CN101255246B - Antistatic thermo-shrinkage material and manufacturing method thereof - Google Patents
Antistatic thermo-shrinkage material and manufacturing method thereof Download PDFInfo
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- CN101255246B CN101255246B CN2007100748277A CN200710074827A CN101255246B CN 101255246 B CN101255246 B CN 101255246B CN 2007100748277 A CN2007100748277 A CN 2007100748277A CN 200710074827 A CN200710074827 A CN 200710074827A CN 101255246 B CN101255246 B CN 101255246B
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- 239000000463 material Substances 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 229920003023 plastic Polymers 0.000 claims abstract description 31
- 239000004033 plastic Substances 0.000 claims abstract description 31
- 239000006229 carbon black Substances 0.000 claims abstract description 23
- 239000000314 lubricant Substances 0.000 claims abstract description 20
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 12
- 238000004132 cross linking Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 230000007613 environmental effect Effects 0.000 claims abstract description 4
- 238000000465 moulding Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 13
- 239000003112 inhibitor Substances 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- -1 Zinic stearas Chemical compound 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 8
- 230000005855 radiation Effects 0.000 claims description 8
- 229910052793 cadmium Inorganic materials 0.000 claims description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 6
- 229920001971 elastomer Polymers 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 6
- 229910052753 mercury Inorganic materials 0.000 claims description 6
- 238000007670 refining Methods 0.000 claims description 6
- 239000005060 rubber Substances 0.000 claims description 6
- 238000007493 shaping process Methods 0.000 claims description 6
- 229920001897 terpolymer Polymers 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 235000019359 magnesium stearate Nutrition 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-OUBTZVSYSA-N Cobalt-60 Chemical compound [60Co] GUTLYIVDDKVIGB-OUBTZVSYSA-N 0.000 claims description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 abstract description 8
- 230000008602 contraction Effects 0.000 abstract description 6
- 238000009825 accumulation Methods 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 229920002943 EPDM rubber Polymers 0.000 abstract 2
- 239000003963 antioxidant agent Substances 0.000 abstract 2
- 230000003078 antioxidant effect Effects 0.000 abstract 2
- 238000003723 Smelting Methods 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 229920005672 polyolefin resin Polymers 0.000 description 4
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 235000019260 propionic acid Nutrition 0.000 description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 3
- 230000002285 radioactive effect Effects 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
The invention discloses a method for producing an anti-static thermal contraction material, comprising the following steps: 1. sufficiently smelting, mixing and granulating, by weight part, 80 parts of ethylene-vinyl acetate copolymer, 20 parts of ethylene propylene diene monomer, 12-20 parts of carbon black, 0.3-1.0 part of antioxidant, 0.5-1.5 parts of plastic processing lubricant; 2. extruding and moulding into pipes or sheet; 3. expanding after radiating and crosslinking the moulded pipes or sheet in step 2, rapidly cooling and setting to obtain the environmental anti-static thermal contraction material. The invention also provides the anti-static thermal contraction material, comprising the component and content according to weight part: 80 parts of ethylene-vinyl acetate copolymer, 20 parts of ethylene propylene diene monomer; 12-20 parts of carbon black, 0.3-1.0 part of antioxidant, 0.5-1.5 parts of plastic processing lubricant. The inventive anti-static thermal contraction material has smaller resistivity, can prevent electrostatic generation and accumulation, and has contractive characteristic during heating.
Description
Technical field
The present invention relates to a kind of heat-shrinkage material and manufacture method thereof with anti-electrostatic, this heat-shrinkage material has less surface resistivity (10
6-11Ω), can prevent that electrostatic from producing and accumulation, the situation in heating can have the characteristic of contraction simultaneously.
Background technology
The conventional plastic material and the surface resistivity of heat-shrinkage material all than higher (greater than 10
12Ω), belong to insulating material, use the coating material of this type of material, usually produce a large amount of high pressure static electricitys on the surface of plastic material and material contracting with heat as electronic product, when this high pressure static electricity is dealt with improperly, will produce electric shock to the electronic product of packaging and damage.
In order to protect electronic product, need to use the wrapping material with electrostatic-proof function, its surface resistivity 10
6-11Ω.Many antistatic packaging materials are arranged at present on the market, as Chinese patent application number 01130781.1 disclosed a kind of antistatic polyolefine film, it is having fast firmly coating and the use occasion that is connected, because often adopt tackiness agent as coating and the fixed form that is connected, and in reality often because of the caking agent ageing failure, cause solid failure, can't give full play to its effect.
Heat-shrinkage material has easy to use, fast, characteristics such as firmly effective, but be not specifically designed to heat-shrinkage material with permanently antistatic purposes, be to use a kind of coating of anti-electrostatic as the disclosed reinforced insulation pyrocondensation belt of Chinese patent ZL99206447.3, because cementability is bad each other for coating and heat-shrink tube surface, coating takes place easily come off in pyrocondensation process and use and cause the anti-static effect variation.
Summary of the invention
The technical problem that will solve of the present invention is: overcome and stick with glue the problem that agent fixed antistatic film comes off easily on traditional antistatic packaging material, and anti-static coating comes off easily and makes the problem of anti-static effect difference, provides a kind of and has the less resistive rate, prevents generation of static electricity and good antistatic thermo-shrinkage material and the manufacture method thereof of accumulation effect.
In order to solve the problems of the technologies described above, the present invention proposes following technical scheme: a kind of manufacture method of anti-electrostatic material contracting with heat, may further comprise the steps: step 1: with 80 parts of content ethylene-vinyl acetate copolymers by weight, 20 parts of terpolymer EP rubbers, carbon black 12-20 part, oxidation inhibitor 0.3-1.0 part, plastic working lubricant 0.5-1.5 part, fully melting mixing granulation; Step 2: be extrusion-molded into tubing or sheet material; Step 3: the tubing or the sheet material of step 2 moulding are expanded with the crosslinked back of high-energy electron irradiation, and cooling and shaping obtains the environmental protection antistatic thermo-shrinkage material fast.
Preferably, in the step 1 with open refining plastics machine or Banbury mixer or twin-screw mixer machine mixing granulator.
Preferably, use the single screw extrusion machine extrusion moulding in the step 2.
Preferably, in the step 3 with high-energy electron with the 10-25Mrad cross-linking radiation, or the energetic ray of emitting with radioelement cobalt Co60 is with the 100-250KGY cross-linking radiation.
Preferably, the material of cross-linking radiation at 80-200 ℃ of expansion 2-5 doubly.
In order to solve the problems of the technologies described above, the present invention also proposes following technical scheme: a kind of antistatic thermo-shrinkage material, and its component and content are:
80 parts of ethylene-vinyl acetate copolymers;
20 parts of terpolymer EP rubbers;
Carbon black 12-20 part;
Oxidation inhibitor 0.3-1.0 part;
Plastic working lubricant 0.5-1.5 part;
Its content by weight.
Preferably, this carbon black is not leaded, cadmium, mercury and chromic amorphous carbon powder.
Preferably, the mixture of one or more that this plastic working lubricant is following material: stearic acid, Zinic stearas, calcium stearate, Magnesium Stearate, polyethylene wax, this plastic working lubricant is not leaded, cadmium, mercury and sexavalent chrome.
The present invention has following beneficial effect: this heat-shrinkage material is antistatic film or coat anti-static coating fixedly, this heat-shrinkage material itself has the function of anti-electrostatic, this heat-shrinkage material has less resistivity, can prevent that electrostatic from producing and accumulation, the situation in heating can have the characteristic of contraction simultaneously.
Description of drawings
Fig. 1 is the schema of the manufacture method of antistatic thermo-shrinkage material of the present invention.
Embodiment
The present invention proposes a kind of antistatic thermo-shrinkage material, and its component and content are: 100 parts in ethylene-vinyl acetate copolymer and terpolymer EP rubber mixture; Carbon black 12-20 part; Oxidation inhibitor 0.3-1.0 part; Plastic working lubricant 0.5-1.5 part; Its consumption by weight.
This carbon black is not leaded, cadmium, mercury and chromic amorphous carbon powder.
The mixture of one or more that this plastic working lubricant is following material: stearic acid, Zinic stearas, calcium stearate, Magnesium Stearate, polyethylene wax, this plastic working lubricant is not leaded, cadmium, mercury and sexavalent chrome.
See also Fig. 1, the manufacture method of above-mentioned anti-electrostatic material contracting with heat may further comprise the steps:
Step 1: with open refining plastics machine or Banbury mixer or twin-screw mixer machine with the described ethylene-vinyl acetate copolymer and the abundant melting mixing granulation of terpolymer EP rubber mixture, carbon black, oxidation inhibitor and plastic working lubricant of metering in proportion;
Step 2: the material that is extruded into tubing, sheet material or other shapes with single screw extrusion machine;
Step 3: with the material of step 2 moulding through radioelement cobalt Co
60With the 10-25Mrad cross-linking radiation, the material of cross-linking radiation is 2-5 times of 80-200 ℃ of expansion with high-energy electron for energetic ray of emitting or high-energy electron accelerator, and cooling and shaping obtains the environmental protection antistatic thermo-shrinkage material fast.
Embodiment one:
Take polyolefin resin and adopt polyethylene (PE), 100 parts; Carbon black, 12 parts; Oxidation inhibitor four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester (be commonly called as: 1010), 1 part; The plastic working lubricant adopts Zinic stearas, 1.5 parts;
With open refining plastics machine or Banbury mixer or twin-screw mixer machine with the described abundant melting mixing granulation of polyolefin resin, carbon black, oxidation inhibitor and plastic working lubricant of metering in proportion;
With the above-mentioned master batch that mixes, be extruded into tubing with conventional plastics single screw extrusion machine, with high-energy electron accelerator or radioelement cobalt Co with certain internal diameter and wall thickness
60The high energy radioactive rays of emitting are heated to 150 ℃ with tubing earlier according to (about 10Mrad or 100KGY) behind the doses, make bore become greater to original 2.5 times with inside and outside differential pressure, and cooling and shaping can obtain heat-shrink tube fast, and this heat-shrink tube surface resistivity is 10
9-10Ω has the function of anti-electrostatic.
Embodiment two:
Take 80 parts of ethylene-vinyl acetate copolymer EVA (VA content 14-18%), 20 parts in ethylene-propylene rubber(EPR); Carbon black, 20 parts; Oxidation inhibitor four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester (be commonly called as: 1010), 0.3 part; The plastic working lubricant adopts Zinic stearas, 0.5 part;
With open refining plastics machine or Banbury mixer or twin-screw mixer machine with the described abundant melting mixing granulation of polyolefin resin, carbon black, oxidation inhibitor and plastic working lubricant of metering in proportion;
With the above-mentioned master batch that mixes, be extruded into sheet material with conventional plastics single screw extrusion machine, with high-energy electron accelerator or radioelement cobalt Co with certain width and thickness
60The high energy radioactive rays of emitting are according to (about 10Mrad or 100KGY) behind the doses, earlier sheet material is heated to 150 ℃, with mechanical force sheet material is stretched to both sides, make its width internal diameter become greater to original 2.5 times, quick cooling and shaping, can obtain having the sheet material of pyrocondensation function, this pyrocondensation sheet surface resistance is 10
6-7Ω has the function of anti-electrostatic.
Embodiment three:
Take 80 parts of ethylene-vinyl acetate copolymer EVA (VA content 14-18%), 20 parts in ethylene-propylene rubber(EPR); Carbon black, 12.5 parts; Oxidation inhibitor four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester (be commonly called as: 1010), 0.5 part; The plastic working lubricant adopts Zinic stearas, 1 part;
With open refining plastics machine or Banbury mixer or twin-screw mixer machine with the described abundant melting mixing granulation of polyolefin resin, carbon black, oxidation inhibitor and plastic working lubricant of metering in proportion;
With the above-mentioned master batch that mixes, be extruded into sheet material with conventional plastics single screw extrusion machine, with high-energy electron accelerator or radioelement cobalt Co with certain width and thickness
60The high energy radioactive rays of emitting are according to (about 10Mrad or 100KGY) behind the doses, earlier sheet material is heated to 150 ℃, with mechanical force sheet material is stretched to both sides, make its width internal diameter become greater to original 2.5 times, quick cooling and shaping, can obtain having the sheet material of pyrocondensation function, this pyrocondensation sheet surface resistance is 10
9-10Ω has the function of anti-electrostatic.
After macromolecular material was filled with carbon black, carbon fiber and graphite etc., the volume specific resistance of material was 10
2-10
9Ω .cm.Wherein carbon black filled is main flow, and carbon black filled type conduction material can be used widely, and its reason is that material price such as carbon black is cheap, and carbon black materials can have bigger choice according to different electroconductibility demands in addition, and the sheet resistance value of its goods can be 10
6-10
11Change in the broad range between the Ω, last, high temperature resistant because carbon black has stable chemical properties, anti-irradiation, acid and alkali-resistance, anti-solvent, the effect of its anti-electrostatic can stablize and keep, and has and prevents electrical quiet lasting, stable effect.
Claims (8)
1. the manufacture method of an anti-electrostatic material contracting with heat, it is characterized in that: this manufacture method may further comprise the steps:
Step 1: with 80 parts of content ethylene-vinyl acetate copolymers by weight, 20 parts of terpolymer EP rubbers, carbon black 12-20 part, oxidation inhibitor 0.3-1.0 part, plastic working lubricant 0.5-1.5 part, fully melting mixing granulation;
Step 2: be extrusion-molded into tubing or sheet material;
Step 3: the tubing or the sheet material of step 2 moulding are expanded with the crosslinked back of high-energy electron irradiation, and cooling and shaping obtains the environmental protection antistatic thermo-shrinkage material fast.
2. according to the manufacture method of the described anti-electrostatic material contracting with heat of claim 1, it is characterized in that: in the step 1 with open refining plastics machine or Banbury mixer or twin-screw mixer machine mixing granulator.
3. according to the manufacture method of the described anti-electrostatic material contracting with heat of claim 1, it is characterized in that: use the single screw extrusion machine extrusion moulding in the step 2.
4. according to the manufacture method of the described anti-electrostatic material contracting with heat of claim 1, it is characterized in that: in the step 3 with high-energy electron with the 10-25Mrad cross-linking radiation, or the energetic ray of emitting with radioelement cobalt Co60 is with the 100-250KGY cross-linking radiation.
5. according to the manufacture method of claim 1 or 4 described anti-electrostatic material contracting with heats, it is characterized in that: the material of cross-linking radiation at 80-200 ℃ of expansion 2-5 doubly.
6. antistatic thermo-shrinkage material, its component and content are:
80 parts of ethylene-vinyl acetate copolymers;
20 parts of terpolymer EP rubbers;
Carbon black 12-20 part;
Oxidation inhibitor 0.3-1.0 part;
Plastic working lubricant 0.5-1.5 part;
Its content by weight.
7. antistatic thermo-shrinkage material according to claim 6 is characterized in that: this carbon black is not leaded, cadmium, mercury and chromic amorphous carbon powder.
8. antistatic thermo-shrinkage material according to claim 6, it is characterized in that: the mixture of one or more that this plastic working lubricant is following material: stearic acid, Zinic stearas, calcium stearate, Magnesium Stearate, polyethylene wax, this plastic working lubricant is not leaded, cadmium, mercury and sexavalent chrome.
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| CN2007100748277A CN101255246B (en) | 2007-06-06 | 2007-06-06 | Antistatic thermo-shrinkage material and manufacturing method thereof |
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| CN2007100748277A CN101255246B (en) | 2007-06-06 | 2007-06-06 | Antistatic thermo-shrinkage material and manufacturing method thereof |
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| CN101701090B (en) * | 2009-10-28 | 2011-11-02 | 江苏达胜热缩材料有限公司 | High-pressure flame retardant single-wall heat-shrinkable pipe and preparation method thereof |
| CN101696294B (en) * | 2009-10-28 | 2011-09-14 | 江苏达胜热缩材料有限公司 | Semi-conducting high-voltage fire retardant single-wall heat-shrinkable tube and preparation method thereof |
| CN101701092B (en) * | 2009-10-28 | 2011-08-31 | 江苏达胜热缩材料有限公司 | Semiconductor high-pressure single-wall heat-shrinkable tube and preparation method thereof |
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| CN103739969A (en) * | 2013-12-16 | 2014-04-23 | 江苏开源环保技术工程有限公司 | Rubber slab with anticorrosion lining special for sodium hypochlorite |
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| CN104212049B (en) * | 2014-08-26 | 2016-06-01 | 大连欧思特科技有限公司 | A kind of heat-shrink tube and preparation method and the application in LED filament encapsulation |
| CN104530543A (en) * | 2014-12-17 | 2015-04-22 | 大连联合高分子材料有限公司 | Halogen-free environmental-friendly flame-retardant bus-bar insulating heat-shrinkable bushing and preparation method thereof |
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Effective date of registration: 20180328 Address after: 523770 Guangdong province Dongguan city Dalang town Fumin Industrial Park Po Po Industrial Zone two Co-patentee after: Changyuan electronic (Group) Co., Ltd. Patentee after: Changyuan Electronics (Dongguan) Co., Ltd. Co-patentee after: Shanghai Changyuan Electronic Material Co., Ltd. Co-patentee after: Tianjin Changyuan Electronic Material Co., Ltd. Address before: 523770 Guangdong province Dongguan city Dalang town Fumin Industrial Park Po Po Industrial Zone two Co-patentee before: Changyuan electronic (Group) Co., Ltd. Patentee before: Changyuan Electronics (Dongguan) Co., Ltd. Co-patentee before: Shanghai Changyuan Electronic Material Co., Ltd. Co-patentee before: Tianjin Changyuan Electronic Material Co., Ltd. Co-patentee before: ChangYuan Group Ltd. |
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