CN110305395B - Flame-retardant resin composition and insulated wire - Google Patents
Flame-retardant resin composition and insulated wire Download PDFInfo
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- CN110305395B CN110305395B CN201811319999.0A CN201811319999A CN110305395B CN 110305395 B CN110305395 B CN 110305395B CN 201811319999 A CN201811319999 A CN 201811319999A CN 110305395 B CN110305395 B CN 110305395B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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- Polymers & Plastics (AREA)
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- Spectroscopy & Molecular Physics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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- Insulated Conductors (AREA)
Abstract
The invention provides a flame-retardant resin composition with high flame retardance and an insulated wire. The flame-retardant resin composition contains an olefin resin, a molybdate flame retardant and a metal hydroxide. The content of the molybdate flame retardant is 3 to 40 parts by mass relative to 100 parts by mass of the olefin resin. The specific gravity of the molybdate flame retardant is 4.0g/cm 3 The following. The molybdate flame retardant has an average particle diameter of 2.5 μm or less. The molybdate flame retardant preferably contains zinc molybdate. The molybdate flame retardant is preferably particles containing inorganic fine particles and zinc molybdate supported on the surfaces of the inorganic fine particles.
Description
Technical Field
The present disclosure relates to a flame-retardant resin composition and an insulated wire.
Background
In order to improve the flame retardancy of the resin composition, a flame retardant is added to the resin composition. As the flame retardant, a metal hydroxide is used. Examples of the metal hydroxide include magnesium hydroxide and aluminum hydroxide. However, the flame retardancy of the resin composition cannot be sufficiently improved by merely adding the metal hydroxide. Patent document 1 discloses that magnesium hydroxide or the like is used in combination with molybdate as a flame retardant to be added to a resin composition.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 5993264 publication
Disclosure of Invention
Problems to be solved by the invention
Even in the technique disclosed in patent document 1, the flame retardancy of the resin composition is still insufficient. An object of one aspect of the present disclosure is to provide a flame-retardant resin composition and an insulated wire having high flame retardancy.
Means for solving the problems
One aspect of the present disclosure is a flame-retardant resin composition containing an olefin resin, a molybdate flame retardant and a metal hydroxide, wherein the molybdate flame retardant is contained in an amount of 3 to 40 parts by mass based on 100 parts by mass of the olefin resin, and the molybdate flame retardant has a specific gravity of 4.0g/cm 3 The molybdate flame retardant has an average particle diameter of 2.5 μm or less. The flame-retardant resin composition according to one aspect of the present disclosure has high flame retardancy.
Another aspect of the present disclosure is an insulated wire having a conductor and a flame-retardant layer disposed on an outer periphery of the conductor, the flame-retardant layer containing the flame-retardant resin composition according to one aspect of the present disclosure. The insulated wire as another aspect of the present disclosure has a flame retardant layer with high flame retardancy.
Drawings
Fig. 1 is a sectional view showing a configuration of an insulated wire 100;
fig. 2 is a sectional view showing a structure of an insulated wire 200.
Description of the symbols
100. 200 method 8230, an insulated wire 110 method 8230, a conductor 120 method 8230, an electric insulation layer 130 method 8230and a flame retardant layer.
Detailed Description
Exemplary embodiments of the present disclosure are explained.
1. Flame-retardant resin composition
The disclosed flame-retardant resin composition contains an olefin resin, a molybdate flame retardant, and a metal hydroxide.
Examples of the olefin resin include polyethylene, ethylene-ethyl acrylate copolymer (EEA), ethylene-vinyl acetate copolymer (EVA), and ethylene-acrylic ester copolymer. As the olefin resin, can use the above 1 kind, can also use 2 or more mixtures. When an olefin resin based on EEA or EVA is used, the flame retardancy of the flame retardant resin composition of the present disclosure can be further improved.
The content of the molybdate flame retardant is 3 to 40 parts by mass relative to 100 parts by mass of the olefin resin. The flame retardancy of the flame-retardant resin composition of the present disclosure can be improved by setting the content of the molybdate flame retardant to 3 parts by mass or more. However, even if the content of the molybdate flame retardant exceeds 40 parts by mass, it is difficult to further improve the flame retardancy of the flame-retardant resin composition of the present disclosure.
The specific gravity of the molybdate flame retardant is 4.0g/cm 3 The following. The molybdate flame retardant has an average particle diameter of 2.5 μm or less. The flame retardancy of the flame retardant resin composition of the present disclosure can be improved by setting the specific gravity and the average particle diameter of the molybdate flame retardant within the above ranges. The reason for this is presumed as follows. The surface of the molybdate flame retardant functions as a catalyst for resin carbonization. The specific gravity of the molybdate flame retardant is 4.0g/cm 3 When the average particle diameter of the molybdate flame retardant is 2.5 μm or less, the surface area of the molybdate flame retardant is increased. As a result, the flame retardancy of the flame retardant resin composition of the present disclosure is improved.
As a method for measuring the specific gravity of the molybdate flame retardant, there is a gas phase substitution method using He gas or the like in a medium. As a method for measuring the average particle diameter of the molybdate flame retardant, there is a method using a laser diffraction scattering particle size distribution measuring apparatus "LS 13 320SW (single wave)" manufactured by Beckman Coulter co.
Examples of the molybdate flame retardant include zinc molybdate, calcium molybdate, and 1-valent salts of molybdic acid. As the molybdate flame retardant, zinc molybdate is preferable. When zinc molybdate is used, the flame retardancy of the flame retardant resin composition of the present disclosure can be further improved as compared to when calcium molybdate is used. In addition, since zinc molybdate is insoluble in water, the insulating properties of the flame retardant resin composition of the present disclosure can be improved when zinc molybdate is used.
The molybdate flame retardant is, for example, particles containing inorganic fine particles and zinc molybdate supported on the surfaces of the inorganic fine particles. The specific gravity of the inorganic fine particles is preferably 3.8g/cm 3 The following. The inorganic fine particles had a specific gravity of 3.8g/cm 3 Hereinafter, the specific gravity of the molybdate flame retardant is easily set to 4.0g/cm 3 The following.
Examples of the inorganic fine particles include magnesium hydroxide, zinc borate, talc, calcium carbonate, and aluminum hydroxide. The inorganic fine particles are preferably flame-retardant inorganic fine particles. When flame-retardant inorganic fine particles are used, the flame retardancy of the flame-retardant resin composition of the present disclosure can be further improved. Examples of the flame-retardant inorganic fine particles include magnesium hydroxide and zinc borate.
Examples of the metal hydroxide include magnesium hydroxide and aluminum hydroxide. The content of the metal hydroxide is 100 parts by mass or more and 250 parts by mass or less with respect to 100 parts by mass of the olefin resin. The content of the metal hydroxide can be appropriately adjusted according to the flame retardancy, tensile strength, elongation and the like required for the flame-retardant resin composition.
The surface of the metal hydroxide is preferably treated with a fatty acid or a silane compound. In this case, the tensile properties of the flame-retardant resin composition of the present disclosure can be made more favorable.
The flame-retardant resin composition of the present disclosure may further contain a resin that functions as a compatibilizing agent and an adhesion enhancer, for example. The flame-retardant resin composition of the present disclosure may further contain, for example, other flame-retardant aids, lubricants, crosslinking agents, carbon black, colorants, antioxidants, and the like.
The flame-retardant resin composition of the present disclosure can be produced by, for example, a method of kneading raw materials using a twin-screw extruder, twin-screw rolls, a mixer, a kneader, or the like.
2. Insulated wire
The insulated wire of the present disclosure has a conductor and a flame retardant layer. The flame retardant layer is disposed on the outer periphery of the conductor. The flame-retardant layer contains the flame-retardant resin composition described in the section "1. Flame-retardant resin composition".
For example, as shown in fig. 1, an insulated wire 100 has a conductor 110, an electrical insulation layer 120, and a flame retardant layer 130. The flame retardant layer 130 is disposed on the outer periphery of the conductor 110.
As the conductor 110, a commonly used metal wire can be used. Examples of the metal wire include a copper wire, a copper alloy wire, an aluminum wire, a gold wire, and a silver wire. The conductor 110 may also have a metal plating layer on its outer circumferential surface. Examples of the metal plating layer include layers made of tin, nickel, and the like. The conductor 110 may also be an aggregate twisted conductor of twisted metal wires. The cross-sectional area and the outer diameter of the conductor 110 can be appropriately designed according to the electrical characteristics required for the insulated wire 100.
The flame retardant layer 130 may be formed by extruding the flame retardant resin composition onto the electrical insulation layer 120 using an extruder.
For example, as shown in fig. 2, an insulated wire 200 has a conductor 110 and a flame retardant layer 130. The flame retardant layer 130 is disposed on the outer periphery of the conductor 110. The insulated wire 200 is basically the same in construction as the insulated wire 100. However, the insulated wire 200 does not have the electrical insulation layer 120. In the insulated wire 200, the flame retardant layer 130 covers the outer peripheral surface of the conductor 110.
The flame retardant layer 130 may be formed by extruding the flame retardant resin composition onto the conductor 110 using an extruder.
3. Examples of the embodiments
(3-1) production of flame-retardant resin composition
Flame-retardant resin compositions of examples 1 to 10 were produced by mixing the components shown in Table 1. Flame-retardant resin compositions of comparative examples 1 to 7 were prepared by mixing the components shown in Table 2.
[ Table 1]
[ Table 2]
The unit of the amount of the components in tables 1 and 2 is part by mass. The EVA in tables 1 and 2 is Evaflex (registered trademark) EV170 manufactured by mitsui chemical co. The EEA in Table 1 is Rexpearl (registered trademark) EEA 1150 manufactured by Japan polyethylene Co. The LDPE in Table 1 is Mirason (registered trademark) 3530 manufactured by DuPont chemical Co., ltd.
The magnesium hydroxide in tables 1 and 2 is Magseeds S4 manufactured by shendao chemical industry co. Magseeds S4 were surface treated with fatty acids.
The molybdate flame retardant A in Table 1 is Kemgard (registered trademark) MZM manufactured by Huber Engineered Materials. The molybdate flame retardant A is composed of particles composed of fine magnesium hydroxide particles and zinc molybdate supported on the surfaces of the fine particles. The magnesium hydroxide fine particles correspond to inorganic fine particles.
Molybdate flame retardant B in Table 1 was Kemgard 1100 manufactured by Huber Engineered Materials. The molybdate flame retardant B is composed of particles composed of magnesium silicate fine particles and zinc molybdate supported on the surfaces of the fine particles. The magnesium silicate fine particles correspond to inorganic fine particles.
Molybdate flame retardant C in Table 1 was Kemgard 700Z manufactured by Huber Engineered Materials. The molybdate flame retardant C is composed of particles composed of fine particles of zinc borate and zinc molybdate supported on the surfaces of the fine particles. The zinc borate fine particles correspond to inorganic fine particles.
Molybdate flame retardant D in Table 1 was Kemgard 911A manufactured by Huber Engineered Materials. The molybdate flame retardant D consists of calcium zinc molybdate.
Molybdate flame retardant E in Table 1 was Kemgard 911B manufactured by Huber Engineered Materials. The molybdate flame retardant E is composed of alkaline zinc molybdate.
Molybdate flame retardant F in Table 1 was Kemgard 425 manufactured by Huber Engineered Materials. The molybdate flame retardant F consists of calcium molybdate.
Specific gravities (g/cm) of the molybdate flame retardants A to F are shown in tables 1 and 2 3 ) And average particle diameter (. Mu.m).
(3-2) evaluation of flame-retardant resin composition
The oxygen index was measured in accordance with JIS K7201-2 for the flame-retardant resin compositions of examples 1 to 10 and comparative examples 1 to 7. The measurement results are shown in tables 1 and 2.
The flame-retardant resin compositions of examples 1 to 10 and comparative examples 1 to 7 were subjected to UL94 vertical burning test. The test piece was 1mm thick and 13mm wide. The combustibility classification based on the test results is shown in the above tables 1 and 2. The "x" in table 2 indicates that the determination result was failed.
Comparative example 1 is the same flame retardant resin composition as in example 1 except that the value of the average particle diameter of the molybdate flame retardant exceeds the specified range of the present disclosure. While the oxygen index of example 1 was 34.8, the oxygen index of comparative example 1 was 29.8, and the oxygen index of example 1 showed a larger value, so that it can be said that the flame retardancy of example 1 was more excellent.
Comparative example 2 is the same flame retardant resin composition as in example 2 except that the value of the average particle diameter of the molybdate flame retardant exceeds the specified range of the present disclosure. While the oxygen index of example 2 was 50.2, the oxygen index of comparative example 2 was 37.1, and the oxygen index of example 2 showed a larger value, so that it can be said that the flame retardancy of example 2 was more excellent.
Comparative example 3 is the same flame retardant resin composition as in example 3 except that the value of the average particle diameter of the molybdate flame retardant exceeds the specified range of the present disclosure. While the oxygen index of example 3 was 49.9, the oxygen index of comparative example 3 was 38.1, and the oxygen index of example 3 showed a larger value, so that it can be said that the flame retardancy of example 3 was more excellent.
Comparative example 4 is the same flame retardant resin composition as example 6 except that the specific gravity of the molybdate flame retardant exceeds the range specified in the present disclosure. While the oxygen index of example 6 was 41.1, the oxygen index of comparative example 4 was 38.2, and the oxygen index of example 6 showed a larger value, so that it can be said that the flame retardancy of example 6 was more excellent.
Comparative example 5 is the same flame retardant resin composition as example 7 except that the specific gravity value of the molybdate flame retardant exceeds the specified range of the present disclosure. While the oxygen index of example 7 was 42.3, the oxygen index of comparative example 5 was 40.8, and the oxygen index of example 7 showed a larger value, so that it can be said that the flame retardancy of example 7 was more excellent.
Comparative example 6 is the same flame retardant resin composition as example 7 except that the value of the average particle diameter of the molybdate flame retardant exceeds the range specified in the present disclosure. While the oxygen index of example 7 was 42.3, the oxygen index of comparative example 6 was 35.5, and the oxygen index of example 7 showed a larger value, so that it can be said that the flame retardancy of example 7 was more excellent.
Comparative example 7 is a flame retardant resin composition similar to example 10 except that the specific gravity of the molybdate flame retardant exceeds the predetermined range of the present disclosure. While the oxygen index of example 10 was 44.8, the oxygen index of comparative example 7 was 35.7, and the oxygen index of example 10 showed a larger value, so that it can be said that the flame retardancy of example 10 was more excellent.
From the above, it is understood that the oxygen index in the flame-retardant resin compositions of examples 1 to 10 is equal to or more than that in the flame-retardant resin compositions of comparative examples 1 to 7.
The flame retardancy in the flame retardant resin compositions of examples 1 to 10 was higher than that in the flame retardant resin compositions of comparative examples 1 to 7.
4. Other embodiments
The embodiments of the present disclosure have been described above, but the present disclosure is not limited to the above embodiments and may be implemented by various modifications.
(1) The functions of 1 component in each of the above embodiments may be shared by a plurality of components, and the functions of a plurality of components may be exhibited by 1 component. Further, a part of the configuration of each of the above embodiments may be omitted. At least a part of the configuration of each of the above embodiments may be added or replaced to the configuration of the other above embodiments. It should be noted that various aspects included in the technical idea specified by the characters described in the patent claims are embodiments of the present disclosure.
(2) The present disclosure can be achieved in various ways other than the flame retardant resin composition and the insulated wire, such as a method for producing a flame retardant resin composition, a method for producing an insulated wire, and a system having an insulated wire as a component.
Claims (4)
1. A flame-retardant resin composition comprising an olefin resin, a molybdate flame retardant and a metal hydroxide,
the content of the molybdate flame retardant is 3 to 40 parts by mass based on 100 parts by mass of the olefin resin,
the specific gravity of the molybdate flame retardant is 4.0g/cm 3 In the following, the following description is given,
the average particle diameter of the molybdate flame retardant is less than 2.5 mu m,
the molybdate flame retardant is particles comprising inorganic fine particles and zinc molybdate supported on the surface of the inorganic fine particles,
the olefinic resin is polyethylene, ethylene-vinyl acetate copolymer or ethylene-acrylate copolymer.
2. The flame-retardant resin composition according to claim 1, wherein the olefin resin is an ethylene-ethyl acrylate copolymer.
3. The flame-retardant resin composition according to claim 1,
the content of the metal hydroxide is 100 parts by mass or more and 250 parts by mass or less with respect to 100 parts by mass of the olefin-based resin.
4. An insulated wire having a conductor and a flame-retardant layer disposed on the outer periphery of the conductor,
the flame-retardant layer contains the flame-retardant resin composition described in any one of claims 1 to 3.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2018059955A JP6547868B1 (en) | 2018-03-27 | 2018-03-27 | Flame retardant resin composition and insulated wire |
| JP2018-059955 | 2018-03-27 |
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| CN110305395B true CN110305395B (en) | 2023-03-17 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002156748A (en) * | 2000-11-21 | 2002-05-31 | Mitsubishi Gas Chem Co Inc | Flame-retardant resist composition |
| JP2011157509A (en) * | 2010-02-02 | 2011-08-18 | Hitachi Chem Co Ltd | Thermosetting insulating resin composition, and prepreg, laminated board, and multilayer printed wiring board using the same |
| JP2013010860A (en) * | 2011-06-29 | 2013-01-17 | Hitachi Chemical Co Ltd | Resin composition for printed wiring board, prepreg, laminate, and printed wiring board |
| JP2014065815A (en) * | 2012-09-26 | 2014-04-17 | Fujikura Ltd | Method for producing flame-retardant resin composition, flame-retardant resin composition, and cable using the same |
| CN106349554A (en) * | 2016-08-31 | 2017-01-25 | 欧宝聚合物江苏有限公司 | Low-smoke-amount non-halogen flame-retardant cable compound and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05262926A (en) * | 1992-03-18 | 1993-10-12 | Tosoh Corp | Flame-retardant polyolefin resin composition |
| EP3272709B1 (en) * | 2015-03-18 | 2019-12-25 | DIC Corporation | Spinel particles, method for producing same, and composition and molding including spinel particles |
-
2018
- 2018-03-27 JP JP2018059955A patent/JP6547868B1/en active Active
- 2018-11-07 CN CN201811319999.0A patent/CN110305395B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002156748A (en) * | 2000-11-21 | 2002-05-31 | Mitsubishi Gas Chem Co Inc | Flame-retardant resist composition |
| JP2011157509A (en) * | 2010-02-02 | 2011-08-18 | Hitachi Chem Co Ltd | Thermosetting insulating resin composition, and prepreg, laminated board, and multilayer printed wiring board using the same |
| JP2013010860A (en) * | 2011-06-29 | 2013-01-17 | Hitachi Chemical Co Ltd | Resin composition for printed wiring board, prepreg, laminate, and printed wiring board |
| JP2014065815A (en) * | 2012-09-26 | 2014-04-17 | Fujikura Ltd | Method for producing flame-retardant resin composition, flame-retardant resin composition, and cable using the same |
| CN106349554A (en) * | 2016-08-31 | 2017-01-25 | 欧宝聚合物江苏有限公司 | Low-smoke-amount non-halogen flame-retardant cable compound and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 钼酸盐阻燃抑烟剂研发现状;张文钲;《中国钼业》;20030228;第27卷(第1期);第7-9页 * |
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| JP6547868B1 (en) | 2019-07-24 |
| CN110305395A (en) | 2019-10-08 |
| JP2019172737A (en) | 2019-10-10 |
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Address after: Tokyo, Japan Patentee after: Bomeilicheng Co.,Ltd. Address before: Tokyo, Japan Patentee before: HITACHI METALS, Ltd. |