WO2024203408A1 - 金属化フィルムとその製造方法及びフィルムコンデンサ - Google Patents

金属化フィルムとその製造方法及びフィルムコンデンサ Download PDF

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Publication number
WO2024203408A1
WO2024203408A1 PCT/JP2024/010098 JP2024010098W WO2024203408A1 WO 2024203408 A1 WO2024203408 A1 WO 2024203408A1 JP 2024010098 W JP2024010098 W JP 2024010098W WO 2024203408 A1 WO2024203408 A1 WO 2024203408A1
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WO
WIPO (PCT)
Prior art keywords
oil
film
masking
hydrocarbon
evaporation temperature
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PCT/JP2024/010098
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English (en)
French (fr)
Japanese (ja)
Inventor
雄基 永尾
真一 小林
裕介 野間
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株式会社指月電機製作所
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Application filed by 株式会社指月電機製作所 filed Critical 株式会社指月電機製作所
Priority to JP2025510479A priority Critical patent/JPWO2024203408A1/ja
Priority to CN202480004492.3A priority patent/CN119998904A/zh
Priority to DE112024000150.5T priority patent/DE112024000150T5/de
Publication of WO2024203408A1 publication Critical patent/WO2024203408A1/ja

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/32—Wound capacitors
    • 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
    • C23C14/04—Coating on selected surface areas, e.g. using masks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/005—Electrodes
    • H01G4/012—Form of non-self-supporting electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/005—Electrodes
    • H01G4/015—Special provisions for self-healing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/14—Organic dielectrics
    • H01G4/18—Organic dielectrics of synthetic material, e.g. derivatives of cellulose

Definitions

  • This invention relates to a metallized film, a method for manufacturing the same, and a film capacitor using the metallized film.
  • a metallized film with a deposition pattern consisting of deposited and non-deposited areas When manufacturing a metallized film with a deposition pattern consisting of deposited and non-deposited areas, the parts of the surface of the dielectric film that will become the non-deposited areas are masked in advance, and then metal is deposited to form the desired deposition pattern on the surface of the dielectric film.
  • One method of masking is the oil mask method, which uses oil as a masking material. Metal does not deposit on areas where the masking oil is attached, so a deposition pattern that corresponds to the shape of the masking oil application (attachment) is formed on the surface of the dielectric film.
  • fluorine oil perfluoropolyether, etc.
  • Fluorine oil has good wettability to the film, so it can suppress defects caused by insufficient oil adhesion to areas that should be masked (missing: defects where metal is deposited in areas where it should not be deposited).
  • fluorine oil has high thermal stability and is not prone to decomposition or other changes when heated, so evaporation is stable, and defects caused by oil evaporating and scattering into unintended areas during metal deposition, masking areas where metal should be deposited (unevenness: defects where metal is not deposited in areas where it should be deposited or the amount of deposition is extremely small), which are caused by this, are unlikely to occur.
  • fluorine oil is decomposed by the electron beam irradiated during metal deposition to improve adhesion between the dielectric film and the cooling roller, generating fluorine ions, which accelerate the deterioration of the deposited metal and become a factor in reducing the reliability of the capacitor.
  • fluorine oil is made of fluorocarbons, which are of concern for their environmental impact, so it is one of the substances whose use should be avoided.
  • Hydrocarbon oils are sometimes used as masking oils, but they have the disadvantage that their evaporation is unstable, meaning that the amount of oil that adheres to the dielectric film varies, resulting in frequent occurrence of unevenness and gaps.
  • evaporated metal deteriorates when it absorbs moisture.
  • silicone oil is sometimes applied to the evaporated surface as an after-oil to form a protective film.
  • silicone oil has the property of being easily permeable to water vapor, so it was not possible to sufficiently suppress moisture absorption by the evaporated metal.
  • the present invention aims to improve metallized films.
  • the metallized film is characterized by the use of a hydrocarbon oil with a 10% evaporation temperature of 237°C or higher and a 90% evaporation temperature of 337°C or lower as a masking oil or after-oil.
  • the contact angle of the hydrocarbon-based oil with respect to the dielectric film is 17.9 to 22.8°.
  • the contact angle of the hydrocarbon-based oil with respect to the polypropylene film is 17.9 to 22.8°.
  • the film capacitor of the present invention is characterized by using any of the metallized films described above.
  • the method for manufacturing a metallized film of the present invention is characterized by including a step of evaporating and adhering a hydrocarbon oil.
  • FIG. 2 is a diagram showing a deposition pattern of a film capacitor according to an embodiment of the present invention.
  • FIG. 2 is a cross-sectional view of a main portion of a metallized film.
  • FIG. 2 is a cross-sectional view of a main portion of a metallized film to which after-oil has been applied.
  • 1 is a graph showing the results of a humidity resistance load test.
  • the film capacitor uses a metallized film 1 shown in Figures 1 and 2.
  • the metallized film 1 has a deposition pattern consisting of a deposition portion 3 and a non-deposited portion 4 on the surface of a dielectric film 2.
  • the deposition portion 3 refers to a portion on which a metal such as aluminum or zinc is deposited.
  • the non-deposited portion 4 refers to a portion on which no metal is deposited.
  • the non-deposited portion 4 is, for example, a margin portion for dividing the deposition portion.
  • the deposition portion 3 divided by the margin portion becomes, for example, a split electrode 5.
  • the split electrodes are connected to each other by a fuse portion 6.
  • Figure 1 shows a cut-out portion of the metallized film 1, and is actually continuous in the film feed direction.
  • the dielectric film is a synthetic resin film.
  • it is a film made of any of polypropylene, polyethylene terephthalate, polyethylene naphthalate, polyphenylene sulfide, polyvinylidene fluoride, and cycloolefin polymer.
  • a polypropylene film is preferable, and a biaxially oriented polypropylene film is more preferable.
  • the surface is subjected to a corona treatment.
  • the thickness of the film is not particularly limited, but is, for example, 2.5 ⁇ m.
  • the non-vapor-deposited portion is formed by the oil mask method.
  • the masking oil used in the oil mask method is a hydrocarbon-based oil that satisfies at least the following condition 1. It is more preferable that the masking oil is a hydrocarbon-based oil that satisfies both conditions 1 and 2. Furthermore, it is even more preferable that the masking oil is paraffin oil among the hydrocarbon-based oils that satisfy both conditions 1 and 2.
  • the 10% evaporation temperature is lower than 237°C, the masking oil will evaporate easily and unevenness will easily occur. Also, if the 90% evaporation temperature is higher than 337°C, gaps will easily occur.
  • the evaporation temperature is a value measured by thermogravimetry based on JIS K0129 (2005). Specifically, the sample masking oil was placed in an aluminum container (without lid) of a simultaneous thermogravimetry and differential thermal analyzer (DTG-60H: manufactured by Shimadzu Corporation), and the temperature was raised from room temperature to 600°C at a rate of 10°C per minute, and the temperatures when the mass had decreased by 10% and when it had decreased by 90% were measured.
  • DTG-60H simultaneous thermogravimetry and differential thermal analyzer
  • the "contact angle” is preferably the contact angle with respect to a polypropylene film, more preferably the contact angle with respect to a biaxially oriented polypropylene film, and even more preferably the contact angle with respect to a corona-treated surface of a biaxially oriented polypropylene film.
  • the contact angle is smaller than 17.9°, the masking oil will tend to spread beyond the intended range, resulting in unevenness. If the contact angle is larger than 22.8°, it will be difficult to adhere the masking oil to the dielectric film, resulting in gaps.
  • the contact angle is a value measured by the sessile drop method based on JIS R3257 (1999). Specifically, at an air temperature of 25°C and a humidity of 50%, 3 ⁇ 0.5 ⁇ L of liquid is dropped onto a sample using a microsyringe, and the sample is allowed to stand. After 1.5 ⁇ 0.1 seconds, the droplet is photographed. The radius r and height h of the droplet are obtained and substituted into the following formula to obtain the contact angle ⁇ .
  • the metallized film is manufactured as follows. First, masking oil is applied to the surface of the dielectric film, for example, by flexographic printing. Specifically, a relief plate having convex portions of approximately the same shape as the non-vapor-deposited portions is prepared, and masking oil is applied to the relief plate. For example, the masking oil stored in an oil tank is first heated using a heat source such as a heater and evaporated. Next, the evaporated masking oil is applied to a roll (adhered: vapor deposition process). Then, the roll is pressed against the relief plate. After that, the relief plate is pressed against the surface of the dielectric film, and the masking oil is transferred (adhered).
  • a heat source such as a heater
  • the evaporated masking oil is applied to a roll (adhered: vapor deposition process). Then, the roll is pressed against the relief plate. After that, the relief plate is pressed against the surface of the dielectric film, and the masking oil is transferred (adhered).
  • the masking oil adhering to the convex portions of the relief plate is transferred, and a masking oil layer 7 is formed on the dielectric film (see Figure 2).
  • the masking oil adhering to the concave portions of the relief plate is not transferred. Therefore, the shape of the transferred masking oil layer 7 is approximately the same as the shape of the convex portions of the relief plate.
  • other methods for applying masking oil include screen printing, gravure printing, offset printing, spraying, and die coating.
  • metal is evaporated onto the surface of the dielectric film onto which the masking oil has been transferred.
  • evaporation is performed by vacuum evaporation.
  • the dielectric film is placed inside a vacuum evaporation machine, and metal is evaporated onto the surface that has been subjected to corona discharge treatment so that the film resistance value becomes a specified value.
  • the metal is heated, for example, by a resistance heating method.
  • the metal is evaporated onto the areas where the masking oil is not attached, forming evaporated areas.
  • the metal is not evaporated onto the areas where the masking oil is attached, forming non-evaporated areas.
  • an evaporated pattern is formed according to the shape of the recesses in the relief plate.
  • the film capacitor of the present invention is manufactured by winding the metallized film having the above-mentioned configuration and forming metal-like electrodes, for example by spraying metal, on both axial ends. Note that stacking may be used instead of winding.
  • Example 1 A metallized film using a hydrocarbon-based oil (paraffin oil) with a 10% evaporation temperature of 237°C, a 90% evaporation temperature of 317°C, and a contact angle of 17.9° as the masking oil.
  • a hydrocarbon-based oil paraffin oil
  • Example 2 A metallized film using a hydrocarbon-based oil (paraffin oil) with a 10% evaporation temperature of 265°C, a 90% evaporation temperature of 337°C, and a contact angle of 22.8° as the masking oil.
  • a hydrocarbon-based oil paraffin oil
  • metallized films were manufactured under the same conditions except for the masking oil, which was different. That is, a biaxially oriented polypropylene film with a length of 8,000 m and a thickness of 2.5 ⁇ m was used as the dielectric film, and the surface was corona-treated. Masking oil was then applied to the corona-treated surface by flexographic printing, and aluminum was then vapor-deposited to form a specified vapor-deposited pattern. As shown in Figure 1, the vapor-deposited pattern has a lattice-like margin (non-vapor-deposited portion 4), and adjacent split electrodes 5 are connected to each other by fuse portions 6.
  • the occurrence of unevenness (a defect where metal is not deposited on areas where it should be, or where the amount of deposition is extremely small) and gaps (a defect where metal is deposited on areas where it should not be) was confirmed.
  • unevenness the presence or absence of unevenness was confirmed visually at a position 1500m from the initial movement, magnified 20 times with a microscope.
  • the width dimension A of the margin portion extending in a direction perpendicular to the film feed direction, the width dimension B of the margin portion extending in a direction parallel to the film feed direction, and the width dimension C of the fuse portion provided between the margin portions extending in a direction parallel to the film feed direction were measured.
  • the reference values are the dimensional accuracy obtained when a fluorine oil with a 10% evaporation temperature of 235°C or higher, a 90% evaporation temperature of 335°C, and a contact angle of 17.9 to 22.8° was used as the masking oil (other conditions were the same as in each example and comparative example).
  • the unit of the average value is mm.
  • Table 2 shows the inspection results. As can be seen from the table, in Examples 1 and 2, unevenness, gaps, and dimensional accuracy are all equivalent to the standards. On the other hand, in Comparative Example 1, unevenness falls below the standards, and in Comparative Example 2, gaps and dimensional accuracy fall below the standards.
  • fluorine oil has problems such as being decomposed by the electron beam irradiated during metal deposition to improve adhesion between the dielectric film and the cooling roller, generating fluorine ions, which accelerate the deterioration of the deposited metal, and being expensive. On the other hand, such problems are less likely to occur with hydrocarbon-based oils, making it possible to manufacture inexpensive, reliable film capacitors.
  • the life span (the rate of capacitance reduction when a voltage of 600 VDC is applied in an environment of 105°C) is almost the same between a film capacitor using fluorinated oil as masking oil and a film capacitor using the metallized film of Example 1 or Example 2.
  • After-oil is an oil that is applied to the deposition surface (the surface on which the deposition portion 3 is formed) of the metallized film.
  • the applied after-oil forms a protective film 8 on the deposition metal (deposition portion 3) (see FIG. 3).
  • the protective film 8 is formed, for example, by heating and evaporating the after-oil filled in an oil tank with a heat source such as a heater, and then attaching the evaporated after-oil to the deposition surface. That is, the application of the after-oil is performed by deposition in the same manner as the application of the masking oil.
  • the difference is that the after-oil is applied directly, whereas the masking oil is applied indirectly via an intermediate such as a roll or letterpress. Note that in FIG. 3, a boundary is drawn between the masking oil layer 7 and the after-oil layer 8, but they may be mixed together and the boundary may be unclear.
  • Hydrocarbon oils used as after-lubricants meet the following condition 1.
  • the after-oil will evaporate easily and the protective film will not be formed stably. Also, if the 90% evaporation temperature is higher than 337°C, when the after-oil is heated to the evaporation temperature using a heat source such as a heater, the temperature difference between positions close to and far from the heat source will tend to be large. As a result, the amount of oil that evaporates will be unstable and the protective film will not be formed stably.
  • the evaporation temperature is a value measured by thermogravimetry based on JIS K0129 (2005). Specifically, the sample masking oil was placed in an aluminum container (without lid) of a simultaneous thermogravimetry and differential thermal analyzer (DTG-60H: manufactured by Shimadzu Corporation), and the temperature was raised from room temperature to 600°C at a rate of 10°C per minute, and the temperatures when the mass had decreased by 10% and when it had decreased by 90% were measured.
  • DTG-60H simultaneous thermogravimetry and differential thermal analyzer
  • the after-oil is preferably a paraffin oil among the hydrocarbon oils.
  • the same oil as the masking oil may be used.
  • a hydrocarbon oil (paraffin oil) that satisfies conditions 1 and 2 may be used as the masking oil and after-oil.
  • the after-oil can be applied to the deposition surface by flexographic printing, screen printing, gravure printing, offset printing, spraying, die coating, etc.
  • Example 11 A metallized film using a hydrocarbon oil (paraffin oil) with a 10% evaporation temperature of 237°C and a 90% evaporation temperature of 317°C as an after-oil.
  • hydrocarbon oil paraffin oil
  • Example 12 A metallized film using a hydrocarbon oil (paraffin oil) with a 10% evaporation temperature of 265°C and a 90% evaporation temperature of 337°C as an after-oil.
  • hydrocarbon oil paraffin oil
  • All of the examples and comparative examples produced metallized films under the same conditions except for the use of different after-oil. That is, a biaxially oriented polypropylene film 8000 m long and 2.5 ⁇ m thick was used as the dielectric film, and the surface was corona-treated. Masking oil was then applied to the corona-treated surface by flexographic printing, and aluminum was then vapor-deposited to form a specified vapor-deposition pattern. As shown in Figure 1, the vapor-deposition pattern has a lattice-like margin (non-vapor-deposited portion 4), and adjacent split electrodes 5 are connected to each other by fuse portions 6. The after-oil was applied directly to the entire vapor-deposition surface by heating and evaporating the after-oil filled in an oil tank with a heater.
  • each of the metallized films of Examples 11 and 12 and Comparative Examples 11 and 12 was wound, and metal-con electrodes were formed by, for example, spraying metal on both axial ends to manufacture a film capacitor with a capacitance of 193 ⁇ F.
  • each film capacitor was placed in an environment of 115°C, and a voltage of 600 VDC was applied for 2000 hours. After 2000 hours had passed, each film capacitor was unwound, and 10 m of the metallized film was removed from each film capacitor, and the amount of light transmitted through the deposition portion 3 in the film thickness direction of each metallized film was measured. The amount of light transmitted was measured using a light emitter and a light receiver (Keyence Corporation Fiber Sensor FS-V21, FU-77V).
  • Table 3 shows the maximum and minimum values of the measured light transmittance.
  • the vapor-deposited metal vapor-deposited portion 3
  • the greater the difference between the maximum and minimum values of light transmittance the more uneven the formation of the protective film is.
  • the difference between the maximum and minimum values of light transmittance is smaller than in Comparative Examples 11 and 12, and the protective film is formed with a roughly constant thickness; in other words, it can be seen that a stable protective film is formed.
  • Hydrocarbon oils have extremely low water vapor permeability. Therefore, if a stable protective film is formed, it is possible to prevent contact between the deposition part 3 and water vapor, and suppress deterioration of the deposition part 3.
  • Figure 4 is a graph showing the results of the humidity load test.
  • the test method involves placing the film capacitor in an environment of 85°C and 85% humidity, applying a voltage of 450 VDC, and examining the change in capacitor capacitance after a specified time has passed.
  • Example 11 refers to a film capacitor using the metallized film of Example 11
  • Comparative Example 13 refers to a film capacitor using the same metallized film as Example 11 except that silicone oil with a 10% evaporation temperature of 193°C and a 90% evaporation temperature of 264°C was used as the after-oil
  • “Comparative Example 14” refers to a film capacitor using the same metallized film as Example 11 except that no after-oil was applied.
  • Example 11 As shown in the figure, the capacitor capacity after about 3,500 hours in Example 11 decreased by only about 0.7%, whereas in Comparative Example 13 it decreased by about 3.1%. Therefore, it can be seen that a higher moisture resistance was obtained compared to when silicone oil was used as an after-oil.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
PCT/JP2024/010098 2023-03-29 2024-03-14 金属化フィルムとその製造方法及びフィルムコンデンサ WO2024203408A1 (ja)

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Application Number Priority Date Filing Date Title
JP2025510479A JPWO2024203408A1 (enrdf_load_stackoverflow) 2023-03-29 2024-03-14
CN202480004492.3A CN119998904A (zh) 2023-03-29 2024-03-14 金属化薄膜与其制造方法以及薄膜电容器
DE112024000150.5T DE112024000150T5 (de) 2023-03-29 2024-03-14 Metallisierte folie, verfahren zu deren herstellung und folienkondensator

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JP2023-054323 2023-03-29

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JP (1) JPWO2024203408A1 (enrdf_load_stackoverflow)
CN (1) CN119998904A (enrdf_load_stackoverflow)
DE (1) DE112024000150T5 (enrdf_load_stackoverflow)
WO (1) WO2024203408A1 (enrdf_load_stackoverflow)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5579867A (en) * 1978-12-11 1980-06-16 Honshu Paper Co Ltd Vacuum evaporation method
WO1987003419A1 (en) * 1985-11-30 1987-06-04 Honshu Seishi Kabushiki Kaisha Zinc-metallized base material for metallized capacitor and process for its production
JP2001279425A (ja) * 2000-03-30 2001-10-10 Matsushita Electric Ind Co Ltd オイルマスキング装置およびこれを備えた真空蒸着器

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5579867A (en) * 1978-12-11 1980-06-16 Honshu Paper Co Ltd Vacuum evaporation method
WO1987003419A1 (en) * 1985-11-30 1987-06-04 Honshu Seishi Kabushiki Kaisha Zinc-metallized base material for metallized capacitor and process for its production
JP2001279425A (ja) * 2000-03-30 2001-10-10 Matsushita Electric Ind Co Ltd オイルマスキング装置およびこれを備えた真空蒸着器

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JPWO2024203408A1 (enrdf_load_stackoverflow) 2024-10-03
DE112024000150T5 (de) 2025-06-18

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