CN101363143A - Nylon 6/ultrafine calcium carbonate particle composite fiber and its preparation method - Google Patents
Nylon 6/ultrafine calcium carbonate particle composite fiber and its preparation method Download PDFInfo
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- CN101363143A CN101363143A CNA2008102004444A CN200810200444A CN101363143A CN 101363143 A CN101363143 A CN 101363143A CN A2008102004444 A CNA2008102004444 A CN A2008102004444A CN 200810200444 A CN200810200444 A CN 200810200444A CN 101363143 A CN101363143 A CN 101363143A
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- nylon
- calcium carbonate
- composite fiber
- ultrafine calcium
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 93
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 49
- 239000000835 fiber Substances 0.000 title claims abstract description 36
- 229920002292 Nylon 6 Polymers 0.000 title claims abstract description 26
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 239000002245 particle Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920001778 nylon Polymers 0.000 claims abstract description 36
- 239000004677 Nylon Substances 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 238000009987 spinning Methods 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000009998 heat setting Methods 0.000 claims abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000000654 additive Substances 0.000 claims abstract description 5
- 239000012756 surface treatment agent Substances 0.000 claims abstract 7
- 239000011859 microparticle Substances 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 8
- 239000007822 coupling agent Substances 0.000 claims description 7
- 238000002074 melt spinning Methods 0.000 claims description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 5
- 235000021355 Stearic acid Nutrition 0.000 claims description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 5
- 239000008117 stearic acid Substances 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- 239000011238 particulate composite Substances 0.000 claims 2
- 230000020169 heat generation Effects 0.000 claims 1
- 150000003014 phosphoric acid esters Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000001035 drying Methods 0.000 abstract description 3
- 238000002844 melting Methods 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000005303 weighing Methods 0.000 abstract description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract 1
- 229910052791 calcium Inorganic materials 0.000 abstract 1
- 239000011575 calcium Substances 0.000 abstract 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 abstract 1
- 239000004753 textile Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 10
- 230000003750 conditioning effect Effects 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Artificial Filaments (AREA)
Abstract
本发明涉及一种尼龙6/超细碳酸钙微粒复合纤维及其制备方法，温度升高至140℃左右，使尼龙软化并使纳米碳酸钙和其它添加剂均匀包粘在尼龙树脂上，而尼龙树脂颗粒间没有严重的粘连。该复合纤维重量组成包括85～100份尼龙切片、0.5～15份超细碳酸钙微粒和0.01～0.5份的表面处理剂；制备：(1)按重量份数称取原料；(2)将碳酸钙微粒和表面处理剂在高速混合机中搅拌混合，加尼龙切片均匀混合，180℃～230℃后停止加热，搅拌冷却，室温出料；(3)干燥后放入螺杆挤出机中进行熔融纺丝，得卷绕丝；(4)将卷绕丝牵伸和热定型处理，得牵伸丝；(5)牵伸丝的后续处理同常规。该纤维有优良力学性能和耐磨性能，可广泛应用于服装和各类产业用纺织品领域。此工艺简单，易控制，成本低，周期短，对环境友好，适于工业化生产。The invention relates to a nylon 6/ultrafine calcium carbonate particle composite fiber and a preparation method thereof. The temperature is raised to about 140° C. to soften the nylon and make nano-calcium carbonate and other additives evenly coated on the nylon resin, and the nylon resin There is no severe adhesion between particles. The weight composition of the composite fiber includes 85-100 parts of nylon chips, 0.5-15 parts of superfine calcium carbonate particles and 0.01-0.5 parts of surface treatment agent; preparation: (1) weighing raw materials by weight parts; (2) mixing carbonic acid Stir and mix the calcium particles and surface treatment agent in a high-speed mixer, add nylon slices and mix evenly, stop heating after 180 ° C ~ 230 ° C, stir and cool, and discharge at room temperature; (3) After drying, put it into a screw extruder for melting Spinning to obtain coiled yarn; (4) drawing and heat-setting the coiled yarn to obtain drawn yarn; (5) the follow-up treatment of drawn yarn is the same as conventional. The fiber has excellent mechanical properties and wear resistance, and can be widely used in the fields of clothing and various industrial textiles. The process is simple, easy to control, low in cost, short in cycle, friendly to the environment and suitable for industrialized production.
Description
Technical field
The invention belongs to the composite fibre field, particularly relate to a kind of nylon 6/ superfine calcium carbonate microparticle complex fiber and preparation method thereof.
Background technology
One of important use of nylon resin is a fiber, is applied to take, all kinds of fabrics for industrial use etc.Higher always because of the nylon market price, therefore, many manufacturers are by the filling-modified cost of raw material that reduces of filler.The polymer/inorganic particle composite is the research focus in material field in recent years, and performances such as its mechanical property, toughness, heat resistance, DIMENSIONAL STABILITY are significantly increased than bulk polymer, and nylon/superfine calcium carbonate microparticle composite is one of them.Studies show that the mechanics of nylon 6/ superfine calcium carbonate microparticle composite, heat-resisting, resistance to compression, anti-solvent, performance such as wear-resisting all obtain raising in various degree, and greatly reduce cost, thereby have improved competitiveness of product.
Current, the research and development of polymer/inorganic particle compound both at home and abroad mainly concentrate on the plastics aspect, and the application of fiber aspect is also less.Chinese patent CN1821307 discloses a kind of method that reduces calcium carbonate granular filling nylon dragon 66 processing temperature of composite material, mix according to specific particle diameter and quality proportioning by calcium carbonate two kinds of different-grain diameters, with special ratios filled nylon-6 6, can obviously reduce the processing temperature of nylon 66, the mechanical performance of gained composite improves more than 30%, also can reach the minimizing energy consumption, the purpose that reduces cost.Chinese patent CN1865546 discloses a kind of polypropylene/clay composite fiber and preparation method thereof, and the fiber that makes has the excellent flame-retardant performance antistatic behaviour.But when nano-calcium carbonate and various property-modifying additive carry out the dry mixed processing usually; it only is a kind of mixing; then this compound is melt extruded the back with twin-screw and become band with a large amount of water quench; use the pelleter granulation; carry out drying after the granulation again; use for following road processing, as Chinese patent application numbers 03126909.5 and 200610034690.8.Obviously have energy consumption height, dust pollution, equipment investment is big, technology is numerous and diverse and because the resin second melting, the shortcoming that nano particle is reunited easily once more.
Summary of the invention
The object of the present invention is to provide a kind of nylon 6/ superfine calcium carbonate microparticle complex fiber and preparation method thereof, utilize the method for mixing heating or adding heating, make the temperature of mixed system be increased to 180 ℃～230 ℃, nylon is softened and nano-calcium carbonate is evenly wrapped with other additive to be bonded on the nylon resin, and do not have serious adhesion between the nylon resin particle.The better performances of this fiber especially has good mechanical, heat-resisting, anti-wear performance, can be widely used in taking and association area such as all kinds of fabrics for industrial use; And its preparation technology is simple, control easily, and production cost is low, and is with short production cycle, environmentally friendly, is specially adapted to suitability for industrialized production.
Nylon 6/ superfine calcium carbonate microparticle complex fiber of the present invention, its weight are formed and are comprised 85～100 parts nylon chips, 0.5～10 part superfine calcium carbonate microparticle and 0.5～1 part surface conditioning agent.
Described nylon chips is spinning level nylon 6 or 66 sections, and its molecular weight is 15500～28000.
The particle diameter of described superfine calcium carbonate microparticle is 0.05～1 μ m, is shaped as spindle, cube, aciculiform, chain or sphere etc.
Described surface conditioning agent is one or more in hard ester acid, titanate coupling agent, aluminate coupling agent, phosphate coupling agent, aluminium titanium composite coupler, the silane coupling agent.
The preparation method of nylon 6/ superfine calcium carbonate microparticle complex fiber of the present invention may further comprise the steps:
(1) takes by weighing 85～100 parts nylon chips, 0.5～15 part superfine calcium carbonate microparticle and 0.01～0.5 part surface conditioning agent by weight;
(2) superfine calcium carbonate microparticle and surface conditioning agent are put into high-speed mixer, the rotating speed of high-speed mixer is 1000～6000r/min, preferred 3000～6000r/min, the time of mixing is 20～30min, add nylon chips again, heat up and continue and stir, utilize the method for mixing heating or adding heating, make the temperature of mixed system be increased to 140 ℃, nylon is softened and nano-calcium carbonate is evenly wrapped with other additive and be bonded on the nylon resin, and do not have serious adhesion that it is mixed between the nylon resin particle, cooling then, discharging;
(3) step (2) gains are put into screw extruder and are carried out melt spinning after the vacuum drying oven intensive drying, and spinning temperature is 260～315 ℃, and spinning speed is 500～2000m/min, makes undrawn yarn;
(4) undrawn yarn is carried out two road drawing-offs under 80～200 ℃ temperature and handle with HEAT SETTING, the drawing-off general times is 3～7 times, thereby makes drafted fibre;
(5) subsequent treatment of drafted fibre makes nylon/superfine calcium carbonate microparticle complex fiber with the fiber production routine techniques.
Beneficial effect of the present invention:
(1) among the present invention pure nylon is carried out spinning, pure fiber of gained and composite fibre are carried out performance relatively, find mechanics, the heat-resistant antifriction better performances of composite fibre, and by adding filler, greatly reduce the production cost of nylon fiber, to promoting that suitability for industrialized production is significant;
(2) have stronger shearing force than traditional to be mixed into main axial flow impeller owing to employing in the super mixer is cut into main peripheral flow impeller, can more effectively carry out surface treatment calcium carbonate microparticle;
(3) adding of stearic acid surface conditioning agent has suitably reduced surface activity of particles, promotes that calcium carbonate microparticle is evenly dispersed on the nylon chips more;
(4) adding of calcium carbonate has strengthened the fracture strength and the modulus of nylon fiber, has reduced the elongation at break of nylon, reduces greatly but excessive calcium carbonate adds fashionable its apparent viscosity that causes, and crystallization nucleation is also had certain influence, so its performance also decreases.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.Calcium carbonate microparticle and surface conditioning agent and nylon chips keep stirring down and heat up, and temperature is controlled between 205～240 ℃, are heated to and determine to stop heating after the temperature, continue to stir and cooling, to the room temperature discharging, treat spinning;
Embodiment 1
The surface conditioning agent stearic acid of 1 part superfine calcium carbonate microparticle and 0.02 part is put into high-speed mixer, rotating speed is 1000r/min, mix 25min, the nylon 6 slice that adds 99 parts again, keep stirring down and heat up, when temperature reaches 145 ℃, stop heating, continue to stir and cooling, to the room temperature discharging.Obtained compound is vacuumize 4h under 90 ℃ temperature, then mixture is put into double screw extruder, under 280 ℃, carry out melt spinning, spinning speed is 700m/min, undrawn yarn is two road drawing-off and HEAT SETTING between 95 ℃ through hot drawing temperature, the total draft multiple is 3 times, thereby obtains finished silk.
Embodiment 2
The surface conditioning agent stearic acid of 3 parts superfine calcium carbonate microparticles and 0.06 part is put into high-speed mixer, rotating speed is 3000r/min, mix 20min, the nylon 66 slice that adds 97 parts again, keep stirring down and heat up, when temperature reaches 145 ℃, stop heating, continue to stir and cooling, to the room temperature discharging.Obtained compound is vacuumize 4h under 90 ℃ temperature, then mixture is put into screw extruder, under 310 ℃, carry out melt spinning, spinning speed is 700m/min, undrawn yarn is two road drawing-off and HEAT SETTING between 210 ℃ through hot drawing temperature, the total draft multiple is 6 times, thereby obtains finished silk.
Embodiment 3
The surface conditioning agent stearic acid of 5 parts superfine calcium carbonate microparticles and 0.1 part is put into high-speed mixer, rotating speed is 3000r/min, mix 20min, the nylon 6 slice that adds 95 parts again, keep stirring down and heat up, when temperature reaches 145 ℃, stop heating, continue to stir and cooling, to the room temperature discharging.Obtained compound is vacuumize 4h under 90 ℃ temperature, then mixture is put into screw extruder, under 280 ℃, carry out melt spinning, spinning speed is 700m/min, undrawn yarn is two road drawing-off and HEAT SETTING between 95 ℃ through hot drawing temperature, the total draft multiple is 3 times, thereby obtains finished silk.
Embodiment 4
The surface conditioning agent odium stearate of 10 parts superfine calcium carbonate microparticles and 0.2 part is put into high-speed mixer, rotating speed is 4000r/min, mix 30min, the nylon 6 slice that adds 90 parts again, keep stirring down and heat up, when temperature reaches 145 ℃, stop heating, continue to stir and cooling, to the room temperature discharging.Obtained compound is vacuumize 4h under 90 ℃ temperature, then mixture is put into screw extruder, under 285 ℃, carry out melt spinning, spinning speed is 700m/min, undrawn yarn is two road drawing-off and HEAT SETTING between 105 ℃ through hot drawing temperature, the total draft multiple is 3 times, thereby obtains finished silk.
Comparative Examples
Select 100 parts of spinning level nylon 6 sections for use, vacuumize 6h under 100 ℃ temperature.Then screw extruder is put in section, directly pure nylon 6 is carried out spinning, spinning temperature is 270 ℃, and spinning speed is 600m/min.Undrawn yarn is two road drawing-off and HEAT SETTING between 90 ℃ through hot drawing temperature, and the total draft multiple is 2.5 times, obtains finished silk.
Obtained nylon 6/ superfine calcium carbonate microparticle complex fiber performance of the present invention and the contrast of Comparative Examples performance are as shown in table 1.
The table 1 nylon 6/ superfine calcium carbonate microparticle complex fiber performance table of comparisons
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102004444A CN101363143B (en) | 2008-09-25 | 2008-09-25 | Nylon 6/ultrafine calcium carbonate particle composite fiber and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102004444A CN101363143B (en) | 2008-09-25 | 2008-09-25 | Nylon 6/ultrafine calcium carbonate particle composite fiber and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101363143A true CN101363143A (en) | 2009-02-11 |
| CN101363143B CN101363143B (en) | 2011-04-27 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2008102004444A Expired - Fee Related CN101363143B (en) | 2008-09-25 | 2008-09-25 | Nylon 6/ultrafine calcium carbonate particle composite fiber and its preparation method |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102808235A (en) * | 2011-05-31 | 2012-12-05 | 上海杰事杰新材料(集团)股份有限公司 | Corrosion resisting polyamide hollow fiber film and preparation method thereof |
| CN104153029A (en) * | 2014-08-21 | 2014-11-19 | 南通美铭锦纶有限公司 | Ultrafine polyamide 6 filament |
| CN104562274A (en) * | 2014-06-30 | 2015-04-29 | 巢湖市翔宇渔具有限公司 | Processing method of fishing net thread |
| CN104775179A (en) * | 2015-03-20 | 2015-07-15 | 巢湖市荷花渔网有限公司 | Processing method of high-toughness fishing net line |
| CN104775176A (en) * | 2015-03-20 | 2015-07-15 | 巢湖市瑞强渔具有限责任公司 | High-performance fishing net line |
| CN106661767A (en) * | 2014-07-01 | 2017-05-10 | 欧米亚国际集团 | Multifilament polyester fibres |
| CN107201571A (en) * | 2017-06-30 | 2017-09-26 | 苏州广能电子科技有限公司 | A kind of console dustproof fiber beam |
| CN113289597A (en) * | 2021-06-17 | 2021-08-24 | 清华大学 | Fiber carrier-based supported catalyst, preparation method thereof and indoor air purification device |
| CN114045595A (en) * | 2021-11-02 | 2022-02-15 | 广东鹏运实业有限公司 | Antistatic and anti-electromagnetic radiation composite fabric and preparation method thereof |
-
2008
- 2008-09-25 CN CN2008102004444A patent/CN101363143B/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102808235A (en) * | 2011-05-31 | 2012-12-05 | 上海杰事杰新材料(集团)股份有限公司 | Corrosion resisting polyamide hollow fiber film and preparation method thereof |
| CN102808235B (en) * | 2011-05-31 | 2015-05-20 | 上海杰事杰新材料(集团)股份有限公司 | Corrosion resisting polyamide hollow fiber film and preparation method thereof |
| CN104562274A (en) * | 2014-06-30 | 2015-04-29 | 巢湖市翔宇渔具有限公司 | Processing method of fishing net thread |
| CN106661767A (en) * | 2014-07-01 | 2017-05-10 | 欧米亚国际集团 | Multifilament polyester fibres |
| CN104153029A (en) * | 2014-08-21 | 2014-11-19 | 南通美铭锦纶有限公司 | Ultrafine polyamide 6 filament |
| CN104775179A (en) * | 2015-03-20 | 2015-07-15 | 巢湖市荷花渔网有限公司 | Processing method of high-toughness fishing net line |
| CN104775176A (en) * | 2015-03-20 | 2015-07-15 | 巢湖市瑞强渔具有限责任公司 | High-performance fishing net line |
| CN107201571A (en) * | 2017-06-30 | 2017-09-26 | 苏州广能电子科技有限公司 | A kind of console dustproof fiber beam |
| CN113289597A (en) * | 2021-06-17 | 2021-08-24 | 清华大学 | Fiber carrier-based supported catalyst, preparation method thereof and indoor air purification device |
| CN114045595A (en) * | 2021-11-02 | 2022-02-15 | 广东鹏运实业有限公司 | Antistatic and anti-electromagnetic radiation composite fabric and preparation method thereof |
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| CN101363143B (en) | 2011-04-27 |
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