CN102378560A - Film having electromagnetic shielding effect and manufacturing method thereof - Google Patents
Film having electromagnetic shielding effect and manufacturing method thereof Download PDFInfo
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- CN102378560A CN102378560A CN2010102564570A CN201010256457A CN102378560A CN 102378560 A CN102378560 A CN 102378560A CN 2010102564570 A CN2010102564570 A CN 2010102564570A CN 201010256457 A CN201010256457 A CN 201010256457A CN 102378560 A CN102378560 A CN 102378560A
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- epoxy resin
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- resin composite
- release
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Abstract
The invention relates to a film, which comprises a release type substrate layer and an epoxy resin composite material layer. The release type substrate layer has a first release type surface and the epoxy resin composite material layer is formed on the first release type surface. And the epoxy resin composite material layer is formed by an epoxy resin composite material that comprises an epoxy resin modified by carboxyl end group polymer, a carbon nano tube and an inorganic dispersion material. Besides, the mass percent of the carbon nano tube accounts for 4.6% to 16% of that of the epoxy resin composite material; and the viscosity of the epoxy resin composite material is from 60000 centipoises to 75000 centipoises. In addition, the invention provides a manufacturing method for the film.
Description
Technical field
The present invention relates to the circuit board technology field, relate in particular to and a kind ofly be applied to board production and have film of electromagnetic shielding action and preparation method thereof.
Background technology
Along with progress of science and technology, the application widely that printed circuit board (PCB) obtains at electronic applications.Application about circuit board sees also document Takahashi, A.Ooki, N.Nagai, A.Akahoshi; H.Mukoh, A.Wajima, M.Res.Lab; High density multilayer printed circuit board for HITAC M-880, IEEE Trans.on Components, Packaging; And Manufacturing Technology, 1992,15 (4): 418-425.
Along with the circuit board product number of plies increases, circuit board product tends to produce the electromagnetic interference phenomenon when real work, influences circuit board signal and transmits.Like this, in circuit board product, electro-magnetic screen layer need be set.At present, the electro-magnetic screen layer of employing adopts the less stainless steel substrates of thickness to make usually, stainless steel substrates is arranged on the coverlay on surface of circuit board product, thereby plays the effect of electromagnetic shielding.Yet the weight of stainless steel substrates is bigger, thereby has increased the weight of circuit board product.And the flexility of stainless steel substrates is relatively poor, and the electro-magnetic screen layer that adopts stainless steel substrates to make influences the flexible PCB performance of destroying or force to yield.Because the price of stainless steel substrates is higher, increased the production cost of circuit board.
Summary of the invention
Therefore, be necessary to provide a kind of film and preparation method thereof, said film can be applied to circuit board to play electromagnetic shielding action.
Below will a kind of film with electromagnetic shielding action and preparation method thereof be described with embodiment.
A kind of film, it comprises release substrate layer and epoxy resin composite material layer.Said release substrate layer has first release surface, and said epoxy resin composite material layer is formed on said first release surface.Said epoxy resin composite material layer is made up of epoxy resin composite material.Said epoxy resin composite material comprises epoxy resin, CNT and the inorganic dispersion of end carboxyl polymer modification, and said CNT shared mass percent in said epoxy resin composite material is 4.6% to 16%.The viscosity of said epoxy resin composite material is 60000 centipoise to 75000 centipoises.
A kind of manufacture method of film comprises step: adopt the end carboxyl polymer that epoxy resin is carried out modification to obtain holding the epoxy resin of carboxyl polymer modification; Even carbon nanotube is scattered in the inorganic dispersion, to obtain the CNT dispersion; The epoxy resin of said end carboxyl polymer modification is mixed with the CNT dispersion and grinds dispersion, and to obtain epoxy resin composite material, said CNT is 4.6% to 16% in the shared mass percent of said epoxy resin composite material; Release substrate layer is provided, and said release substrate layer has first release surface; First release surface of said epoxy resin composite material being coated insulated base material layer forms the epoxy resin composite material layer; And with said epoxy resin composite material layer semi-solid preparation.
Than prior art; The film that the present technique scheme provides; It comprises the epoxy resin composite material layer; Have finely dispersed CNT in the said epoxy resin composite material layer and have electromagnetic shielding action, said film can directly fit in the surface of circuit board with it or be arranged in the internal layer of multilayer circuit board, and said film has the effect of electromagnetic shielding.Than stainless steel substrates of the prior art, can increase the performance of destroying or force to yield of flexible PCB, and can reduce the production cost of circuit board.The manufacture method of the film that the present technique scheme provides can simply be produced the film with electromagnetic shielding action.
Description of drawings
Fig. 1 is the cutaway view of the film that provides of present technique scheme implementation mode.
Fig. 2 is the cutaway view of the release substrate layer that provides of present technique scheme implementation example.
Fig. 3 is the cutaway view after release substrate layer surface forms the epoxy resin composite material layer that present technique scheme implementation example provides.
The main element symbol description
Epoxy resin composite material layer 120
Embodiment
Film with electromagnetic shielding action that the present technique scheme is provided below in conjunction with embodiment and preparation method thereof further specifies.
See also Fig. 1, the present technique scheme provides a kind of film 100, and it comprises release substrate layer 110, epoxy resin composite material layer 120 and the release separator 130 that stacks gradually.
Epoxy resin composite material layer 120 is used to play electromagnetic shielding action.The power of the electromagnetic interference that the thickness of epoxy resin composite material layer 120 can shield is according to actual needs set.Epoxy resin composite material layer 120 is arranged between second release surface 131 of first release surface 111 and release separator 130 of release substrate layer 110, and its thickness is about 8 microns to 25 microns.Epoxy resin composite material layer 120 is a semi-cured state.Epoxy resin composite material in the epoxy resin composite material layer 120 comprises epoxy resin, CNT, inorganic dispersion, curing agent, catalyst, solvent and the antifoaming agent of end carboxyl polymer modification.
The epoxy resin of said end carboxyl polymer modification is the product behind epoxy resin and the end carboxyl polymer generation copolymerization; To be the terminal epoxy radicals of epoxy resin react with the carboxyl of the end of end carboxyl polymer and generate an ester group, thereby obtain comprising the polymer of the epoxy resin repetitive alternately and the repetitive of end carboxyl polymer.Wherein, epoxy resin can be bisphenol A type epoxy resin, and the end carboxyl polymer can be liquid polybutadiene acrylonitrile (CTBN).In the present embodiment, the epoxide equivalent of the epoxy resin of employing before unmodified is 180 to 195, is preferably 188, and the oxygen equivalent of going back of the epoxy resin after the carboxyl polymer modification is 323 to 352, is preferably 337.The mass percent of epoxy resin in epoxy resin composite material of end carboxyl polymer modification is about 55% to 65%, preferably is about 60%.
CNT is as electric conducting material, and it is dispersed in the epoxy resin of end carboxyl polymer modification, to play electromagnetic shielding action.CNT shared mass percent in composite material is 4.6% to 16%.How many electric conductivities that can obtain composite material according to actual needs of the content of CNT are confirmed in the composite material.The content of CNT is many more in the epoxy resin composite material, and the resistance of epoxy resin composite material is more little, and the content of CNT is few more in the composite material, and the resistance of epoxy resin composite material is big more.
Inorganic dispersion is used for dispersing Nano carbon tubes, so that CNT can be uniformly distributed in the epoxy resin composite material.Said inorganic dispersion is nanoclay or nano mica powder.Said nanoclay is 2: 1 a phyllosilicate, and it specifically can (Montmorillonite, molecular formula be M for montmorillonite
x(Al
4-xMg
x) Si
8O
20(OH)
4), (Hectorite, molecular formula is M to hectorite
x(Mg
6-xLi
x) Si
8O
20(OH)
4) or saponite (Saponite, molecular formula is M
xMg
6(Si
8-xAl
x) O
20(OH)
4) etc.Wherein, CNT is 8 to 12 to 1 with the mass ratio of inorganic dispersion.Said inorganic dispersion is preferably the nano mica powder.
Said curing agent is used for composite material is played induration.In the present embodiment, the curing agent of employing is dicyandiamide (Dicyandiamine), and said curing agent is about 5% in the shared mass percent of epoxy resin composite material.The consumption of curing agent should be corresponding with the epoxy resin of end carboxyl polymer modification, and the epoxy resin of its middle-end carboxyl polymer modification is about 13 to 14 to 1 with the mass ratio of curing agent.
Said catalyst is 2-undecyl imidazole (2-Undecylimidazole), and the content of catalyst is corresponding each other with the content of the epoxy resin of end carboxyl polymer modification.Catalyst shared quality percentage composition in epoxy resin composite material is about 0.5% to 1%, is preferably 0.65%.Said solvent is diethylene glycol ether acetate alone (Diethylene glycol monoethyl ether acetate), and the content of said solvent in epoxy resin composite material is about 20% to 25%, is preferably 24%.This solvent is used to dissolve above-mentioned other components, to form uniform liquid dispersed system.Said antifoaming agent is used for eliminating the foam of above-mentioned epoxy resin composite material, and the mass percent of said antifoaming agent in epoxy resin composite material is about 2%.Said antifoaming agent can be the 2183H antifoaming agent of the pure political affairs in commercially available Taiwan company production.
Preferably; In the epoxy resin composite material, the quality percentage composition of the epoxy resin of end carboxyl polymer modification is about 60.3%, and the quality percentage composition of CNT is about 7.8%; The quality percentage composition of inorganic dispersion is about 0.6%; The quality percentage composition of curing agent is about 4.5%, the quality percentage composition of catalyst is about 0.65%, and the quality percentage composition of solvent is about 24.3%, and the quality percentage composition of antifoaming agent is about 1.85%.Inorganic dispersion is selected mica powder for use.The viscosity of the epoxy resin composite material in the present embodiment can reach 60000 to 75000 centipoises, its can be easily with circuit board in coverlay or other glue-line bonding each other.Preferably, the viscosity of epoxy resin composite material is about 70000 centipoises.
The present technique scheme also provides a kind of said manufacture method with film 100 of electromagnetic shielding action, and said manufacture method comprises the steps:
The first step is made said epoxy resin composite material.
Stating epoxy resin composite material in the present embodiment can adopt following method to make:
At first, adopt end carboxyl polymer modified epoxy to obtain holding the epoxy resin of carboxyl polymer modification.
To hold carboxyl polymer and epoxy resin to be positioned over jointly and be positioned in the reaction vessel, and to keep reaction temperature be 120 degrees centigrade that reaction is about 3 hours under stirring condition, thereby obtain holding epoxy resin after the carboxyl polymer modification.In the present embodiment, the epoxy resin of employing is bisphenol A type epoxy resin, and its epoxide equivalent is 188.The end carboxyl polymer that adopts can be liquid polybutadiene acrylonitrile (CTBN), and the epoxide equivalent of the epoxide resin after the modification that obtains after the reaction is 337.Through above-mentioned reaction, a terminal epoxy radicals of epoxy resin mutually combines with a terminal carboxyl of end carboxyl polymer, and removes the water of a molecule, thereby obtains an ester group.Thereby than the epoxy resin that does not carry out modification, the epoxy resin after the modification has good flexibility.Certainly, the epoxy resin of employing is not limited to the bisphenol A type epoxy resin that present embodiment provides, and it also can be the epoxy resin of other types.The end carboxyl polymer that adopts also is not limited to the liquid polybutadiene acrylonitrile that provides in the present embodiment, and it also can be polymer such as terminal carboxyl polyester.
Then, even carbon nanotube is scattered in the inorganic dispersion to form finely dispersed CNT dispersion.
Adopt physics mode that CNT is scattered in the inorganic dispersion.Said inorganic dispersion can be laminar nano clay or mica powder.In the present embodiment, the inorganic dispersion of selecting for use is the laminar nano clay.Configuration quality is than 8 to 1 to 12 to 1 CNT and laminar nano clay, and through stirring or the mode of concussion is mixed, makes even carbon nanotube be scattered in the layered nanoclay.The laminar nano clay that adopts can be 2: 1 phyllosilicate, and it specifically can be montmorillonite, hectorite or saponite etc.The CNT that adopts can be SWCN, also can be multi-walled carbon nano-tubes.
At last, epoxy resin, CNT dispersion, solvent, curing agent, catalyst and the antifoaming agent of end carboxyl polymer modification mixed and grind dispersion, thereby obtain epoxy resin composite material.
In the present embodiment, adopt three drum-types to grind dispersion machine described end carboxyl polymer modified epoxy, CNT dispersion, solvent, curing agent, catalyst and antifoaming agent are ground dispersion.Above-mentioned end carboxyl polymer modified epoxy, CNT dispersion, solvent, curing agent, catalyst and antifoaming agent are devoted three drum-types according to above-mentioned content separately to be ground in the dispersion machine; Start three drum-types and grind dispersion machine to grind dispersion; Thereby make above-mentioned each form in the solid uniform ingredients be scattered in the liquid component, thereby form finely dispersed epoxy resin composite material.In the present embodiment; In above-mentioned each composition, the quality percentage composition of the epoxy resin of end carboxyl polymer modification is about 60.3%, and the quality percentage composition of CNT is about 7.8%; The quality percentage composition of inorganic dispersion is about 0.6%; The quality percentage composition of curing agent is about 4.5%, the quality percentage composition of catalyst is about 0.65%, and the quality percentage composition of solvent is about 24.3%, and the quality percentage composition of antifoaming agent is about 1.85%.
In order to obtain the epoxy resin composite material of different surfaces resistivity, the consumption of CNT dispersion is controlled in the time of can feeding intake through change.The mass percent that accounts for composite material when CNT is between 4.6% to 16%, and epoxy resin composite material surface resistivity constant interval is about between 100,000 ohm to ten ohm.Wherein, the content of CNT is big more in the epoxy resin composite material, and the surface resistivity of epoxy resin composite material is more little.
Through the epoxy resin composite material that said method is made, its viscosity can reach 70000 centipoises, and outward appearance presents black, and is faint reflective.Amplify under 100 times of observations no hole at microscope.And have good attachment characteristic and a scolding tin characteristic, and can acid and alkali resistance and the corrosion of solvent.When temperature is 25 degrees centigrade, be that 10% hydrochloric acid or quality percentage composition are to soak 0.5 hour in 10% the sodium hydroxide solution, all do not have peeling phenomenon at the quality percentage composition.In acetone, soak and carry out hundred lattice after 17 hours and adhere to test, also do not have peeling phenomenon.
See also Fig. 2, in second step, release substrate layer 110 is provided.
In the present embodiment, release substrate layer 110 is the PET mould release membrance, and it has first release surface 111.
See also Fig. 3, in the 3rd step, said epoxy resin composite material is coated first release surface 111 to form epoxy resin composite material layer 120.
In the present embodiment, adopt slit type coater that the epoxy resin composite material of liquid state is coated first release surface 111 of release substrate layer 110, to form epoxy resin composite material layer 120.In the present embodiment owing to adopt slit type coater to be coated with, the thickness that can control the epoxy resin composite material layer 120 of formation meet the demands and coating even.In the present embodiment, the thickness of the epoxy resin composite material layer 120 of formation is 8 microns to 25 microns, is preferably 10 to 20 microns.Epoxy resin composite material layer 120 has the first surface 121 away from release substrate layer 110.
In the 4th step, the epoxy resin composite material layer 120 that coating on first release surface 111 of release substrate layer 110 forms is handled, so that epoxy resin composite material layer 120 semi-solid preparation.
In the present embodiment, the method that epoxy resin composite material layer 120 semi-solid preparation adopt is that prebake conditions is handled.
The time that continues epoxy resin composite material layer 120 being carried out prebake conditions is about 15 minutes, and the temperature that keeps during prebake conditions is about 80 degrees centigrade to 90 degrees centigrade.Handle through carrying out prebake conditions, make that the partial solvent in the epoxy resin composite material layer 120 volatilizees, make epoxy resin composite material layer 120 be in semi-cured state.
It is understandable that; Carrying out the temperature of prebake conditions duration and baking can confirm according to the thickness of the epoxy resin composite material layer 120 of reality; When epoxy resin composite material layer 120 thickness are big, can time proper extension or temperature that handle suitably be heightened, and when epoxy resin composite material layer 120 thickness hour; Can suitable shortening of the time of handling or temperature suitably be reduced, can form the semi-solid preparation membrane structure to guarantee epoxy resin composite material layer 120.
Please consult Fig. 3 and Fig. 1 in the lump, the 5th step, the release separator 130 of on the first surface 121 of epoxy resin composite material layer 120, fitting.
The release separator 130 of fitting is used in storage and transportation epoxy resin composite material layer 120 being protected.Release separator 130 can be release PET film, and it can be various release liners.Release separator 130 has second release surface, 131, the second release surface 131 and fits each other with the first surface 121 of epoxy resin composite material layer 120.When the film 100 of making formation directly is used for circuit board making, the release separator 130 of on the first surface 121 of epoxy resin composite material layer 120, also can not fitting.
After this step, can further include film 100 is cut, film 100 is made into the shape that needs, use with convenient.When the film 100 that making forms is not directly used, can film 100 be positioned over storage under the low temperature environment, the temperature of storage can be approximately 5 degrees centigrade.When film 100 is applied to circuit board making, can the release separator 130 of film 100 be removed, then epoxy resin composite material layer 120 directly is pressed on the surface of the coverlay of the circuit board that is formed with the conducting wire, to play the effect of electromagnetic shielding.And release substrate layer 110 separated with epoxy resin composite material layer 120.The film 100 that the present technique scheme provides also can be formed between the two adjacent insulating barriers of multilayer circuit board, to play electromagnetic shielding action.
The film that the present technique scheme provides; It comprises the epoxy resin composite material layer; Have finely dispersed CNT in the said epoxy resin composite material layer and have electromagnetic shielding action; Said film can directly fit in the surface of circuit board with it or be arranged in the internal layer of multilayer circuit board, and said film has the effect of electromagnetic shielding.Than stainless steel substrates of the prior art, can increase the performance of destroying or force to yield of flexible PCB, and can reduce the production cost of circuit board.The manufacture method of the film that the present technique scheme provides can simply be produced the film with electromagnetic shielding action.
It is understandable that, for the person of ordinary skill of the art, can make other various corresponding changes and distortion by technical conceive according to the present invention, and all these change the protection range that all should belong to claim of the present invention with distortion.
Claims (10)
1. film; It comprises release substrate layer and epoxy resin composite material layer; Said release substrate layer has first release surface; Said epoxy resin composite material layer is formed at said first release surface, and said epoxy resin composite material layer is made up of epoxy resin composite material, and said epoxy resin composite material comprises epoxy resin, CNT and the inorganic dispersion of end carboxyl polymer modification; Said CNT is 4.6% to 16% in the shared mass percent of said epoxy resin composite material, and the viscosity of said epoxy resin composite material is 60000 centipoise to 75000 centipoises.
2. film as claimed in claim 1 is characterized in that, the epoxy resin of said end carboxyl polymer modification is the bisphenol A type epoxy resin of liquid polybutadiene acrylonitrile modification.
3. film as claimed in claim 1 is characterized in that, the mass percent of epoxy resin in epoxy resin composite material of said end carboxyl polymer modification is 55% to 65%.
4. film as claimed in claim 1 is characterized in that, said inorganic dispersion is nanoclay or nano mica powder.
5. film as claimed in claim 1 is characterized in that, said CNT is 8 to 12 to 1 with the mass ratio of inorganic dispersion.
6. film as claimed in claim 1 is characterized in that, the thickness of said epoxy resin composite material layer is 8 microns to 25 microns.
7. film as claimed in claim 1 is characterized in that said film also comprises release separator, and said release separator has second release surface, and said second release surface and epoxy resin composite material layer are in contact with one another away from the surface of release substrate layer.
8. the manufacture method of a film comprises step:
Adopt the end carboxyl polymer that epoxy resin is carried out modification to obtain holding the epoxy resin of carboxyl polymer modification;
Even carbon nanotube is scattered in the inorganic dispersion, to obtain the CNT dispersion;
The epoxy resin of said end carboxyl polymer modification is mixed with the CNT dispersion and grinds dispersion, and to obtain epoxy resin composite material, said CNT is 4.6% to 16% in the shared mass percent of said epoxy resin composite material;
Release substrate layer is provided, and said release substrate layer has first release surface;
First release surface of said epoxy resin composite material being coated insulated base material layer forms the epoxy resin composite material layer; And
With said epoxy resin composite material layer semi-solid preparation.
9. the manufacture method of film as claimed in claim 8 is characterized in that, said epoxy resin composite material adopts slit type coater to coat first release surface of insulated base material layer, and the thickness of said epoxy resin composite material layer is 8 microns to 25 microns.
10. the manufacture method of film as claimed in claim 8; It is characterized in that; The fit step of release separator of the surface that the manufacture method of said film also is included in the said epoxy resin composite material layer of semi-solid preparation; Said release separator has second release surface, and said epoxy resin composite material layer fits between second release surface of first release surface and release separator of said release substrate layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010256457.0A CN102378560B (en) | 2010-08-18 | 2010-08-18 | Film having electromagnetic shielding effect and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010256457.0A CN102378560B (en) | 2010-08-18 | 2010-08-18 | Film having electromagnetic shielding effect and manufacturing method thereof |
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| Publication Number | Publication Date |
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| CN102378560A true CN102378560A (en) | 2012-03-14 |
| CN102378560B CN102378560B (en) | 2015-05-20 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000208984A (en) * | 1999-01-13 | 2000-07-28 | Toray Ind Inc | Electromagnetic wave shielding material and manufacture thereof |
| CN101163390A (en) * | 2007-11-29 | 2008-04-16 | 中国航空工业第一集团公司北京航空材料研究院 | Method of producing carbon nano-tube nonwoven cloth electromagnetic shielding composite material |
| CN101578009A (en) * | 2008-05-06 | 2009-11-11 | 富葵精密组件(深圳)有限公司 | Circuit board base film, circuit board substrate and circuit board |
| CN101613517A (en) * | 2008-06-27 | 2009-12-30 | 联茂电子股份有限公司 | The resin prepreg body is formed glue, heat radiation film and manufacture method thereof |
-
2010
- 2010-08-18 CN CN201010256457.0A patent/CN102378560B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000208984A (en) * | 1999-01-13 | 2000-07-28 | Toray Ind Inc | Electromagnetic wave shielding material and manufacture thereof |
| CN101163390A (en) * | 2007-11-29 | 2008-04-16 | 中国航空工业第一集团公司北京航空材料研究院 | Method of producing carbon nano-tube nonwoven cloth electromagnetic shielding composite material |
| CN101578009A (en) * | 2008-05-06 | 2009-11-11 | 富葵精密组件(深圳)有限公司 | Circuit board base film, circuit board substrate and circuit board |
| CN101613517A (en) * | 2008-06-27 | 2009-12-30 | 联茂电子股份有限公司 | The resin prepreg body is formed glue, heat radiation film and manufacture method thereof |
Non-Patent Citations (2)
| Title |
|---|
| MARIA D.M.SALINAS-RUIZ ETAL.: "rubber-toughened epoxy loaded with carbon nanotubes:structure-property relationships", 《J MATER SCI》 * |
| 梅启林等: "多壁碳纳米管-有机蒙脱土协同增韧环氧树脂", 《复合材料学报》 * |
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Address after: Guangdong city of Shenzhen province Baoan District Songgang street Chuanyan Luo Lu Yan Co-patentee after: Peng Ding Polytron Technologies Inc Patentee after: Peng Ding Holdings (Shenzhen) Limited by Share Ltd Address before: 518000 Guangdong city of Shenzhen province Baoan District Songgang streets Yan Chuanyan Luzhen Luo Ding Technology Park plant A1 building to building A3 Co-patentee before: Peng Ding Polytron Technologies Inc Patentee before: Fuku Precision Components (Shenzhen) Co., Ltd. |
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