硅的化合物优选为聚硅氧烷，聚硅氧烷在金属层的表面形成一层保护层，可以有效的阻止金属被氧化。聚硅氧烷，是一类以重复的Si-O键为主链，硅原子上直接连接有机基团的聚合物，液态的聚硅氧烷一般被称为硅油。聚硅氧烷具有优良的耐热性和耐寒性、电绝缘性、耐候性和防水性，非常适合作为电容器使用的金属化薄膜的金属保护层。列举但不限于如甲基硅油、乙基硅油、苯基硅油、甲基苯基硅油等都可以作为金属化薄膜的保护层材料。对于聚硅氧烷还可以对其进行改性处理，改性聚硅氧烷是指带有硅氢基、环氧基、羟基、羧基、胺基、乙烯基、巯基、碳原子数4以上的烷基或酸酐基中的一种或多种的聚硅氧烷。相对于未改性的聚硅氧烷，改性的聚硅氧烷能够提供更好的耐湿热性能。改性硅油因其具有官能团，其反应活性更高，在对保护层进行诸如等离子处理等改性时，更加容易形成交联、无机化反应，同时，改性的聚硅氧烷更容易与金属发生反应，提高聚硅氧烷与金属的结合力，对于氧化性气体的阻隔效果更好。
金属层或金属层的外表面含有氟元素时，含氟的化合物优选为全氟聚醚，全氟聚醚具有极佳的耐热性和氧化安定性，化学性质稳定，不能被水以及常见的溶剂溶解，且全氟聚醚的表面张力非常低，当在金属的表面形成一层全氟聚醚的油膜时，氧化性气体很难透过油膜对金属层造成腐蚀，所以全氟聚 醚是作为金属化薄膜保护层材料的极佳选择。其中当全氟聚醚在20℃下的粘度在40-120mm 2/s，40℃下的粘度在25-60mm 2/s时，此粘度范围内的全氟聚醚可以提供更好的耐湿热性能。粘度过低，全氟聚醚的分子量低，容易进入金属层，对于金属层的保护作用比较差。而粘度过高的全氟聚醚，分子量高，沸点也高，不利于喷镀加工。
金属层的厚度很薄，只有几个到几十个纳米，微观结构下的金属层也并非完全致密的状态。液态的保护层物质会进入金属层，分散在金属层内，从而不能在金属的表面形成一层有效的保护层，隔绝氧化性气体的能力大大削弱。当使用含硅的化合物作为本发明中金属层的保护层时，优选在金属化薄膜的断面方向至少有一处硅元素富集，富集的硅元素形成保护膜，能够有效的阻隔金属层与空气的接触，从而保护金属化薄膜。硅元素的富集状态的判定方法与氧元素的判定方法相同，即对于使用氧元素富集状态同样的断面STEM-EDX测试方法得到硅元素在金属化薄膜断面上的硅元素的分布，根据在金属层和保护层断面方向上的硅元素含量的极大值的数目来判定硅元素富集位置的数量。
而且当使用的保护层材料为含硅的化合物的时候，金属化薄膜中进一步优选存在无机化的硅元素。其效果是，无机化的含硅化合物更加致密，能够提供更好的阻隔能力，同时也增强了保护层和金属层之间的结合能力，保护层和金属层之间结合能力的提高，使保护层更好的附着在金属层上，形成更长效的保护。无机化的硅元素可以通过对有机的硅化合物进行等离子处理等方法得到，由于无机化的硅元素分散在有机硅化合物中，不会因为无机硅化合物的脆性导致保护层的破裂而导致耐湿热性能的下降。
通过XPS分析测定金属化薄膜中存在代表无机化的硅元素的峰的测试方法如下：对金属化薄膜的金属面的金属化区域使用XPS(Thermo scientific K-Alpha)进行表面分析，分析条件如下：使用Monochromatic Al Kα 1，2线(1486.6eV)，X射线的直径为400μm，光电子脱出的角度为90°。得到的XPS 谱线采用Savitzky and Golay smoothing进行平滑处理，C1s在284.6eV进行校准。检查104eV处是否有峰存在，有峰存在说明存在无机化的硅元素。
飞行时间二次离子质谱(TOF-SIMS)也可以判断金属化薄膜中是否含有无机硅，且可以定量的表征硅的无机化程度。当使用的保护层材料为含硅的化合物的时候，进一步优选地，针对金属化薄膜通过飞行时间二次离子质谱(TOF-SIMS)分析可测定出硅的无机化程度为0.1以上。所述的TOF-SIMS是通过用一次离子激发样品表面，根据产生的二次离子因质量不同而飞行到探测器的时间不同来测定离子质量的极高分辨率的测量技术。测试方法如下：对金属化薄膜的金属面的金属化区域使用TOF-SIMS进行表面分析，分析条件如下：使用ION-TOF公司生产的TOF.SIMS 5型飞行时间二次离子质谱仪，1次电子为Bi3 ++，以测得的【 76SiO 3 -】和【 75SiO 2CH 3 -】的强度比作为硅的无机化程度。进一步优选硅的无机化程度为0.15以上。
当使用含硅的物质作为保护层时，优选的硅元素含量为0.005-0.3μg/cm 2。含硅物质的量太少，则可能不能形成足够的保护层，可能不能很好的保护金属层。含硅物质过多，蒸镀的膜卷在存放过程中金属化薄膜之间的可能会形成滑移，在卷绕电容器芯子的时候可能造成加工困难。卷好的电容器芯子中的膜与膜之间可能会形成滑移，在热压工序中可能产生更大的滑移，导致喷金层可能不能很好的与金属化薄膜上的金属接触，最终做成的电容器性能可能下降甚至失效。实验证明当硅元素的含量为0.005～0.3μg/cm 2时，含硅物质既能形成有效的保护层，又能够不影响电容器的加工性能。
当使用含氟的物质作为保护层时，优选的氟元素的含量为5μg/cm 2-40μg/cm 2。与含硅化合物作为保护层物质类似的，含氟的物质含量如果太少，则可能不能形成足够的保护层，可能不能很好的保护金属层。含氟物质过多，可能会使金属化薄膜之间的形成滑动，在卷绕电容器芯子的时候，膜与膜之间可能会形成滑移，加工性能受到影响。当氟元素的含量为5μg/cm 2-40μg/cm 2。含氟物质既能形成有效的保护层，又能够不影响电容器的生产性能。
作为生产电容器使用的金属化薄膜的基材，常用的薄膜均可作为本发明的金属化薄膜的基膜，优选采用聚丙烯、聚乙烯、聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯、聚苯硫醚、聚碳酸酯、聚苯乙烯或聚偏氟乙烯等薄膜作为基膜。
进一步的，本发明所述的金属层的外表面具有保护层，所述的保护层含有聚硅氧烷或全氟聚醚中的一种或多种。
进一步的，所述聚硅氧烷是改性聚硅氧烷，即带有硅氢基、环氧基、羟基、羧基、胺基、乙烯基、巯基、碳原子数4以上的烷基或酸酐基中的一种或多种的聚硅氧烷。所述聚硅氧烷优选为带有环氧基、羟基中的一种或多种的聚硅氧烷。
使用上述的金属化薄膜制成电容器，耐湿热性优良，在高温高湿的环境下，电容器容量的下降速度会明显降低，电容器的使用寿命大大延长。
具体实施方式
通过以下实施例对本发明做更详细的描述，但所述实施例不构成对本发明的限制。以下实施例采用优选条件，实施例列举方法并不构成对于其他实施方法的限制。
实施例与对比例中使用的测试方法如下。
490eV处的强度与498eV处的强度的比简称为“Zn比”(其中耐湿热处理前称为“前Zn比”，耐湿热处理后称为“后Zn比”)。将耐湿热处理后的金属化薄膜使用XPS(Thermo scientific K-Alpha)进行表面测定，在485eV-505eV之间得到Zn LMM的峰，通过XPS软件对其进行处理，区分0价锌(490eV)和+2价锌(498eV)的峰，通过峰强度的比计算0价锌与+2价锌的强度比。测试的具体方法如下：将105℃、100％RH处理3hr前后的金属化薄膜分别使用XPS进行表面分析。分析条件如下：使用Monochromatic Al Kα 1，2线(1486.6eV)，X射线的直径为400μm，光电子脱出的角度为90°。得 到的XPS谱线采用Savitzky and Golay smoothing进行平滑处理，C1s在284.6eV进行校准。在谱线上得到490eV和498eV处的强度值，其比值即为所需数据。
硅的无机化程度：使用一台ION-TOF公司生产的TOF.SIMS 5型飞行时间二次离子质谱仪对金属化薄膜的金属面进行测试，1次电子为Bi3 ++，以测得的【 76SiO 3 -】和【 75SiO 2CH 3 -】的强度比作为硅的无机化程度。
金属化薄膜中元素富集状态的测试：将金属化薄膜使用STEM-EDX(JEOL公司JEM-ARM200F Dual-X，检出器：JEOL公司JED2300)进行断面分析。分析条件如下：使用树脂包埋-FIB(SIINT公司SMI3200SE、日立公司FB-2000A-2和FEI公司Strata 400S)的方法制备金属化薄膜的断面，对得到的样品断面在200kV下进行STEM-EDX的分析，得到各元素在断面方向上的分布状态。富集状态判定方法如下：在金属层到保护层的范围内，确定在氧、铝和硅元素的各自含量分布曲线上存在极大值点的数目n，判定为有n处该元素富集。
金属化薄膜耐湿热性测试：将金属化薄膜使用夹子悬挂在高温高湿试验机(Espec，EHS-221MD)内，设置条件105℃、100％RH，处理时间3h。
电容器耐湿热评价：基于下述方法来确定容量衰减比例，即“ΔC/C”。将本发明金属化薄膜(金属面宽度14.0mm×白边宽度2.0mm)使用直径3.0mm的卷芯卷绕成制成电容器芯子，错边0.6mm。根据基膜不同在相应条件下进行热压，在电容器芯子的两个端面进行喷金然后焊接直径0.8mm的导线，装入14mm的电容器盒子中，灌封环氧树脂，固化后即得到所需的电容器。将制好的电容器在310VAc，85℃、85％RH下处理1000h，测试处理前后电容器容量C，并计算
ΔC/C＝(C 处理后-C 处理前)/C 处理前
锌铝含量比例测算Al％(铝占锌铝合金质量百分数)：对金属化薄膜使用XRF(X射线荧光光谱仪：理学公司，ZSX Primus III+)测试锌和铝的面密 度AD Zn和AD Al，单位为μg/cm 2。利用得到的面密度计算金属化薄膜中铝的比例。
Al％＝AD Al/(AD Zn+AD Al)
硅元素含量AD Si：将金属化薄膜使用XRF(X射线荧光光谱仪：理学ZSX Primus III+)测试硅元素的面密度，单位为μg/cm 2。
氟元素含量AD F：将金属化薄膜使用氧弹-离子色谱法(DIONEX公司，ICS-1600)测试金属化薄膜中的氟元素含量C F，单位：％。将薄膜样品剪碎放入装有吸收液的氧弹中，冲入氧气点火，摇晃后静置使燃烧后得到的含氟的物质被彻底吸收后取出吸收液，定容。再将定容好的吸收液使用离子色谱进行测定。再经过换算为氟元素的面密度，单位为μg/cm 2。计算方法如下，
AD F＝C F×(D 基膜×10 -4×ρ 基膜)×10 6
其中D 基膜和ρ 基膜分别为基膜的厚度和密度，单位分别为μm和g/cm 3，计算过程中因为金属层的量相对于基膜非常低，忽略不计。
无机化的硅元素的存在判定：将耐金属化薄膜使用XPS(Thermo scientific K-Alpha)进行表面测定，在104eV处如果有明显的峰存在，即判定为存在无机化的硅元素。测试的具体方法如下：将105℃、100％RH处理3hr前后的金属化薄膜分别使用XPS进行表面分析。分析条件如下：使用Monochromatic Al Kα 1，2线(1486.6eV)，X射线的直径为400μm，光电子脱出的角度为90°。得到的XPS谱线采用Savitzky and Golay smoothing进行平滑处理，C1s在284.6eV进行校准。在谱线上得到观察104eV处是否存在明显的峰。
粘度：测量样品在25℃下的运动粘度，单位为mm 2/s。
实施例与对比例中使用的保护层成分列于表1：
表1
编号 商品名 成分 制造商 粘度(25℃，mm 2/s)
A DY-E701 环氧改性聚硅氧烷 大易化工 100
B PMX-0156 醇羟基改性聚硅氧烷 道康宁 72
C KF-6000 醇羟基改性聚硅氧烷 信越 35
D X-22-163C 环氧改性聚硅氧烷 信越 120
E KF-6003 醇羟基改性聚硅氧烷 信越 110
F X-22-162C 羧基改性聚硅氧烷 信越 220
G X-21-5841 硅醇改性聚硅氧烷 信越 30
H KF-9701 硅醇改性聚硅氧烷 信越 60
I Fomblin Y06/6 全氟聚醚 苏威 64
J Fomblin Y04 全氟聚醚 苏威 38
K X-22-161A 氨基改性聚硅氧烷 信越 25
L SH702 甲基苯基聚硅氧烷 道康宁 45
M SH704 甲基苯基聚硅氧烷 道康宁 43
N HIVACF4 甲基苯基聚硅氧烷 信越 37
O KF-96 二甲基聚硅氧烷 信越 50
P KF-99 二甲基聚硅氧烷 信越 100
具体实施方法如下：
使用聚丙烯PP(东丽株式会社产
Figure PCTCN2019083601-appb-000001
)和聚酯PET(东丽株式会社产
Figure PCTCN2019083601-appb-000002
)作为基膜制作金属化薄膜。
首先，对基膜进行等离子处理，去除表面的灰尘等异物，并提高基膜的表面张力，使金属与基膜的附着力增强，同时可以在基膜上形成一层氧富集层。如聚丙烯薄膜的表面张力大约在31mN/m，这样的表面张力下，金属与聚丙烯薄膜的附着力非常的弱，轻微的碰擦就会导致金属的脱落。薄膜经过处理后，聚丙烯基膜的表面张力达到37-43mN/m，金属在基膜上的附着力明显增强。等离子处理的气氛以氧气、氮气或氧气和氮气的混合气体为宜，等离子处理功率以0.2kW以上为宜，优选0.5kW以上。各实施例和对比例中，如无特别说明，等离子处理的气氛为氧气和氮气的混合气体，功率为1kW。
在处理好的基膜上喷镀油性物质的，喷镀油性物质的部位在进行金属蒸镀时，由于金属无法附着在油性物质上，从而形成没有金属的空白留边。空白留边为电容器的制作提供了两层金属之间的绝缘，没有空白留边则无法制成电容器。
继而，对基膜在进行金属蒸镀，形成金属层。根据需要调整合适的锌和铝的蒸镀量，得到额定电阻的金属化薄膜。对于铝元素的富集可以采取先镀铝、再镀锌、再镀铝的方法得到；也可以通过先镀铝、再镀锌铝合金的方法得到。后者利用锌铝合金中锌和铝的熔点和沸点的差异，在特点的温度区间内进行蒸镀取得时，锌先被蒸镀到基膜上，随着锌的蒸镀，锌的比例减少，铝被蒸镀出来，随着锌铝合金线的不断送入蒸镀源，锌和铝依次被蒸镀到基膜上的过程循环进行，从而在金属化薄膜上形成另一位置的铝的富集。
镀上金属层的薄膜利用喷油装置喷镀上保护层，喷镀的是含硅化合物时金属化薄膜上的硅元素的含量为0.005-0.3μg/cm 2，优选为0.01-0.08μg/cm 2。喷镀的是含氟化合物时金属化薄膜上的氟元素的含量为5-40μg/cm 2，优选为8-30μg/cm 2。含硅化合物在金属表面形成保护层时，形成硅元素的富集。含硅化合物和含氟化合物都含有氧，当其在金属表面形成保护层时，氧元素也会富集。
保护层再经过等离子处理形成交联结构和无机化结构，交联结构使保护层更加致密，隔绝能力更好；交联结构和无机化结构使使保护层可以更加紧密的附着在金属层表面，从而实现长久的保护功能。等离子处理的气氛以氧气、氮气或氧气和氮气的混合气体为宜，等离子处理功率以2kW以上为宜，优选3kW以上。各实施例和对比例中，如无特别说明，等离子处理的气氛为氧气，功率为5kW。
如果是两面金属化薄膜则将上述单面蒸镀好的薄膜再次经过上述步骤在基膜的另外一面形成具有保护层的金属化薄膜。
将不同金属配比、保护层材料按照上述方法制成金属化薄膜，将耐湿热处理前后的金属化薄膜使用XPS、TOF-SIMS、XRF和氧弹-离子色谱等方法进行分析金属化薄膜的化学组成状态和结构。将金属化薄膜按照前述方法制成电容器后进行耐湿热评价，评价耐湿热处理前后容量变化。
实施例1-4使用东丽的PP薄膜(
Figure PCTCN2019083601-appb-000003
厚度6μm)作为基材，在氧气和氮气的混合气体中(2Pa)中对基材的某一个面进行等离子处理后，在此面的局部喷镀上Fomblin Y04形成白边，再在此面上依次镀上铝、锌和铝，再喷镀上保护层，继而在氧气(2Pa)的环境下进行等离子处理，处理得到的金属化薄膜收卷，分切。得到幅宽方向上金属面宽度14.0mm×白边宽度2.0mm的卷状金属化薄膜。锌和铝的比例、保护层的种类列于表2，保护层的涂布量相同。继而，将金属化薄膜制成电容器。分别对金属化薄膜和电容器进行测试分析，得到的结果列于表2。
实施例5和6在实施例2的实施方式上稍作调整，金属蒸镀采用依次镀铝和锌，调整保护层改性含硅化合物种类，分别采用低涂布量和高涂布量的保护层，其他实施方法与实施例2相同，实施条件及测试结果列于表3。
实施例7和8在实施例2的实施方式上稍作调整，采用金属蒸镀时的铝和锌的比例，分别采用高铝含量配方和低铝含量配方，调整保护层使用的改性含硅化合物的种类，其他实施方法与实施例2相同，实施条件及测试结果列于表3。
实施例9和10在实施例2的实施方法上稍作调整，将保护层的物质变更为含氟化合物，含氟化合物的涂布量也加以调整，其他实施方法与实施例2相同，实施条件及测试结果列于表4。
实施例11和12在实施例2的实施方法上加以调整，将基膜变更为东丽的PET(
Figure PCTCN2019083601-appb-000004
厚度6μm)，调整保护层使用的改性含硅化合物的种类及涂布量，其他实施方法与实施例2相同，实施条件及测试结果列于表4。
实施例13和14在实施例2的基础上进行调整，分别使用实施例1和实施例3使用的保护层物质，调整保护层物质的涂布量，其他实施方式与实施例2相同，实施条件及测试结果列于表5。
实施例15和16在实施例2的基础上进行调整，在基膜的两面进行等离子处理、空白留边、金属蒸镀和保护层喷镀，调整保护层的物质及其涂布量，其他实施方式与实施例2相同，实施条件及测试结果列于表5。
实施例17-20在实施例2的基础上进行调整，变更保护性物质为未改性含硅化合物，调整保护层物质的涂布量，其他实施方式与实施例2相同，实施条件及测试结果列于表6。
对比例1-6在实施例2的基础上进行调整，调整部分如下：对比例1调整铝和锌的比例，不喷镀保护层；对比例2不喷镀保护层；对比例3不对基膜进行等离子处理，喷镀的保护层物质为未改性含硅化合物，喷镀保护层后不进行等离子处理；对比例4蒸镀的金属为纯铝，喷镀的保护层物质为未改性的含硅化合物，喷镀保护层后不进行等离子处理；对比例5调整了蒸镀的铝和锌的比例，并采用先镀铝再镀锌的方式制备金属层，喷镀的保护层为未改性的含硅化合物，喷镀保护层后不进行等离子处理。对比例6采用先镀铝再镀锌的方式制备金属层，喷镀的保护层为未改性的含硅化合物。其他实施方式与实施例2相同，实施条件及测试结果列于表7和表8。 表2
编号 实施例1 实施例2 实施例3 实施例4
基膜 PP PP PP PP
保护层 DY-E701 PMX-0156 KF-6000 X-22-163C
金属 单面 单面 单面 单面
前Zn比 0.72 0.72 0.72 0.72
后Zn比 0.42 0.35 0.33 0.38
氧富集状态 2处 2处 2处 2处
Al％(％) 1 3 7 10
Al富集状态 2处 2处 2处 2处
Si富集状态 1处 1处 1处 1处
无机硅 有 有 有 有
硅无机化程度 0.35 0.24 0.30 0.28
AD Si(μg/cm 2) 0.02 0.02 0.02 0.02
AD F(μg/cm 2) 0.02 0.08 0.05 0.09
ΔC/C(％) -1.3 -1.6 -0.9 -1.3
表3
编号 实施例5 实施例6 实施例7 实施例8
基膜 PP PP PP PP
保护层 KF-6003 X-22-162C X-21-5841 KF-9701
金属 单面 单面 单面 单面
前Zn比 0.72 0.72 0.75 0.57
后Zn比 0.21 0.27 0.23 0.21
氧富集状态 2处 2处 2处 2处
Al％(％) 3 3 20 0.5
Al富集状态 1处 1处 2处 2处
Si富集状态 1处 1处 1处 1处
无机硅 有 有 有 有
硅无机化程度 0.19 0.15 0.34 0.35
AD Si(μg/cm 2) 0.003 0.7 0.02 0.02
AD F(μg/cm 2) 0.05 0.02 0.03 0.01
ΔC/C(％) -2.4 -2.5 -1.7 -0.9
表4
编号 实施例9 实施例10 实施例11 实施例12
基膜 PP PP PET PET
保护层 Fomblin Y06/6 Fomblin Y04 X-22-161A X-22-163C
金属 单面 单面 单面 单面
前Zn比 0.72 0.72 0.72 0.72
后Zn比 0.32 0.28 0.27 0.26
氧富集状态 2处 2处 2处 2处
Al％(％) 3 3 3 3
Al富集状态 2处 2处 2处 2处
Si富集状态 无 无 1处 1处
无机硅 无 无 有 有
硅无机化程度 未测定 未测定 0.29 0.21
AD Si(μg/cm 2) 0.002 0.002 0.08 0.1
AD F(μg/cm 2) 15 25 0.03 0.02
ΔC/C(％) -1.2 -1.8 -3.1 -1.9
表5
编号 实施例13 实施例14 实施例15 实施例16
基膜 PP PP PP PP
保护层 DY-E701 KF-6000 X-21-5841 SH702
金属 单面 单面 双面 双面
前Zn比 0.72 0.72 0.72 0.72
后Zn比 0.29 0.24 0.24 0.18
氧富集状态 2处 2处 4处 4处
Al％(％) 3 3 3 3
Al富集状态 2处 2处 4处 4处
Si富集状态 1处 1处 2处 无
无机硅 有 有 有 有
硅无机化程度 0.36 0.21 0.33 0.07
AD Si(μg/cm 2) 0.08 0.06 0.2 0.3
AD F(μg/cm 2) 0.01 0.03 0.05 0.04
ΔC/C(％) -0.6 -0.9 -1.5 -4.5
表6
编号 实施例17 实施例18 实施例19 实施例20
基膜 PP PP PP PP
保护层 SH704 HIVAC F4 KF-96 KF-99
金属 单面 单面 单面 单面
前Zn比 0.72 0.72 0.72 0.72
后Zn比 0.17 0.12 0.15 0.16
氧富集状态 2处 2处 2处 2处
Al％(％) 3 3 3 3
Al富集状态 2处 2处 2处 2处
Si富集状态 无 无 无 无
无机硅 有 有 有 有
硅无机化程度 0.08 未测定 0.09 0.05
AD Si(μg/cm 2) 0.02 0.03 0.03 0.03
AD F(μg/cm 2) 0.04 0.03 0.08 0.02
ΔC/C(％) -4.0 -5.9 -3.9 -5.4
表7
编号 对比例1 对比例2 对比例3 对比例4
基膜 PP PP PP PP
保护层 - - SH702 SH702
金属 单面 单面 单面 单面
前Zn比 0.76 0.72 0.72 0.001
后Zn比 0.01 0.01 0.07 0.001
氧富集状态 1处 1处 无 1处
Al％(％) 40 3 3 100
Al富集状态 无 2处 2处 无
Si富集状态 无 无 无 无
无机硅 有 有 无 无
硅无机化程度 未测定 未测定 0.05 0.03
AD Si(μg/cm 2) 0.001 0.001 0.04 0.03
AD F(μg/cm 2) 0.01 0.05 0.03 0.03
ΔC/C(％) -28.1 -15.3 -10.5 -14.3
表8
编号 对比例5 对比例6
基膜 PP PP
保护层 SH702 SH702
金属 单面 单面
前Zn比 0.72 0.72
后Zn比 0.05 0.06
氧富集状态 1处 1处
Al％(％) 7 3
Al富集状态 1处 1处
Si富集状态 无 无
无机硅 无 无
硅无机化程度 0.04 0.06
AD Si(μg/cm 2) 0.04 0.05
AD F(μg/cm 2) 0.01 0.03
ΔC/C(％) -19.1 -12.2

Claims (14)

  1. 一种金属化薄膜，其特征在于：基材薄膜的至少一侧具有金属层，所述的金属层指含有金属单质或金属化合物的层，且所述的金属化薄膜经105℃、100％RH处理3hr后，经XPS测定的490eV处的强度与498eV处的强度的比大于0.1。
  2. 根据权利要求1所述的金属化薄膜，其特征在于：经105℃、100％RH处理3hr后，经XPS测定的490eV处的强度与498eV处的强度的比大于0.2。
  3. 根据权利要求1所述的金属化薄膜，其特征在于：所述的金属化薄膜中含有氧元素，且金属层断面方向至少有两处氧元素富集。
  4. 根据权利要求1所述的金属化薄膜，其特征在于：所述的金属化薄膜中含有铝元素，且铝元素和锌元素的重量比为1∶99-10∶90。
  5. 根据权利要求4所述的金属化薄膜，其特征在于：所述的金属化薄膜断面方向至少有两处铝元素富集。
  6. 根据权利要求1所述的金属化薄膜，其特征在于：所述的金属层或金属层的外表面含有硅元素和/或氟元素。
  7. 根据权利要求6所述的金属化薄膜，其特征在于：所述的金属化薄膜的断面方向至少有一处硅元素富集。
  8. 根据权利要求6所述的金属化薄膜，其特征在于：XPS分析显示金属化薄膜中存在代表无机化的硅元素的峰。
  9. 根据权利要求6所述的金属化薄膜，其特征在于：硅元素的含量为0.005～0.3μg/cm 2。
  10. 根据权利要求7所述的金属化薄膜，其特征在于：通过飞行时间二次离子质谱分析测定的硅的无机化程度为0.1以上。
  11. 根据权利要求6所述的金属化薄膜，其特征在于：氟元素的含量为5～40μg/cm 2。
  12. 根据权利要求1所述的金属化薄膜，其特征在于：所述的基材薄膜是聚丙烯、聚乙烯、聚酯、聚苯硫醚、聚碳酸酯、聚苯乙烯或聚偏氟乙烯薄膜中的一种。
  13. 根据权利要求1所述的金属化薄膜，其特征在于：所述的金属层的外表面具有保护层，所述的保护层含有聚硅氧烷或全氟聚醚中的一种或多种。
  14. 根据权利要求13所述的金属化薄膜，其特征在于：所述聚硅氧烷是改性聚硅氧烷，所述改性聚硅氧烷是带有硅氢基、环氧基、羟基、羧基、胺基、乙烯基、巯基、碳原子数4以上的烷基或酸酐基中的一种或多种的聚硅氧烷。
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