Patent Grant
10305210
This application is based upon and claims the benefit of priority from the prior Japanese Patent Application No. 2017-010170, filed on Jan. 24, 2017, the entire contents of which are incorporated herein by reference.
1. Technical Field
The present invention relates to a terminal plating material, and a terminal, a terminal-equipped electric wire and a wire harness using the same. More specifically, the present invention relates to a terminal plating material, and a terminal, a terminal-equipped electric wire and a wire harness using the same, which also have high abrasion resistance while minimizing an increase in contact resistance.
2. Background Art
In recent years, demands for hybrid vehicles and electric vehicles have increased, and a high current flows through the terminals of the charging connector used in these vehicles.
However, tin plating generally used in gasoline vehicles is high in electric resistance, thus it tends to generate heat. Also, since heat resistance is not so high, there is a fear that the tin plating deteriorates due to this heat. For this reason, it has been suggested to use silver or silver alloy plating with low electric resistance instead of tin plating for terminals used in hybrid vehicles and electric vehicles.
For example, Japanese Unexamined Patent Application Publication No. 2009-79250 discloses a member in which a silver or silver alloy layer having an antimony concentration of 0.1% by mass or less is formed on at least a part of the surface of a copper or copper alloy member, and a silver alloy layer having a Vickers hardness of Hv 140 or more is formed as an outermost layer on the silver or silver alloy layer.
However, since a charging connector used in hybrid vehicles and electric vehicles is repeatedly inserted and removed, it was necessary to increase the layer thickness even in the silver or silver alloy layer of Japanese Unexamined Patent Application Publication No. 2009-79250. On the other hand, when the layer thickness is increased, there are problems that the plating time increases and the amount of plating materials to be used also needs to be increased. Also, even in the case of a terminal with silver or silver alloy plating, contact resistance may not be so small in some cases, so that a terminal with a further reduced contact resistance has been required.
The present invention has been made in view of such problems of the prior art. An object of the present invention is to provide a terminal plating material, and a terminal, a terminal-equipped electric wire, and a wire harness using the same, which also have high abrasion resistance while minimizing an increase in contact resistance.
A terminal plating material according to a first aspect of the present invention is a terminal plating material including a metal substrate, and a silver-tin alloy plating layer containing a silver-tin alloy, arranged on the metal substrate, wherein the silver-tin alloy plating layer contains an intermetallic compound of silver and tin, a Vickers hardness of the surface of the silver-tin alloy plating layer in the terminal plating material is 250 Hv or more, and a surface roughness of the silver-tin alloy plating layer is 0.60 μmRa or less.
A terminal plating material according to a second aspect of the present invention relates to the terminal plating material of the first aspect, and the Vickers hardness of the silver-tin alloy plating layer in the terminal plating material after being heated at 50° C. to 200° C. for 20 minutes or more is 250 Hv or more.
A terminal according to a third aspect of the present invention is formed from the terminal plating material of the first or second aspect.
A terminal-equipped electric wire according to a fourth aspect of the present invention includes the terminal of the third aspect.
A wire harness according to a fifth aspect of the present invention includes the terminal-equipped electric wire of the fourth aspect.
According to the present invention, abrasion resistance of the terminal plating material, and the terminal, the terminal-equipped electric wire and the wire harness using the same also can be increased while minimizing an increase in contact resistance.
Hereinbelow, the terminal plating material, and the terminal, the terminal-equipped electric wire and the wire harness using the same according to this embodiment will be described in detail with reference to the drawings. The dimensional ratios in the drawings are exaggerated for convenience of explanation and may differ from the actual ratios.
[Terminal Plating Material 1]
A terminal plating material 1 of this embodiment includes a metal substrate 2, and a silver-tin alloy plating layer 3 containing a silver-tin alloy, arranged on the metal substrate 2. Therefore, the terminal plating material 1 of this embodiment has low electrical resistance as compared to the conventional tin plating and the like, and is less likely to generate heat even in places where a high current flows like hybrid vehicles and electric vehicles.
Also, the silver-tin alloy plating layer 3 contains an intermetallic compound of silver and tin. The Vickers hardness of the surface of the silver-tin alloy plating layer 3 in the terminal plating material 1 is 250 Hv or more. Therefore, the terminal plating material 1 of this embodiment has high abrasion resistance, and when used as a terminal, the plating layer is hardly worn even when the terminal is repeatedly inserted and removed. Furthermore, the surface roughness of the silver-tin alloy plating layer 3 is 0.60 μmRa or less. Therefore, contact resistance is small, heat generation when used as a terminal is suppressed, and power consumption can be reduced. Details of each configuration of this embodiment will be described hereinbelow.
(Metal Substrate 2)
The metal substrate 2 is a material to be plated with the silver-tin alloy plating layer 3. As the material for forming the metal substrate 2, at least one kind selected from the group consisting of metals with high conductivity, for example, copper, copper alloys, aluminum, aluminum alloys, iron and iron alloys can be used. The specific shape of the metal substrate 2 is not particularly limited, and it may be a shape according to the use.
(Silver-Tin Alloy Plating Layer 3)
The silver-tin alloy plating layer 3 is arranged on the metal substrate 2. The silver-tin alloy plating layer 3 has a role of protecting the metal substrate 2 from corrosion. From the viewpoint of corrosion prevention and moldability, the silver-tin alloy plating layer 3 preferably entirely covers the metal substrate 2.
The ratio of the content (% by mass) of silver to tin in the silver-tin alloy plating layer 3 is preferably silver:tin=65:35 to 80:20. In addition to silver and tin, the silver-tin alloy plating layer 3 preferably contains at least one element selected from the group consisting of In, Zn, Ti and Sb. This is because an intermetallic compound with silver is produced by containing such an element in the silver-tin alloy plating layer 3, and an improvement in the Vickers hardness of the surface of the silver-tin alloy plating layer 3 is expected.
The silver-tin alloy plating layer 3 contains an intermetallic compound of silver and tin. In this embodiment, the silver-tin alloy plating layer 3 contains the intermetallic compound, so that the hardness of the silver-tin alloy plating layer 3 can be improved. Such an intermetallic compound is precipitated by controlling the concentration of silver and tin in the plating solution. Examples of the intermetallic compound include Ag3Sn and the like. Examples of the intermetallic compound in the case where the silver-tin alloy plating layer 3 contains at least one element selected from the group consisting of In, Zn, Ti and Sb, in addition to silver and tin, include Ag3In, AgZn, AgTi, Ag7Sb, and the like.
The Vickers hardness of the surface of the silver-tin alloy plating layer 3 in the terminal plating material 1 is 250 Hv or more. In this embodiment, by setting the Vickers hardness of the surface of the silver-tin alloy plating layer 3 within such a range, abrasion resistance can be improved. The Vickers hardness of the surface of the silver-tin alloy plating layer 3 is preferably 280 Hv or more. The Vickers hardness can be measured according to Japanese Industrial Standard JIS Z2244:2009 (Vickers hardness Test-Test Method). In addition, the Vickers hardness can be measured at a test temperature of 25° C. and a test force of 3 gf.
The Vickers hardness of the surface of the silver-tin alloy plating layer 3 in the terminal plating material 1 after being heated at 50° C. to 200° C. for 20 minutes or more is preferably 250 Hv or more. When silver or a silver alloy is placed under a high temperature environment, silver crystal grains become large and the hardness of the silver or the silver alloy may decrease. However, in this embodiment, the silver-tin alloy plating layer 3 contains an intermetallic compound of silver and tin. Therefore, by setting the Vickers hardness of the surface of the silver-tin alloy plating layer 3 in the terminal plating material 1 after being heated at 50° C. to 200° C. for 20 minutes or more to the above-mentioned range, it is possible to make it difficult to reduce abrasion resistance even when the terminal plating material 1 is used under a high temperature environment. The Vickers hardness of the surface of the silver-tin alloy plating layer 3 in the terminal plating material 1 after being heated at 50° C. to 200° C. for 20 minutes or more is more preferably 280 Hv or more. The Vickers hardness can be measured according to JIS Z2244:2009. In addition, the Vickers hardness can be measured at a test temperature of 25° C. and a test force of 3 gf.
The surface roughness of the silver-tin alloy plating layer 3 is 0.60 μmRa or less. By setting the surface roughness of the silver-tin alloy plating layer 3 in such a range, contact resistance can be reduced. The surface roughness of the silver-tin alloy plating layer 3 is preferably 0 μmRa or more and 0.25 μmRa or less. The surface roughness is the arithmetical mean roughness and can be measured according to JIS B0601:2013 (Geometrical Product Specifications (GPS)-Surface texture: Profile method-Terms, definitions and surface texture parameters).
The thickness of the silver-tin alloy plating layer 3 is preferably 0.1 μm or more, and more preferably 1 μm or more, from the viewpoint of corrosion resistance. Also, the thickness of the silver-tin alloy plating layer 3 is preferably 30 μm or less, and more preferably 20 μm or less, from the viewpoint of productivity and cost reduction.
The silver-tin alloy plating layer 3 can be formed, for example, by preparing a silver-tin alloy plating bath by mixing a tin salt in a silver plating bath, and plating the metal substrate 2 by immersing it in the silver-tin alloy plating bath. Plating is preferably performed by constant current electrolysis because it is easy to control the film thickness.
The silver-tin plating bath used for the silver-tin alloy plating layer 3 can contain, for example, a silver salt, a tin salt, a conductive salt, a brightener, and the like. Examples of the material used for the silver salt include silver cyanide, silver iodide, silver oxide, silver sulfate, silver nitrate, silver chloride, and the like. Also, examples of the conductive salt include potassium cyanide, sodium cyanide, potassium pyrophosphate, potassium iodide, sodium thiosulfate, and the like. Examples of the brightener include metal brighteners such as antimony, selenium and tellurium, and organic brighteners such as benzenesulfonic acid and mercaptan.
Examples of the material used for the tin salt of the silver-tin alloy plating layer 3 include organic stannous sulfonates such as stannous methanesulfonate, stannous salts such as stannous pyrophosphate, stannous chloride, stannous sulfate, stannous acetate, stannous sulfamate, stannous gluconate, stannous tartrate, stannous oxide, stannous fluoroborate, stannous succinate, stannous lactate, stannous citrate, stannous phosphate, stannous iodide, stannous formate and stannous fluorosilicate, and stannic salts such as sodium stannate and potassium stannate.
The current density in the case of electroplating the silver-tin alloy plating layer 3 is preferably 0.3 A/dm2 or more, and more preferably 0.9 A/dm2 or more. When the current density is increased, silver-tin alloy plating can be performed in a faster time, and productivity is improved. However, when the current density is increased, the surface becomes rough and the surface roughness Ra increases. Therefore, the upper limit of the current density is set so as to satisfy the condition of the surface roughness in consideration of various factors such as productivity, composition of the plating bath, ion concentration, and shape of the object to be plated. The plating bath temperature in the case of electroplating the silver-tin alloy plating layer 3 is preferably 0° C. to 50° C., and more preferably 20° C. to 40° C. By setting the plating bath temperature in such a range, the silver-tin alloy plating layer 3 can be effectively formed by a complex effect.
(Nickel Plating Layer 4)
As shown in
The method of forming the nickel plating layer 4 is not particularly limited, but the metal substrate 2 can be placed in a nickel plating bath and plated by a known plating method.
The nickel plating bath can contain, for example, a nickel salt, a pH buffering agent, a brightener, and the like. Examples of the material used for the nickel salt include nickel sulfate, nickel chloride, nickel sulfamate, and the like. Examples of the pH buffering agent include boric acid, citric acid, nickel acetate, and the like. Examples of the brightener include sulfanates, saccharin, sulfonamide, sulfinic acid, naphthalene, sodium naphthalenesulfonate, nickel acetate, and the like.
The current density in the case of electroplating the nickel plating layer 4 is preferably 2.0 A/dm2 to 15.0 A/dm2, and more preferably 2.0 A/dm2 to 10.0 A/dm2. The plating bath temperature in the case of electroplating the nickel plating layer 4 is preferably 45° C. to 65° C. It is preferable since nickel plating can be performed with a high current density by setting the plating bath temperature in such a range.
(Silver Strike Plating Layer 5)
As shown in
The method of forming the silver strike plating layer 5 is not particularly limited, but the metal substrate 2 or the metal substrate 2 on which the nickel plating 4 has been applied can be placed in a silver strike plating bath and plated by a known plating method.
The silver strike plating bath can contain, for example, a silver salt, a conductive salt, a brightener, and the like. Examples of the material used for the silver salt include silver cyanide, silver iodide, silver oxide, silver sulfate, silver nitrate, silver chloride, and the like. Also, examples of the conductive salt include potassium cyanide, sodium cyanide, potassium pyrophosphate, potassium iodide, sodium thiosulfate, and the like. Examples of the brightener include metal brighteners such as antimony, selenium and tellurium, benzenesulfonic acid, mercaptan, and the like.
The current density in the case of electroplating the silver strike plating layer 5 is preferably 1.6 A/dm2 or more, and more preferably 2.0 A/dm2 or more. The upper limit of the current density is set in consideration of various factors such as productivity, composition of the plating bath, ion concentration, and shape of the object to be plated. The plating bath temperature in the case of electroplating the silver strike plating layer 5 is preferably 20° C. to 30° C. It is preferable since the possibility of burning can be reduced by setting the plating bath temperature in such a range.
The contact resistance of the terminal plating material 1 of this embodiment is preferably 0 mΩ or more and 5.0 mΩ or less. By setting the contact resistance of the terminal plating material 1 in such a range, it is possible to reduce heat generation and power consumption when used as a terminal. The contact resistance of the terminal plating material 1 is more preferably 0 mΩ or more and 2.5 mΩ or less, and further preferably 0 mΩ or more and 1.0 mΩ or less. Contact resistance can be measured using, for example, an electrical contact simulator CRS-1103-AL manufactured by Yamasaki Seiki Kenkyusho, Inc.
The terminal plating material 1 of this embodiment includes the metal substrate 2, and the silver-tin alloy plating layer 3 containing a silver-tin alloy, arranged on the metal substrate 2. Moreover, the silver-tin alloy plating layer 3 contains an intermetallic compound of silver and tin, the Vickers hardness of the surface of the silver-tin alloy plating layer 3 in the terminal plating material 1 is 250 Hv or more, and the surface roughness of the silver-tin alloy plating layer 3 is 0.60 μmRa or less. Therefore, when the terminal plating material 1 of this embodiment is used as a terminal, the abrasion resistance is also high while minimizing the increase in contact resistance.
[Terminal 10]
A terminal 10 of this embodiment is formed from a terminal plating material 1. Therefore, the terminal 10 of this embodiment has also high abrasion resistance while minimizing the increase in contact resistance as compared to the terminal plated with conventional silver or silver alloy. From the viewpoint of corrosion prevention and moldability, the silver-tin alloy plating layer 3 of the terminal 10 preferably entirely covers the metal substrate 2 of the terminal 10.
[Terminal-Equipped Electric Wire 20]
As shown in
The terminal 10 shown in
The electric wire connection part 12 includes a conductor crimping part 14 for caulking the conductor 31 of the electric wire 30 and a covering material caulking part 15 for caulking the electric wire covering material 32 of the electric wire 30.
The conductor crimping part 14 is in direct contact with the conductor 31 exposed by removing the electric wire covering material 32 at the terminal portion of the electric wire 30, and has a bottom plate part 16 and a pair of conductor caulking pieces 17. The pair of conductor caulking pieces 17 is extended upward from both side edges of the bottom plate part 16. The pair of conductor caulking pieces 17 is bent inward so as to wrap around the conductor 31 of the electric wire 30, whereby the conductor 31 can be caulked so as to closely contact the upper face of the bottom plate part 16. The conductor crimping part 14 is formed in a substantially U shape in cross section by the bottom plate part 16 and the pair of conductor caulking pieces 17.
The covering material caulking part 15 is in direct contact with the electric wire covering material 32 at the terminal portion of the electric wire 30, and has a bottom plate part 18 and a pair of covering material caulking pieces 19. The pair of covering material caulking pieces 19 is extended upward from both side edges of the bottom plate part 18. The pair of covering material caulking pieces 19 is bent inward so as to wrap around the portion with the electric wire covering material 32, whereby the electric wire covering material 32 can be caulked in a state of closely contacting the upper face of the bottom plate part 18. The covering material caulking part 15 is formed in a substantially U shape in cross section by the bottom plate part 18 and the pair of covering material caulking pieces 19. The portion from the bottom plate part 16 of the conductor crimping part 14 to the bottom plate part 18 of the covering material caulking part 15 is continuously formed as a common bottom plate part.
The electric wire 30 has the conductor 31 and the electric wire covering material 32 covering the conductor 31. As the material of the conductor 31, a metal having high conductivity can be used. As the material of the conductor 31, for example, copper, a copper alloy, aluminum, an aluminum alloy or the like can be used. In recent years, weight reduction of electric wire is required. Therefore, it is preferable that the conductor 31 is made of lightweight aluminum or an aluminum alloy.
As the material of the electric wire covering material 32 covering the conductor 31, a resin capable of ensuring electrical insulation can be used. As the material of the electric wire covering material 32, for example, an olefin type resin can be used. Specifically, as the material of the electric wire covering material 32, at least one kind selected from the group consisting of polyethylene (PE), polypropylene (PP), ethylene copolymer and propylene copolymer can be used as a main component. In addition, as the material of the electric wire covering material 32, polyvinyl chloride (PVC) can also be used as a main component. Among them, it is preferable that the material of the electric wire covering material 32 contains polypropylene or polyvinyl chloride as a main component since flexibility and durability are high. The main component herein refers to a component of 50% by mass or more of the entire electric wire covering material.
The terminal 10 can be manufactured, for example, as follows. First, as shown in
The terminal-equipped electric wire 20 of this embodiment has the terminal 10. Therefore, the terminal-equipped electric wire 20 of this embodiment has high abrasion resistance at the terminal 10 portion, as compared to the conventional terminal plated with silver or silver alloy, and an increase in contact resistance can be minimized. Therefore, the terminal-equipped electric wire 20 of this embodiment can be suitably also used in places like hybrid vehicles and electric vehicles.
[Wire Harness]
A wire harness 40 of this embodiment includes the terminal-equipped electric wire 20. Specifically, as shown in
In
The wire harness 40 of this embodiment includes the terminal-equipped electric wire 20. Therefore, the wire harness 40 of this embodiment has high abrasion resistance at the terminal 10 portion, as compared to the conventional terminal plated with silver or silver alloy, and an increase in contact resistance can be minimized. Therefore, the wire harness 40 of this embodiment can be suitably also used in places like hybrid vehicles and electric vehicles.
Hereinbelow, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.
First, pretreatment of a metal substrate as a material to be plated was performed. Specifically, the metal substrate was washed by alkali degreasing, and immersed in 10% sulfuric acid for 2 minutes for pickling, followed by water washing. For the metal substrate, a C1020-H copper plate specified in JIS H3100:2012 (Copper and copper alloy sheets, plates and strips) was used.
Next, a nickel plating layer was formed on the surface of the metal substrate. Specifically, the pretreated metal substrate was immersed in a plating bath for a nickel plating layer, and was subjected to constant current electrolysis under the conditions of a current density of 5 A/dm2, an electrolysis time of 30 seconds, and a plating bath temperature of 55° C., using a DC stabilized power supply. After completion of the electrolysis, the metal substrate was taken out from the plating bath and washed with water. As a result, a metal substrate having a nickel plating layer formed on the entire surface of the metal substrate was obtained. The composition of the plating bath for a nickel plating layer is 240 g/L of nickel sulfate, 45 g/L of nickel chloride, and 30 g/L of boric acid. The thickness of the nickel plating layer was 1.0 μm. In addition, PA18-5B manufactured by TEXIO TECHNOLOGY CORPORATION was used as the DC stabilized power supply.
Next, a silver strike plating layer was formed on the nickel plating layer. Specifically, the metal substrate on which the nickel plating layer was formed was immersed in a plating bath for a silver strike plating layer, and was subjected to constant current electrolysis under the conditions of a current density of 2.5 A/dm2, an electrolysis time of 1 min, and a plating bath temperature of 25° C., using a DC stabilized power supply. After completion of the electrolysis, the metal substrate was taken out from the plating bath and washed with water. As a result, a metal substrate having a silver strike plating layer formed on the entire surface of the metal substrate on which the nickel plating layer was formed was obtained. The composition of the plating bath for a silver strike plating layer is 4.2 g/L of silver cyanide and 80 g/L of potassium cyanide. The thickness of the silver strike plating layer was 0.3 μm. In addition, PA18-5B manufactured by TEXIO TECHNOLOGY CORPORATION was used as the DC stabilized power supply.
Next, a silver-tin alloy plating layer was formed on the silver strike plating layer. Specifically, the metal substrate on which the silver strike plating layer was formed was immersed in a plating bath for a silver-tin alloy plating layer prepared as shown in Tables 1 and 2, and was subjected to constant current electrolysis under the conditions shown in Tables 1 and 2, at a plating bath temperature of 25° C., using a DC stabilized power supply. The electrolysis time was adjusted so that the thickness of the silver-tin alloy plating layer to be formed was 5 μm. In addition, PA18-5B manufactured by TEXIO TECHNOLOGY CORPORATION was used as the DC stabilized power supply.
[Evaluation]
Evaluation was performed on the test samples of examples and comparative examples by the following method. The results are also shown in Table 1 and Table 2.
(Composition of Silver-Tin Alloy Plating Layer)
The composition of the silver-tin alloy plating layer was confirmed by analyzing the obtained test sample with a scanning electron microscope (SEM)-energy dispersive X-ray spectroscopy (EDX).
(Intermetallic Compound of Silver-Tin Alloy Plating Layer)
The intermetallic compound of the silver-tin alloy plating layer was confirmed by X-ray crystal structure analysis of the obtained test sample using an X-ray diffractometer (XRD).
(Vickers Hardness)
The Vickers hardness was evaluated by measuring the surface of the obtained test sample according to JIS Z2244:2009, using a micro hardness tester DUH-211 manufactured by Shimadzu Corporation. The test temperature was set at 25° C., and the test force was set at 3 gf. The Vickers hardness was evaluated by measuring before and after heating the test sample. The test sample after heating was heated at 160° C. for 150 hours and then cooled to 25° C., and the Vickers hardness was measured.
(Abrasion Resistance)
The abrasion resistance was evaluated by performing a sliding test. The sliding test was evaluated using a sliding test apparatus CRS-B1050 manufactured by Yamasaki Seiki Kenkyusho, Inc. The conditions of the sliding test are as follows.
The case where the abrasion depth after the sliding test was 5 μm or less was evaluated as “X”, and the case where the abrasion depth exceeding 5 μm was evaluated as “Y”.
(Surface Roughness)
For the surface roughness, the arithmetical mean roughness of the surface of the obtained test sample was measured according to JIS B0601:2013, using a contact type surface roughness measuring instrument Alpha-Step D500 manufactured by KLA-Tencor Corporation.
(Contact Resistance)
For the contact resistance, the surface of the obtained test sample was measured using an electrical contact simulator CRS-1103-AL manufactured by Yamasaki Seiki Kenkyusho, Inc. The measurement conditions of contact resistance are as follows.
(Contact Reliability)
The contact reliability was evaluated as “X” when the contact resistance measured as described above was 5.0 mΩ or less, and “Y” when the contact resistance exceeded 5.0 mΩ.
From the results in Table 1, the test samples of Examples 1 to 4 contain the intermetallic compound of silver and tin, and the Vickers hardness and surface roughness are within the predetermined ranges. Therefore, abrasion resistance and contact reliability were good. On the other hand, from the results in Table 2, the laminates of Comparative Examples 1 to 4 did not have the intermetallic compound of silver and tin, or the Vickers hardness or surface roughness was not within the predetermined range. Therefore, it could not be said that abrasion resistance and contact reliability were sufficient.
While the present invention has been described above by reference to the examples and the comparative examples, the present invention is not intended to be limited to the descriptions thereof, and various modifications will be apparent to those skilled in the art within the scope of the present invention.
| Number | Date | Country | Kind |
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| 2017-010170 | Jan 2017 | JP | national |
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| Number | Date | Country | |
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| 20180212350 A1 | Jul 2018 | US |
