WO2024122515A1 - フィルムヒーターの製造方法 - Google Patents

フィルムヒーターの製造方法 Download PDF

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Publication number
WO2024122515A1
WO2024122515A1 PCT/JP2023/043355 JP2023043355W WO2024122515A1 WO 2024122515 A1 WO2024122515 A1 WO 2024122515A1 JP 2023043355 W JP2023043355 W JP 2023043355W WO 2024122515 A1 WO2024122515 A1 WO 2024122515A1
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WIPO (PCT)
Prior art keywords
film
conductive layer
coating layer
manufacturing
film heater
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2023/043355
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English (en)
French (fr)
Japanese (ja)
Inventor
英夫 村田
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Proterial Ltd
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Proterial Ltd
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Publication date
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Priority to JP2024562769A priority Critical patent/JPWO2024122515A1/ja
Priority to CN202380083077.7A priority patent/CN120304008A/zh
Priority to KR1020257018009A priority patent/KR20250107205A/ko
Publication of WO2024122515A1 publication Critical patent/WO2024122515A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/20—Heating elements having extended surface area substantially in a two-dimensional [2D] plane, e.g. plate-heater
    • H05B3/34—Heating elements having extended surface area substantially in a two-dimensional [2D] plane, e.g. plate-heater flexible, e.g. heating nets or webs
    • H05B3/36—Heating elements having extended surface area substantially in a two-dimensional [2D] plane, e.g. plate-heater flexible, e.g. heating nets or webs heating conductor embedded in insulating material
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/18—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor the conductor being embedded in an insulating material
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/20—Heating elements having extended surface area substantially in a two-dimensional [2D] plane, e.g. plate-heater
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
    • H05B2203/013—Heaters using resistive films or coatings
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
    • H05B2203/017—Manufacturing methods or apparatus for heaters

Definitions

  • the present invention relates to a method for manufacturing a film heater.
  • These heaters are made by spirally winding a metal wire or foil strip that serves as a heating element around a heat-resistant, strong, insulated thread wire to form a heating wire, and then weaving this into a cloth to form a high-density wiring shape (Patent Document 1), or by photoetching a copper plate into a shape that will form a thin, long wiring path, and then embedding it in resin of the required shape to make a heater (Patent Document 2).
  • An object of the present invention is to provide a new thin heater, i.e., a film heater, which can be manufactured inexpensively.
  • the present inventors have conducted extensive research into a heating element that is thin and can be manufactured at low cost. As a result, they have discovered that a film heater having a resistance value that serves as a heating element can be obtained at low cost by forming a thin film on a film and separating it into pieces of a predetermined size, and have arrived at the present invention.
  • the present invention is a method for manufacturing a film heater, characterized in that a film having a base film, a conductive layer formed on the upper surface of the base film, and a coating layer formed on the upper surface of the conductive layer is separated into a predetermined shape to form a heating element.
  • the base film is preferably made of an insulating resin.
  • the conductive layer has a thickness of 1000 nm or less, and the coating layer has a thickness of 10 to 200 nm.
  • the conductive layer and the coating layer are preferably formed by a sputtering method, and the conductive layer preferably has an electrical resistivity of 10 ⁇ cm or less and is mainly composed of any one of Al, Cu, and Ag.
  • the covering layer is preferably made of a non-magnetic alloy film containing any one of Ti, Cr, Mo, and Ni as a main component.
  • the coating layer is preferably an alloy containing Mo as a main component and containing 60 at % or less of Ni and Ti in total.
  • the coating layer is preferably an alloy containing Ni as a main component and Cu, Mn, and Mo in a total amount of 60 at % or less.
  • the present invention makes it possible to provide a film heater that is thin, lightweight, and inexpensive to manufacture, replacing expensive heaters made by processing copper wire or copper foil.
  • FIG. 2 is a schematic cross-sectional view of a film heater according to the present invention.
  • 1 is a photograph showing the appearance of a film heater according to an embodiment of the present invention.
  • the film heater of the present invention is the method of manufacturing the film heater, in which a conductive layer and a coating layer covering it are formed on a film, and then the film heater is separated into a predetermined size to produce a heater with a predetermined resistance value.
  • the film heater of the present invention is described in detail below.
  • the film heater of the present invention can be used, for example, in applications where a thin, lightweight, and space-saving design is required, such as steering heaters for automobiles and handlebar heaters for motorcycles, for heating areas touched by the human body, or in applications where flexibility and moisture resistance are required, such as surface heating and corrosion resistance due to condensation, for promoting the vaporization of liquefied fuel or wrapping around pipes for heating low-temperature gaseous fuel.
  • the film heater obtained by the manufacturing method of the present invention comprises a base film, a conductive layer formed on the upper surface of the base film, and a coating layer formed on the upper surface of the conductive layer.
  • Copper is a conductor with low resistance, and in order to make it into a heating element, it is necessary to make it into a thin wire with a small cross-sectional area and to make the path long in order to increase the resistance. For this reason, as mentioned above, the method of making a heater by insulating the copper wire processed into a thin wire so that it does not short circuit even when it is densely packed, and weaving it into a fiber and fixing it in a specified shape so that the path is long, or the method of making a heater by embedding copper foil in a resin by forming it into a thin specified shape through a photoetching process is used.
  • the photoetching process requires processing using expensive exposure machines, photoresists, and chemicals, and then cleaning with organic solvents and large amounts of pure water, etc., which results in high costs.
  • the diameter of the generally available thin wire required for the above method is about several hundred ⁇ m, and even copper foil made by making the copper plate even thinner has a thickness of about several tens of ⁇ m. Wires and foils thinner than this require further special processing, which makes them expensive and difficult to handle.
  • the present invention makes it possible to inexpensively manufacture film heaters, which are film-shaped heating elements, by adjusting the thickness of a thin conductive layer formed on a base film and cutting the base film into heating elements with a specified resistance value, and can also contribute to reducing the environmental burden that accompanies improved electricity efficiency in automobiles and motorcycles, for example. It is also possible to cut the film having the thin conductive layer of the present invention into stripes to make a film heater, but to heat a wide area, it is also possible to cut it into a ladder or spiral shape having the necessary resistance.
  • the method for separating the film may be by cutting with a blade such as scissors or a cutter knife, or by irradiating it with a laser to burn it into a complex shape.
  • the base film of the film heater of the present invention is preferably made of insulating resin. This is to prevent the conductive layer from coming into contact with other metals, etc., and causing an electrical short circuit.
  • insulating resin For example, an inexpensive PET film or a more heat-resistant polyimide film may be used, and the film may be selected according to the temperature range in which heat is generated. The thinner the film, the easier it is to cut into film heaters, as long as it has the strength required for handling the film heater and the flexibility required for easy handling.
  • a coating of the same components as the coating layer may be formed between the base film and the conductive layer as a base layer.
  • the thickness can be set to 10 to 200 nm.
  • the preferred lower thickness limit of the base layer can be set to 20 nm, and the preferred upper thickness limit of the base layer can be set to 100 nm.
  • the sputtering method is preferably used to form the conductive layer or coating layer for the film heater of the present invention.
  • the sputtering method is the most suitable for preventing deterioration or shrinkage of the resin film due to heat and for stable formation over a large area.
  • the conductive layer of the film heater of the present invention must be thin yet conductive, and an alloy with a main component of Al, Cu, or Ag (containing 80 at% or more) or a pure metal with a purity of 98% or more is suitable, which can easily achieve an electrical resistivity of 10 ⁇ cm or less.
  • cheaper Al or Cu is preferable to expensive Ag, and considering long-term reliability such as heating at high temperatures and electromigration, it is even better to use Cu as the main component, which has a higher melting point than Al.
  • the coating layer used in the film heater of the present invention protects the conductive layer from the external environment.
  • a non-magnetic alloy film mainly composed of Ti, Cr, Mo, or Ni is desirable because it is required to have environmental resistance to suppress corrosion of the conductive layer and to improve adhesion with the film substrate (base film) when a coating film of the same composition as the coating layer is formed as an underlayer.
  • the reason why it is non-magnetic is that the magnetron sputtering method, which has a high film formation speed, is used, and with a magnetic material, a target material with a very thin thickness is required to obtain the film formation speed, which shortens the life of the target material and reduces productivity.
  • environment resistance refers to the ability to suppress surface deterioration in a high-temperature and high-humidity environment and when heated in the air, and can be confirmed by discoloration, and can be quantitatively evaluated, for example, by reflectance.
  • Cr and Ti are metals with high corrosion resistance, but Cr has a large internal stress when formed by sputtering, which may cause the film to warp.
  • Ti and Ni may thermally diffuse into Cu at high temperatures, which may increase the electrical resistance.
  • Mo is an element that has low stress and is difficult to thermally diffuse into Al, Ag, and Cu, which are conductive films, making it easy to suppress warping of the film, but it has low resistance to high temperatures and high humidity, and is a high-melting point metal that makes it easily brittle, and has the disadvantage that the film is prone to cracking when bent. For this reason, in order to improve the moisture resistance and to form an amorphous structure that is less susceptible to cracking, it is preferable to use a Mo alloy to which Ni and/or Ti have been added, with the combined Ni and Ti content being 60 at % or less, and more preferably, 20 to 40 at % Ni and 5 to 30 at % Ti.
  • the coating layer when soldering is preferably made of a Ni alloy with added Cu, Mn, and Mo, and the total content of Cu, Mn, and Mo is 60 at % or less, more preferably 10 to 40 at %, Mn is 7 to 25 at %, and Mo is 5 to 30 at %.
  • the conductive layer of the film heater of the present invention is preferably thin, and tends to be 1000 nm or less, since the resistance value decreases and it is difficult to generate heat if the conductive layer is too thin, and 100 nm or less is preferable. On the other hand, if the conductive layer is too thin, it is likely to break due to electromigration or stress due to curvature when the film is bent, so it is considered that 100 nm or more is preferable.
  • a more preferable upper limit of the conductive layer thickness is 800 nm, and a more preferable upper limit of the conductive layer thickness is 600 nm or less.
  • the thickness of the coating layer is preferably at least 10 nm or more in order to suppress deterioration of the conductive layer due to moisture that penetrates the film surface or the film. If it is less than 10 nm, the continuity of the film tends to decrease and the protective function tends to become insufficient. In addition, if it is too thick, it takes time to form and productivity decreases, so the upper limit of the coating layer thickness is preferably 200 nm or less. A more preferable lower limit of the coating layer thickness is 30 nm, and a more preferable upper limit of the coating layer thickness is 100 nm. It is also possible to form a composite film that functions both as wiring and a magnetic shield by forming a magnetic film having soft magnetic properties, such as Permalloy, on the upper or lower surface of the covering layer.
  • a magnetic film having soft magnetic properties such as Permalloy
  • Example 1 A 100 ⁇ m thick PET film was cut into 200 x 100 mm as a base film for producing a film heater.
  • a sputtering device model number SME-200E, manufactured by ULVAC, Inc., was used to form the conductive layer and the coating layer.
  • the target material attached to the sputtering device had a diameter of 100 mm and a thickness of 5 mm.
  • the conductive layer was made from a plate of oxygen-free copper with a purity of 4N, and the coating layer was made by sintering powders of Mo, Ni-Mo alloy, and Ti to have Mo-30Ni-20Ti (atomic %). These targets were brazed to a copper backing plate and then attached to the sputtering device.
  • the cut PET film was fixed to a substrate holder of a sputtering apparatus, and the apparatus was evacuated to 5 ⁇ 10 ⁇ 5 Pa. Then, Ar, a sputtering gas, was introduced to an atmosphere of 0.5 Pa. A Mo-Ni-Ti alloy was formed to a thickness of 30 nm at a power of 300 W in the atmosphere of 0.5 Pa. Then, a Cu conductive layer was formed to a thickness of 500 nm at a power of 500 W. Then, a Mo-Ni-Ti alloy was formed to a thickness of 30 nm under the same conditions as the underlayer. The cross section of the layer structure is shown in FIG. 1. For comparison, only a Cu conductive layer was formed to a thickness of 500 nm on the PET film. The electrical resistivity of this Cu film was 2.1 ⁇ cm.
  • a PET film with a Cu conductive layer and a Mo-Ni-Ti coating layer, and a PET film with only a Cu conductive layer were cut into 25 x 50 mm pieces and left in a high-temperature, high-humidity chamber set at a relative humidity of 85% and a temperature of 85°C for 300 hours.
  • the Mo-Ni-Ti coating layer was formed, the film showed almost no discoloration and retained a metallic luster, but the film with only a Cu conductive layer discolored to a brownish color. It was confirmed that moisture resistance can be greatly improved by forming a Mo-Ni-Ti coating layer.
  • the PET film with the coating layer and conductive layer formed was cut into a length of 200 mm and a width of 3 mm using a rotary cutter (Model RC-B4, manufactured by Lion Office Machinery Co., Ltd.), and a voltage of 5 V was applied to both ends.
  • the temperature of the top surface of the film was measured, and it was confirmed that the temperature rose from approximately 20°C before the voltage was applied to approximately 45°C, making it a heater that felt warm.
  • Example 2 A polyimide film with a thickness of 50 ⁇ m was cut into 280 ⁇ 100 mm as a base film for producing a film heater.
  • a sputtering device with model number CS-200 manufactured by ULVAC, Inc. was used to form the conductive layer and the coating layer.
  • the target material attached to the sputtering device had a diameter of 100 mm and a thickness of 5 mm.
  • the conductive layer it was processed from a plate of oxygen-free copper with a purity of 4N, and for the coating layer, Ni-30Cu-15Mo-10Mn (atomic %) was prepared by weighing out predetermined amounts of electrolytic Ni, oxygen-free copper blocks, and massive Mn and Mo raw materials, and then producing an ingot by melting and casting in a vacuum melting furnace, followed by machining. These targets were brazed to a copper backing plate and then attached to the sputtering device.
  • the cut polyimide film was fixed to a substrate holder in a sputtering device and evacuated to 7 ⁇ 10 ⁇ 5 Pa, after which Ar, a sputtering gas, was introduced to form a 500 nm conductive layer of Cu at 500 W in an atmosphere of 0.5 Pa, and then a 20 nm Ni-Cu-Mo-Mn alloy coating layer was formed at 300 W.
  • the cross section of the layer structure is shown in Figure 1 (however, the underlayer 2 was not formed). For comparison, only a 500 nm conductive Cu film was formed on the polyimide film.
  • a polyimide film with a Cu conductive layer and Ni-Cu-Mo-Mn coating layer was compared with a polyimide film with only a Cu conductive layer. It was confirmed that the film with the coating layer showed less warping and was flatter, and that warping could be reduced.
  • This film was cut to 25 x 50 mm and left in a high-temperature, high-humidity chamber set at a relative humidity of 85% and a temperature of 85°C for 300 hours.
  • the film with the Ni-Cu-Mo-Mn coating layer When the film with the Ni-Cu-Mo-Mn coating layer was left in a high-temperature, high-humidity chamber set at 85% relative humidity and 85°C for 300 hours, the film with the Ni-Cu-Mo-Mn coating layer showed almost no discoloration and retained a metallic luster, but the film with only the Cu conductive layer discolored to a brownish color. It was confirmed that moisture resistance can be greatly improved by forming a Ni-Cu-Mo-Mn coating layer.
  • the polyimide film with only the Cu conductive layer and the polyimide film with the coating layer and conductive layer were cut into stripes 5 mm wide and 100 mm long using a rotary cutter (Model RC-B4, manufactured by Lion Office Machinery Co., Ltd.), and the conductor part of the copper-coated wiring with Sn-based solder attached to the end was soldered by pressing a soldering iron heated to about 280°C against the stripes, melting them and pressing them together. When checked with a tester, electrical continuity was confirmed. With the film with only the Cu conductive layer, the solder joint was burned and discolored, and when the copper-coated wiring was pulled, it easily peeled off from the solder joint.
  • the 50 ⁇ m thick polyimide film with the coating layer and conductive layer formed was cut into a crank shape with a width of approximately 5mm, a folded length of approximately 70mm, and a height of approximately 80mm, as shown in Figure 2, and wrapped around a steering wheel with a grip diameter of ⁇ 30mm and wrapped in synthetic leather with an outer diameter of 360mm.
  • a voltage of 12V was applied to both ends, and the temperature of the top surface of the film was measured, rising from approximately 20°C before the voltage was applied to approximately 50°C, confirming that it acted as a heater.
  • Example 3 As a base film for producing a film heater, a polyimide film with a thickness of 50 ⁇ m was cut to 290 ⁇ 100 mm in the same manner as in Example 2, and a sputtering device with model number CS-200 manufactured by ULVAC, Inc. was used to form a conductive layer and a coating layer.
  • a target material made of Mo-20Ni-30Ti (atomic %) sintered for the coating layer and an Al target material with a purity of 4N manufactured by Sumitomo Chemical were used to form 500 nm of Al to become the conductive layer at 500 W in the same manner as in Example 2, and then a Mo-Ni-Ti alloy was formed to become the coating layer at 50 nm at a power of 300 W.
  • a comparative example was also prepared in which only an Al conductive layer was formed to 500 nm on a polyimide film.
  • the Al film is easily scratched because it is soft, but it was confirmed that the laminated film on which the Mo-Ni-Ti coating layer was formed was hardly scratched.
  • the polyimide film with the coating layer and conductive layer formed was cut into a length of 290 mm and a width of 5 mm using a rotary cutter (Model RC-B4, manufactured by Lion Office Machinery Co., Ltd.), and a voltage of 5 V was applied to both ends to measure the temperature of the top surface of the film. The temperature rose from approximately 20°C before the voltage was applied to approximately 50°C, confirming that the film became a heater that felt warm. From these results, it was confirmed that the Al film could be used as a film heater, just like the Cu film.

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PCT/JP2023/043355 2022-12-05 2023-12-04 フィルムヒーターの製造方法 Ceased WO2024122515A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2024562769A JPWO2024122515A1 (https=) 2022-12-05 2023-12-04
CN202380083077.7A CN120304008A (zh) 2022-12-05 2023-12-04 膜加热器的制造方法
KR1020257018009A KR20250107205A (ko) 2022-12-05 2023-12-04 필름 히터의 제조 방법

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JP2022194431 2022-12-05
JP2022-194431 2022-12-05

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08250264A (ja) * 1995-03-08 1996-09-27 Matsushita Electric Ind Co Ltd フィルム状ヒーター、保温座席、蒸着ボートおよび加熱炉
CN103974471A (zh) * 2013-02-01 2014-08-06 Kmt纳米科技（香港）有限公司 纳米复合导流电热膜及其制备方法
CN106028486A (zh) * 2016-05-17 2016-10-12 上海科比斯光学科技有限公司 一种复合导电膜及其制备方法和应用

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1022065A (ja) 1996-07-04 1998-01-23 Nec Eng Ltd シートヒータ
CN103988574B (zh) 2011-12-09 2016-05-04 产机控制系统股份有限公司 布加热器

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08250264A (ja) * 1995-03-08 1996-09-27 Matsushita Electric Ind Co Ltd フィルム状ヒーター、保温座席、蒸着ボートおよび加熱炉
CN103974471A (zh) * 2013-02-01 2014-08-06 Kmt纳米科技（香港）有限公司 纳米复合导流电热膜及其制备方法
CN106028486A (zh) * 2016-05-17 2016-10-12 上海科比斯光学科技有限公司 一种复合导电膜及其制备方法和应用

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CN120304008A (zh) 2025-07-11
KR20250107205A (ko) 2025-07-11
JPWO2024122515A1 (https=) 2024-06-13

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