CN104981138B - A kind of manufacturing method for being electromagnetically shielded heat dissipation film - Google Patents
A kind of manufacturing method for being electromagnetically shielded heat dissipation film Download PDFInfo
- Publication number
- CN104981138B CN104981138B CN201410140979.2A CN201410140979A CN104981138B CN 104981138 B CN104981138 B CN 104981138B CN 201410140979 A CN201410140979 A CN 201410140979A CN 104981138 B CN104981138 B CN 104981138B
- Authority
- CN
- China
- Prior art keywords
- film
- heat dissipation
- electromagnetic shielding
- film layer
- alloy
- 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.)
- Expired - Fee Related
Links
- 230000017525 heat dissipation Effects 0.000 title claims abstract description 106
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000000853 adhesive Substances 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 13
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- 239000000696 magnetic material Substances 0.000 claims abstract description 7
- 230000009471 action Effects 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- 239000007791 liquid phase Substances 0.000 claims abstract description 3
- 230000001070 adhesive effect Effects 0.000 claims description 19
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 15
- 238000010521 absorption reaction Methods 0.000 claims description 13
- 230000001681 protective effect Effects 0.000 claims description 12
- 229910045601 alloy Inorganic materials 0.000 claims description 11
- 239000000956 alloy Substances 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 10
- 239000002390 adhesive tape Substances 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 239000003822 epoxy resin Substances 0.000 claims description 7
- 229920000647 polyepoxide Polymers 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 6
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000006096 absorbing agent Substances 0.000 claims description 4
- -1 iron-silicon-aluminum Chemical compound 0.000 claims description 4
- 239000002905 metal composite material Substances 0.000 claims description 4
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 229910001004 magnetic alloy Inorganic materials 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 239000005060 rubber Substances 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 229910000531 Co alloy Inorganic materials 0.000 claims description 2
- 229910000914 Mn alloy Inorganic materials 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- PUBULPPJKOUWSM-UHFFFAOYSA-N [Fe].[Cd].[Li] Chemical compound [Fe].[Cd].[Li] PUBULPPJKOUWSM-UHFFFAOYSA-N 0.000 claims description 2
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 claims description 2
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910000838 Al alloy Inorganic materials 0.000 claims 2
- QHCZEKMIMJAYOR-UHFFFAOYSA-N [Fe].[Zn].[Nb] Chemical compound [Fe].[Zn].[Nb] QHCZEKMIMJAYOR-UHFFFAOYSA-N 0.000 claims 2
- 229920002379 silicone rubber Polymers 0.000 claims 2
- 239000004945 silicone rubber Substances 0.000 claims 2
- 229910000599 Cr alloy Inorganic materials 0.000 claims 1
- GXTNDOSGOPRCEO-UHFFFAOYSA-N [Cr].[Fe].[Zn] Chemical compound [Cr].[Fe].[Zn] GXTNDOSGOPRCEO-UHFFFAOYSA-N 0.000 claims 1
- RFIJBZKUGCJPOE-UHFFFAOYSA-N [Fe].[Ni].[Zn] Chemical compound [Fe].[Ni].[Zn] RFIJBZKUGCJPOE-UHFFFAOYSA-N 0.000 claims 1
- OYCMCIMILVVEHY-UHFFFAOYSA-N [Mg].[Mn].[Fe] Chemical compound [Mg].[Mn].[Fe] OYCMCIMILVVEHY-UHFFFAOYSA-N 0.000 claims 1
- LNRYQGINUXUWLV-UHFFFAOYSA-N [Mn].[Fe].[Zn] Chemical compound [Mn].[Fe].[Zn] LNRYQGINUXUWLV-UHFFFAOYSA-N 0.000 claims 1
- KSIIOJIEFUOLDP-UHFFFAOYSA-N [Si].[Fe].[Ni] Chemical compound [Si].[Fe].[Ni] KSIIOJIEFUOLDP-UHFFFAOYSA-N 0.000 claims 1
- 239000002313 adhesive film Substances 0.000 claims 1
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 claims 1
- 239000000788 chromium alloy Substances 0.000 claims 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 claims 1
- BIJOYKCOMBZXAE-UHFFFAOYSA-N chromium iron nickel Chemical compound [Cr].[Fe].[Ni] BIJOYKCOMBZXAE-UHFFFAOYSA-N 0.000 claims 1
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 claims 1
- GOECOOJIPSGIIV-UHFFFAOYSA-N copper iron nickel Chemical compound [Fe].[Ni].[Cu] GOECOOJIPSGIIV-UHFFFAOYSA-N 0.000 claims 1
- 229910021484 silicon-nickel alloy Inorganic materials 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 230000004888 barrier function Effects 0.000 abstract 3
- 239000004575 stone Substances 0.000 abstract 1
- 239000012808 vapor phase Substances 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 31
- 229910002804 graphite Inorganic materials 0.000 description 31
- 239000010439 graphite Substances 0.000 description 31
- 238000012360 testing method Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000011889 copper foil Substances 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 239000011358 absorbing material Substances 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910000702 sendust Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000003522 acrylic cement Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910000604 Ferrochrome Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010063385 Intellectualisation Diseases 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Landscapes
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
Abstract
The present invention provides a kind of electromagnetic shielding heat dissipation film and its manufacturing methods.The electromagnetic shielding heat dissipation film includes heat dissipation film layer, barrier film layer and suction wave film layer, and heat dissipation film layer therein is compound stone ink film, and barrier film layer is metal film, and it is to be mixed with the organic adhesive agent film of soft magnetic material powder to inhale wave film layer.The step of manufacturing the electromagnetic shielding heat dissipation film be：Step 1, heat dissipation film is covered in smooth high temperature resistant film layer and forms heat dissipation film layer, step 2, metal film is deposited on heat dissipation film surface by vapor phase method or liquid phase method or both combined method and forms barrier film layer, step 3, the organic binder bond for being mixed with soft magnetic material powder, which is coated in, to deposit has metal film heat dissipation film surface and cures under the action of high temperature or catalyst, 4, and the high temperature resistant film layer of stripping heat dissipation film surface obtains electromagnetic shielding heat dissipation film of the present invention.
Description
Technical Field
The invention relates to an electromagnetic shielding heat dissipation film and a manufacturing method thereof, in particular to an electromagnetic shielding heat dissipation film with electromagnetic shielding and heat dissipation functions, which is used for electromagnetic shielding and electromagnetic noise suppression in the motor and electronic industries.
Background
With the rapid development of electronic technology, electronic products with various personalized entertainment functions are increasingly popularized, and the electronic products are rapidly developed in the directions of intellectualization, integration, lightness, thinness, multi-functionalization and the like.
However, as the speed and frequency of data transmission and the integration degree of circuit boards increase, there is an increasing demand for improving the environment of electromagnetic interference to reduce interference of adjacent components. In addition, when the intelligent device works, electromagnetic waves can be continuously emitted outwards, the maximum power can reach 2w, and the influence on the surrounding environment is great. Therefore, in order to avoid interference with each other and the surrounding environment during operation, some unnecessary radiation must be limited. Therefore, the use of a wave-absorbing material that can absorb and dissipate magnetic energy can avoid this problem, as proposed in EP0667643B1, which blends a magnetic material with rubber to form a wave-absorbing film layer.
The principle of the wave-absorbing material for shielding electromagnetic waves is that absorbed electromagnetic waves are converted into heat energy, which can cause the temperature of an electronic device to rise, not only can reduce the wave-absorbing effect of the wave-absorbing film, but also can reduce the power consumption and the stability of the electronic device.
The synthetic graphite film (JP 1985181129A) is gradually becoming a hot spot in heat conductive materials due to its ultra-high thermal conductivity (800-. But because of its small specific gravity (<2g/cm3) The heat capacity and heat flux are limited, and the heat cannot be conducted out in time. Therefore, the heat capacity of the synthetic graphite film is improved and stably combined with the wave-absorbing material, so that the heating problem of the wave-absorbing material can be effectively solved and the processing reliability of the wave-absorbing material is improved.
The invention provides an electromagnetic shielding heat dissipation film, wherein a heat conduction layer is a synthetic graphite film, very high thermal diffusivity is provided, a metal shielding layer is arranged on the electromagnetic shielding heat dissipation film through a deposition method, the thermal capacity of a graphite film layer is effectively increased, and the thermal resistance between the two layers is greatly reduced because a metal layer is directly deposited on the surface of the graphite layer. Be provided with the layer of absorbing wave on the metal shielding layer surface, in the use, pierce through the layer of absorbing wave and the electromagnetic wave part that does not absorb can be by the metal level reflection thereby the secondary passes through the layer of absorbing wave to by the secondary absorption, effectual increase electromagnetic wave absorption effect.
Disclosure of Invention
The invention provides a comprehensive solution with excellent electromagnetic shielding efficiency and heat dissipation function, and provides an electromagnetic shielding heat dissipation film, aiming at the technical problems of electromagnetic shielding and heat dissipation of the existing electronic products. The electromagnetic shielding heat dissipation film can be conveniently attached to an electronic device, and can achieve the functions of heat dissipation and electromagnetic shielding while meeting the ultra-thin size requirement.
The electromagnetic shielding heat dissipation film comprises a heat dissipation film layer, a shielding film layer and a wave-absorbing film layer, wherein the heat dissipation film layer is a graphite film layer, the shielding film layer is a metal film, and the wave-absorbing film layer is an organic binder film mixed with soft magnetic material powder.
Preferably, according to the electromagnetic shielding heat dissipation film provided by the invention, a protection film is attached to one side of the heat dissipation film, a double-faced adhesive tape and a release film are attached to one side of the wave absorption film, after the release film is peeled, one side of the wave absorption film is attached to an electronic device through the double-faced adhesive tape, and the protection film has the functions of protecting the film layer and insulating.
Preferably, according to the electromagnetic shielding heat dissipation film provided by the invention, a protective film is attached to one side of the wave absorption film of the electromagnetic shielding heat dissipation film, a double-sided adhesive and a release film are attached to one side of the heat dissipation film, after the release film is peeled, one side of the heat dissipation film is attached to an electronic device through the double-sided adhesive, and the protective film has the functions of protecting the film layer and insulating.
Preferably, according to the electromagnetic shielding heat dissipation film provided by the invention, the double-sided adhesive and the release film are attached to one side of the wave absorption film and one side of the heat dissipation film of the electromagnetic shielding heat dissipation film, the electromagnetic shielding heat dissipation film is attached to the surface of the electronic device after the release film is peeled off, and other functional components can be attached to the outer surface of the electromagnetic shielding heat dissipation film through the double-sided adhesive.
Preferably, according to the electromagnetic shielding heat dissipation film of the present invention, the heat dissipation film layer is a synthetic graphite film, the thickness of the synthetic graphite film is 10um-50um, and the thermal conductivity is 800-2000W/m.k. The high thermal conductivity of the synthetic graphite film can ensure that the heat emitted by the electronic device on the heating point is rapidly diffused to the whole graphite film, thereby realizing the high-efficiency heat dissipation performance by increasing the heating area.
Preferably, according to the electromagnetic shielding heat dissipation film of the present invention, the synthetic graphite film of the heat dissipation film layerThe synthesis method comprises the steps of under the protection of inert gas, using 5-20 parts of polyimide filmOThe C/min speed is increased from room temperature to 500OC/min and keeping the temperature for 1-5 hours, and then keeping the temperature for 5-10 hoursORaising the temperature to 800-OC, keeping the temperature for 1-5 hours, and then keeping the temperature for 5-10 hoursORaising the temperature to 2600-OAnd C, preserving the heat for 1-5 hours, cooling to obtain a graphite film, and rolling the sintered graphite film to obtain a graphite film product with required thickness and smooth surface.
Preferably, according to the electromagnetic shielding heat dissipation film of the present invention, the shielding film layer is a metal film made of gold, silver, copper, nickel, iron, aluminum, zinc, titanium, chromium, cobalt or alloy. The metal film is a single metal film or a metal composite film formed by two or more layers of different metals, and the thickness of the metal composite film is 5nm-50 um.
Preferably, according to the electromagnetic shielding heat dissipation film of the present invention, the metal film of the shielding film layer is formed by a Physical Vapor Deposition (PVD) method, a Chemical Vapor Deposition (CVD) method, an evaporation coating method, a magnetron sputtering method, a chemical plating method, an electroplating method, or a composite process thereof.
Preferably, according to the electromagnetic shielding heat dissipation film provided by the invention, the wave absorbing film comprises 50-90% of wave absorbing agent and 10-40% of organic binder, the thickness of the wave absorbing film is 20um-1mm, and the magnetic permeability of the wave absorbing film at the frequency of 1MHz is more than 50.
Preferably, according to the electromagnetic shielding heat dissipation film of the present invention, the wave absorber is made of soft magnetic alloy powder, including but not limited to ni-zn-fe alloy, ni-cu-fe alloy, zn-cr-fe alloy, mn-zn-fe alloy, nb-zn-fe alloy, sendust alloy, nicr-fe alloy, znoz alloy, nicl alloy, sendust alloy, iron-cobalt alloy, ferrochrome alloy, sendust alloy, sendais alloy, mgmnfe alloy, cobalt-nickel alloy, lithium-manganese alloy or lithium-cadmium-iron alloy.
Preferably, according to the electromagnetic shielding heat dissipation film of the present invention, the organic binder is a polymer material, including but not limited to phenolic resin, urea-formaldehyde resin, epoxy resin, acrylic resin, polyvinyl butyral resin, vinyl acetate and its copolymer, silicone gum resin, polyurethane, rubber resin or their polymer.
The invention also provides a manufacturing method of the electromagnetic shielding heat dissipation film, which comprises the following steps:
step 1, attaching a heat dissipation film on a high-temperature resistant film layer with a smooth surface;
step 2, depositing a metal film on the surface of the heat dissipation film in the step 1 by a gas phase method or a liquid phase method or a combination method of the two methods,
step 3, mixing the soft magnetic material powder and the organic binder, stirring at a high speed, uniformly mixing, coating the surface of the metal film obtained in the step 2 in a reverse coating mode, a mesh roller coating mode, a blade coating mode, a spraying mode or a slit coating mode and the like, curing at a high temperature or under the action of a catalyst,
and 4, stripping the high-temperature-resistant film layer on the surface of the heat dissipation film to obtain the electromagnetic shielding heat dissipation film.
Preferably, according to the above manufacturing method, the material of the high temperature resistant film is a material that does not deform at a temperature greater than 100 ℃, such as high temperature resistant plastic, glass, stainless steel, and ceramic.
The electromagnetic shielding heat dissipation film comprises a graphite heat dissipation film layer, a metal film layer and a wave absorbing film layer, wherein each layer of the multilayer structure has unique functions, and all the layers can cooperate with each other to enhance the overall heat dissipation and electromagnetic shielding effects.
In terms of heat dissipation function, the metal layer has a relatively high density (such as copper 8.9 g/cm)3) Therefore, the heat capacity is relatively large, when the heat productivity of the electronic device is relatively large, the heat sink can store a part of heat to reduce the temperature, and the heat conduction can be assisted because of the high heat conductivity (such as copper 400W/m.k). The wave-absorbing layer has an alloy filling ratio as high as 50-90 percentMay act as a heat sink to store heat.
In the aspect of electromagnetic shielding, the metal film and the wave-absorbing film both have electromagnetic shielding functions, but the shielding mechanisms are different. The metal film is a shielding material mainly used for reflection loss, and the wave absorption film achieves the function of shielding electromagnetic waves through magnetic hysteresis loss. After the metal film and the wave-absorbing film are combined, in the application process, the electromagnetic wave is absorbed and lost through the wave-absorbing film, and the unabsorbed part penetrates through the wave-absorbing film and is consumed through the reflection loss of the metal film. After being reflected by the metal film, the residual electromagnetic waves can pass through the wave absorbing film again, so that the residual electromagnetic waves are absorbed by the wave absorbing film for the second time, and the electromagnetic shielding effect is greatly enhanced. The graphite itself is used as a conductive material, has a certain electromagnetic shielding effect, and can form a certain shielding effect on electromagnetic waves projected through the metal film.
From the view of the whole design structure, the metal film is manufactured on the graphite film through deposition, and bonding substances with high heat resistance, such as double faced adhesive tape and the like, are not arranged between the graphite film and the metal film, so that the heat is ensured to be rapidly conducted between the graphite film and the metal film. In addition, because the nano-sized micropores are distributed on the surface of the graphite film, metal can be deposited on the micropores through a deposition method, so that the contact area between the metal and the graphite film is increased, the attachment effect is more firm than that of adhesion, and the graphite film is not easy to peel off due to graphite delamination. Finally, the graphite film has lower surface energy, and is not easy to coat organic binder on the graphite film, and the metal film as the middle layer can effectively increase the binding performance of the wave absorbing film on the graphite film.
Drawings
The invention is explained in more detail below with reference to the drawings.
Fig. 1 is a structural view of an embodiment of an electromagnetic shielding heat dissipation film according to the present invention.
Fig. 2 is a structural view of another embodiment of the electromagnetic shielding heat dissipation film according to the present invention.
Fig. 3 is a structural view of still another embodiment of the electromagnetic shielding heat dissipation film according to the present invention.
Fig. 4 is an electromagnetic shielding performance graph of example 1.
Fig. 5 is an electromagnetic shielding performance graph of example 2.
Fig. 6 is a flow chart of a method for manufacturing the electromagnetic shielding heat dissipation film according to the present invention.
Detailed Description
The invention will now be further described with reference to specific embodiments thereof with reference to the accompanying drawings.
Example 1: as shown in fig. 1, the electromagnetic shielding heat dissipation film includes a heat dissipation film layer 11, a shielding film layer 12 and a wave-absorbing film layer 13, wherein the heat dissipation film layer 11 is a 25um graphite film, the heat conductivity of the graphite film is 1600W/m · k, the shielding film layer 12 is a copper foil, the thickness of the copper foil is 20um, the wave-absorbing film 13 is a film containing 80% by weight of iron-nickel alloy powder and 20% by weight of epoxy resin adhesive, the thickness of the wave-absorbing film is 50mm, and the magnetic conductivity of the wave-absorbing film is 120 at 1 MHz.
Example 2: as shown in fig. 1, a heat dissipation film layer 11 in the electromagnetic shielding heat dissipation film is a 10um graphite film, the heat conductivity thereof is 1900W/m · k, a shielding film layer 12 is an aluminum foil, the thickness thereof is 40um, a wave absorbing film 13 is a film containing 70% by weight of iron-nickel alloy powder and 30% by weight of epoxy resin adhesive, the thickness thereof is 30mm, and the magnetic permeability thereof is 90 at 1 MHz.
Example 3: as shown in fig. 2, the electromagnetic shielding heat dissipation film includes a heat dissipation film layer 11, a shielding film layer 12 and a wave-absorbing film layer 13, wherein the heat dissipation film layer 11 is a 25um graphite film, the heat conductivity of the graphite film is 1600W/m · k, the shielding film layer 12 is a copper foil, the thickness of the copper foil is 20um, the wave-absorbing film 13 is a film containing 80% by weight of iron-nickel alloy powder and 20% by weight of epoxy resin adhesive, the thickness of the wave-absorbing film is 50mm, and the magnetic conductivity of the wave-absorbing film is 120 at 1 MHz. A25 um PET protective film 14 (polyethylene terephthalate) is attached to the wave-absorbing film 13, a 10um acrylic adhesive double-sided adhesive 15 and a PET release film layer 16 coated with silicone oil on the contact surface are attached to the surface of the graphite film 11, and the thickness is 50 um.
Example 4: as shown in fig. 3, the electromagnetic shielding heat dissipation film includes a heat dissipation film layer 11, a shielding film layer 12 and a wave-absorbing film layer 13, wherein the heat dissipation film layer 11 is a 25um graphite film, the heat conductivity of the graphite film is 1600W/m · k, the shielding film layer 12 is a copper foil, the thickness of the copper foil is 20um, the wave-absorbing film 13 is a film containing 80% by weight of iron-nickel alloy powder and 20% by weight of epoxy resin adhesive, the thickness of the wave-absorbing film is 50mm, and the magnetic conductivity of the wave-absorbing film is 120 at 1 MHz. A 25um PET protective film 14 (polyethylene terephthalate) is attached to the graphite film 11, a 10um acrylic adhesive double-sided adhesive 15 and a silicone oil-coated PET release film layer 16 are attached to the surface of the wave-absorbing film 13, and the thickness is 50 um.
Shielding effectiveness test: the shielding effectiveness (dB) was tested by an Agilent E5061A vector network tester, DN1015 shielding effectiveness testing apparatus, following the ASTM-D-4935 test standard, the results of which are shown in FIGS. 4 and 5. From the test results, the electromagnetic wave shielding effectiveness of example 1 is 96dB on average, and the electromagnetic wave shielding effectiveness of example 1 is 85dB on average in the frequency range of 0-1 GHz.
Thermal conductivity test experiment: the thermal conductivity test was conducted by a relaxation resistant LFA 447 thermal conductivity tester in accordance with ASTM-E-1461 test standard, the results of which are set forth in Table 1. From the test results, the thermal conductivity of example 1 was 1605.317W/m.k, while that of example 2 was 1909.385W/m.k.
The test results of the shielding effectiveness and the heat conductivity show that the high-heat-dissipation wave-absorbing composite film has remarkably excellent electromagnetic shielding and heat dissipation effects compared with a composite material adhered with a heat-conducting film and a wave-absorbing film.
TABLE 1 thermal conductivity test results
| Sample (I) | Ambient temperature (. degree. C.) | Model (model) | Coefficient of thermal diffusion (mm)2/s） | Coefficient of thermal conductivity (W/m. K) |
| Example 1 | 25.0 | In Plan, isotropic | 933.324 | 1605.317 |
| Example 2 | 25.0 | In Plan, isotropic | 1110.108 | 1909.385 |
Example 5: the invention provides a method for manufacturing an electromagnetic shielding heat dissipation film, as shown in fig. 6, the method comprises the following steps:
step 1, using a compound machine to paste a heat dissipation film on a stainless steel sheet with a smooth surface,
step 2, using Chemical Vapor Deposition (CVD) method to use Cu which is a divalent complex of Cu(II)(hfac)2As a precursor, hydrogen gas is used as a carrier gas at 250 deg.CoAnd C, depositing a 10nm metal copper film layer on the graphite heat-conducting film under normal pressure. Then, copper sulfate is taken as electroplating solution, a copper film layer is continuously electroplated and grown on the copper film formed by the CVD method until the thickness of the copper film reaches 25um,
and 3, uniformly mixing the iron-nickel magnetic alloy powder mixed with 80 wt% and the epoxy resin adhesive mixed with 20 wt% in a stirring tank, coating the mixture on the surface of the copper film layer by using a coating machine, and curing to form the wave-absorbing film layer of 50 umm.
And 4, peeling the stainless steel sheet contacted with the graphite film to obtain the electromagnetic shielding heat dissipation film.
When the electromagnetic shielding heat dissipation film is applied, the double-sided adhesive tape can be attached to the graphite film side or the wave absorption film side of the electromagnetic shielding heat dissipation film and is attached to the surface of an electronic element needing heat dissipation and electromagnetic shielding, so that the effects of reducing the temperature of the equipment and preventing electromagnetic interference are achieved.
The electromagnetic shielding heat dissipation film is characterized in that a protective film is attached to one side of a heat dissipation film of the electromagnetic shielding heat dissipation film, a double-faced adhesive tape and a release film are attached to one side of the wave absorption film, after the release film is peeled, one side of the wave absorption film is attached to an electronic device through the double-faced adhesive tape, and the protective film plays a role in protecting the film layer and insulating the electronic device.
The electromagnetic shielding heat dissipation film is characterized in that a protective film is attached to one side of the wave absorption film, a double-faced adhesive tape and a release film are attached to one side of the heat dissipation film, after the release film is peeled, one side of the heat dissipation film is attached to an electronic device through the double-faced adhesive tape, and the protective film has the functions of protecting the film layer and insulating.
The electromagnetic shielding heat dissipation film is characterized in that double-sided adhesive and release films are attached to one side of the wave absorption film and one side of the heat dissipation film, the electromagnetic shielding heat dissipation film is attached to the surface of an electronic device after the release films are peeled, and other functional components can be attached to the outer surface of the electromagnetic shielding heat dissipation film through the double-sided adhesive.
Claims (1)
1. A manufacturing method of an electromagnetic shielding heat dissipation film is characterized by comprising the following steps:
the electromagnetic shielding heat dissipation film comprises a heat dissipation film layer, a shielding film layer and a wave absorbing film layer;
the heat dissipation film layer is a synthetic graphite film, the thickness of the heat dissipation film layer is 10-50 mu m, and the heat conductivity is 800-2000W/m.k;
the shielding film layer is a metal film made of gold, silver, copper, nickel, iron, aluminum, zinc or alloy, the metal film is a single metal film or a metal composite film formed by two or more layers of different metals, and the thickness of the metal composite film is 5nm-50 um;
the wave-absorbing film layer is an organic adhesive film mixed with soft magnetic material powder; the wave absorbing film layer consists of 70-90% of wave absorbing agent and 10-30% of organic binder, the thickness of the wave absorbing film layer is 20um-1mm, and the magnetic conductivity at the frequency of 1MHz is more than 50;
the wave absorber is made of soft magnetic alloy powder and comprises nickel-zinc-iron alloy, nickel-copper-iron alloy, zinc-chromium-iron alloy, manganese-zinc-iron alloy, niobium-zinc-iron alloy, iron-silicon-aluminum alloy, nickel-chromium-iron alloy, niobium-zinc-iron alloy, iron-nickel alloy, iron-aluminum alloy, iron-cobalt alloy, iron-chromium alloy, iron-silicon-nickel alloy, iron-silicon-aluminum-nickel alloy, magnesium-manganese-iron alloy, cobalt-nickel alloy, lithium-manganese alloy or lithium-cadmium-iron alloy;
the organic binder is a high molecular material and comprises phenolic resin, urea resin, epoxy resin, acrylic resin, polyvinyl butyral resin, vinyl acetate and a copolymer thereof, organic silicone rubber resin, polyurethane, rubber resin or a polymer of the organic silicone rubber resin and the polyurethane;
the manufacturing method comprises the following steps:
step 1, attaching a heat dissipation film on a high-temperature resistant film layer with a smooth surface; the high-temperature resistant film is made of a material which does not deform at the temperature of more than 100 ℃;
step 2, depositing a metal film on the surface of the heat dissipation film in the step 1 by a gas phase method or a liquid phase method or a combination method of the two methods;
step 3, coating an organic binder mixed with soft magnetic material powder on the surface of the metal film formed in the step 2 and curing the organic binder at high temperature or under the action of a catalyst;
step 4, stripping the high-temperature-resistant film layer on the surface of the heat dissipation film to obtain the electromagnetic shielding heat dissipation film;
in addition, the first and second substrates are,
one side of the electromagnetic shielding heat dissipation film or one side of the wave absorbing film is attached with a double-sided adhesive tape so as to be attached to an electronic device;
or,
one side of the radiating film of the electromagnetic shielding radiating film is attached with a protective film, one side of the wave-absorbing film is attached with a double-sided adhesive and a release film, after the release film is peeled, one side of the wave-absorbing film is attached to an electronic device through the double-sided adhesive, and the protective film plays a role in protecting the film layer and insulating;
or,
one side of the wave absorbing film of the electromagnetic shielding heat dissipation film is attached with a protective film, one side of the heat dissipation film is attached with a double-sided adhesive and a release film, after the release film is peeled, one side of the heat dissipation film is attached to the electronic device through the double-sided adhesive, and the protective film plays a role in protecting the film layer and insulating;
or,
the electromagnetic shielding heat dissipation film is characterized in that double-sided adhesive and release films are attached to one side of the wave absorption film and one side of the heat dissipation film of the electromagnetic shielding heat dissipation film, the electromagnetic shielding heat dissipation film is attached to the surface of an electronic device after the release films are peeled off, and other functional components can be attached to the outer surface of the electromagnetic shielding heat dissipation film through the double-sided adhesive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410140979.2A CN104981138B (en) | 2014-04-10 | 2014-04-10 | A kind of manufacturing method for being electromagnetically shielded heat dissipation film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410140979.2A CN104981138B (en) | 2014-04-10 | 2014-04-10 | A kind of manufacturing method for being electromagnetically shielded heat dissipation film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104981138A CN104981138A (en) | 2015-10-14 |
| CN104981138B true CN104981138B (en) | 2018-06-15 |
Family
ID=54277069
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410140979.2A Expired - Fee Related CN104981138B (en) | 2014-04-10 | 2014-04-10 | A kind of manufacturing method for being electromagnetically shielded heat dissipation film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104981138B (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI722136B (en) * | 2016-03-29 | 2021-03-21 | 拓自達電線股份有限公司 | Conductive paint and manufacturing method of shielding package body using the same |
| CN106433560A (en) * | 2016-07-27 | 2017-02-22 | 重庆市鸿富诚电子新材料有限公司 | Method for preparing wave absorbing materials by tape casting |
| CN106190022A (en) * | 2016-07-27 | 2016-12-07 | 重庆市鸿富诚电子新材料有限公司 | A kind of absorbing material |
| CN106455442B (en) * | 2016-11-02 | 2019-03-15 | 上海博息电子科技有限公司 | A kind of ultra-thin graphene height leads composite material |
| CN108074821B (en) * | 2016-11-16 | 2022-02-01 | 利诺士尖端材料有限公司 | Graphite sheet for electromagnetic wave shielding and heat dissipation composite sheet, electromagnetic wave shielding and heat dissipation composite sheet comprising same and preparation method thereof |
| CN106531902B (en) * | 2016-11-16 | 2020-12-29 | 广州宏庆电子有限公司 | Ultrathin flexible heat dissipation film and manufacturing method thereof |
| CN110167752B (en) * | 2017-04-07 | 2021-10-15 | 松下知识产权经营株式会社 | Graphite composite film and method for producing same |
| KR101922938B1 (en) * | 2017-09-29 | 2018-11-29 | 일진머티리얼즈 주식회사 | Multi-functional composite sheet having function of controlling electromagnetic wave, thermal radiation, and absorbing impact |
| CN109268902B (en) * | 2018-08-22 | 2020-04-07 | 安徽和邦纺织科技有限公司 | Electromagnetic shielding protective curtain for microwave oven |
| CN109575744B (en) * | 2018-10-19 | 2020-12-08 | 苏州铂韬新材料科技有限公司 | Coating piece with rust-proof wave-absorbing function and preparation method thereof |
| CN109550668B (en) * | 2018-10-19 | 2021-12-28 | 苏州铂韬新材料科技有限公司 | Composite film with three-in-one functions of heat conduction and wave absorption shielding and preparation method thereof |
| CN109608884B (en) * | 2018-11-29 | 2020-09-04 | 深圳先进技术研究院 | Heat-conducting shielding organic silicon material and preparation method thereof |
| CN110446397B (en) * | 2019-06-19 | 2021-02-26 | 京东方科技集团股份有限公司 | Heat dissipation shielding film and application thereof |
| CN110488403A (en) * | 2019-09-04 | 2019-11-22 | 东莞市利锦电子有限公司 | A kind of reflector plate and its processing technology of stainless steel high reflectance |
| CN110845802A (en) * | 2019-10-25 | 2020-02-28 | 昆山汉品电子有限公司 | Manufacturing method of shielding heat dissipation type wave-absorbing material and adhesive tape structure thereof |
| CN111410920A (en) * | 2020-03-23 | 2020-07-14 | 苏州微邦材料科技有限公司 | Wave-absorbing shielding adhesive film and preparation method thereof |
| CN113997647B (en) * | 2020-07-28 | 2024-01-05 | Oppo广东移动通信有限公司 | Composite heat conduction shielding material, preparation method and electronic equipment |
| CN112533465B (en) * | 2020-11-27 | 2023-08-01 | 南昌正业科技有限公司 | Preparation method of electromagnetic wave protective film for FPC |
| CN112867377A (en) * | 2020-12-16 | 2021-05-28 | 苏州驭奇材料科技有限公司 | Heat-conducting wave absorber and preparation method and application thereof |
| CN116997170B (en) * | 2023-07-13 | 2024-04-26 | 苏州铂韬新材料科技有限公司 | A microwave absorbing film and a method for preparing the same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN202603134U (en) * | 2012-05-30 | 2012-12-12 | 苏州沛德导热材料有限公司 | Wave-absorbing graphite flake |
| CN203181498U (en) * | 2013-03-25 | 2013-09-04 | 深圳市跨越电子有限公司 | A graphite film with high thermal conductivity |
| WO2014027673A1 (en) * | 2012-08-16 | 2014-02-20 | 住友ベークライト株式会社 | Em-shielding film and method for covering electronic component |
| CN203537743U (en) * | 2013-10-28 | 2014-04-09 | 朱向忠 | Electromagnetic shielding wave-absorbing heat-conducting film |
| CN103718664A (en) * | 2011-07-26 | 2014-04-09 | 加川清二 | Electromagnetic wave absorption film having high heat dissipation properties |
-
2014
- 2014-04-10 CN CN201410140979.2A patent/CN104981138B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103718664A (en) * | 2011-07-26 | 2014-04-09 | 加川清二 | Electromagnetic wave absorption film having high heat dissipation properties |
| CN202603134U (en) * | 2012-05-30 | 2012-12-12 | 苏州沛德导热材料有限公司 | Wave-absorbing graphite flake |
| WO2014027673A1 (en) * | 2012-08-16 | 2014-02-20 | 住友ベークライト株式会社 | Em-shielding film and method for covering electronic component |
| CN203181498U (en) * | 2013-03-25 | 2013-09-04 | 深圳市跨越电子有限公司 | A graphite film with high thermal conductivity |
| CN203537743U (en) * | 2013-10-28 | 2014-04-09 | 朱向忠 | Electromagnetic shielding wave-absorbing heat-conducting film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104981138A (en) | 2015-10-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104981138B (en) | A kind of manufacturing method for being electromagnetically shielded heat dissipation film | |
| CN204350556U (en) | A kind of electromagnetic shielding heat dissipation film | |
| US11272646B2 (en) | Electromagnetic interference (EMI) shielding film, circuit board, and preparation method for EMI shielding film | |
| US10881039B1 (en) | Electromagnetic interference shielding film, circuit board, and preparation method for electromagnetic interference shielding film | |
| CN102711428B (en) | Ultra-thin shielding film of a kind of high screening effectiveness and preparation method thereof | |
| CN104972708B (en) | One kind inhales the difunctional composite of wave dispersion heat and its manufacture method | |
| CN105007704B (en) | Composite radiating inhales ripple film | |
| CN102286254A (en) | High-peeling-strength conductive adhesive film with through holes and preparation method thereof | |
| US20210161040A1 (en) | Electromagnetic interference shielding film, circuit board, and preparation method for electromagnetic interference shielding film | |
| JP2020510985A (en) | Electromagnetic wave shielding film, its manufacturing method and application | |
| CN101448362A (en) | Ultra-thin shielding film and circuit board capable of changing circuit impedance, and method for preparing same | |
| CN202941075U (en) | Combined-type graphite heat radiation sheet | |
| KR20170076361A (en) | Complex sheets with shielding and absorbing of electromagnetic waves and thermal dissipation, and methods of manufacturing the same | |
| CN209652218U (en) | Nickel plating copper foil shielding tape | |
| CN104972709A (en) | High-heat-dissipation wave-absorbing composite film and manufacturing method thereof | |
| CN105744816B (en) | Electromagnetic wave shielding composite film | |
| CN202030694U (en) | High peel strength conductive glue film with through holes | |
| CN112341972A (en) | Flexible wave-absorbing material and preparation method thereof, wave-absorbing adhesive tape and preparation method thereof | |
| KR102001719B1 (en) | Metal composite sheet | |
| TW201325425A (en) | Electromagnetic wave shielding composited films and flexible printed circuit boards with the composite film | |
| CN113956808A (en) | Copper foil adhesive tape for enhancing signals and manufacturing method thereof | |
| CN203876309U (en) | Wave-absorbing heat-dissipating bi-functional compound device | |
| KR20180135156A (en) | Metal composite and metal tape for shielding electromagnetic wave and electromagnetic radiation | |
| JP7506150B2 (en) | Electromagnetic wave shielding film | |
| KR101546452B1 (en) | EMI shielding film manufactured by electroplating and printed circuit board using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180615 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |