CN104278349A - Antistatic and flame retardant copolyester fiber and preparation method thereof - Google Patents
Antistatic and flame retardant copolyester fiber and preparation method thereof Download PDFInfo
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- CN104278349A CN104278349A CN201310275288.9A CN201310275288A CN104278349A CN 104278349 A CN104278349 A CN 104278349A CN 201310275288 A CN201310275288 A CN 201310275288A CN 104278349 A CN104278349 A CN 104278349A
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- adipic acid
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Abstract
The invention belongs to the technical field of polymer materials, and relates to an antistatic and flame retardant copolyester fiber and a preparation method thereof. The copolyester fiber comprises the following components by weight: 100 parts of polybutylene terephthalate/ polybutylene adipate, 1-5 parts of polyethylene glycol, 0.2-1.3 parts of an antistatic agent, 2-10 parts of a phosphorus based flame retardant and 0.1-4 parts of inorganic nano powder. The antistatic and flame retardant copolyester fiber has the strength no less than 2.58cN / dtex and the elongation at about 30%, is soft in hand feeling and good in antistatic property, flame retardant properties and mechanical properties, and has the widespread application prospect.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of polyester fiber and preparation method thereof.
Background technology
Polyester fiber is the synthetic fiber that output is maximum in the world at present, and have excellent combination property and wide application prospect, but polyester fiber is a kind of hydrophobic fiber, the specific insulation under the status of criterion reaches 10
13more than Ω cm, easily produces electrostatic, and belongs to Flammable fibers, and these reasons limit the Application Areas of polyester fiber.
Japan Patent JP47-36459 relates to and a kind ofly adopts the fiber being added in aliphatic alcohol polyethenoxy phosphate and obtaining in polyester resin, though its antistatic behaviour has persistent form, effect is bad.Chinese patent 20110071051.X discloses a kind of preparation method of flame-retardant anti-dripping copolyester fibers, inorganic clay is dispersed in water copolymerization again after the lamella of nano-scale.The method has the defect being difficult to overcome, and is unfavorable for large-scale industrial production.Chinese patent CN200410072375.5 discloses a kind of manufacture method of multi-functional PET staple fibre, there is fire retardant-antistatic composite multifunction PET cut into slices by adding phosphorus flame retardant and inorganic antistatic agent copolymerization in polyester polymerization process, the polyester staple fiber with composite multifunction is spun into again by this kind of section, but the bad control of its building-up process.
The present invention, by polyester and phosphorus flame retardant, antistatic additive co-blended spinning, makes the fiber with complex function, thus expands the purposes of this fibrous material.Simultaneously in melt spinning process of the present invention by lengthening cooling distance, thus effectively improve in Direct-spinning of PET Fiber process and not easily cool, easily the problem of bonding, also improves the combination property of material simultaneously.
Summary of the invention
The object of the invention is to the defect for overcoming prior art and copolyester fiber of a kind of anti-flammability and antistatic property and preparation method thereof is provided.
The present invention is directed to poly terephthalic acid/adipic acid fourth diester polyester fiber to carry out modification, make it have good combination property, widen its Application Areas, and method is simple, easy to operate, conventional terylene spinning equipment can be used, do not need particular purchased and transformation.
To achieve these goals, the present invention is by the following technical solutions:
A kind of copolyester fiber, be made up of the component comprising following weight portion:
The structural formula of described poly terephthalic acid/adipic acid fourth diester is:
Described poly-adipic acid/butylene terephthalate is random copolymerization, is made up of above-mentioned two repetitives, wherein, and 1≤x≤50,1≤y≤50.
Described molecular weight polyethylene glycol is 5000-20000.
Described antistatic additive is anionic antistatic agents, and be preferably the antistatic additive containing organic sulfonic acid salt, general formula is (R-SO
3)
nm, wherein R is C
8-C
18straight chained alkyl or alkyl phenyl, M is alkali metal or alkaline-earth metal ions, be preferably Na, K or Mg etc., n is 1 or 2.
Described antistatic additive is neopelex, pentadecyl sulfonic acid sodium or sodium stearyl sulfonate, preferred neopelex.
Neopelex is in white or pale yellow powder or graininess, and its molecular structural formula is:
Described fire retardant be selected from 2-hydroxyethylbenzene phosphoric acid, 2-hydroxyethyl methyl phosphate, 2-hydroxyethyl methyl phosphoric acid or two (p-carboxy phenyl) phenyl phosphine oxide (BCPPO) one or more, the structural formula of its correspondence is:
Described inorganic nanometer powder is one or more in nano level silica, calcium carbonate or magnesium carbonate or barium sulfate.
A preparation method for above-mentioned copolyester fiber, comprises the following steps:
(1) poly terephthalic acid/adipic acid fourth diester, polyethylene glycol are carried out vacuumize respectively, make its moisture content be less than 200ppm;
(2) 100 parts of poly terephthalic acids/adipic acid fourth diester, 1-5 part polyethylene glycol, 0.2-1.3 part anionic antistatic agents 2-10 part phosphorus flame retardant, 0.1-4 part inorganic nanometer powder are carried out blended 3-10min, melt spinning is carried out through screw type spinning machine, after cooling, carry out oiling, preliminary draft, winding process, obtain the copolyester fiber that even structure, fiber number are controlled;
(3) copolyester fiber obtained in step (2) is carried out drawing-off processing, obtain antistatic-fire retardation copolyester fiber.
The spinning temperature of described step (2) is 250-290 DEG C, and spinning speed is 800-1200m/min.
In described step (3), the processing multiplying power of traction processing is 1.5-3.5, and volume speed is 300-800m/min, and processing temperature is 60-90 DEG C, wherein processes multiplying power and refers to draft ratio.
A preparation method for above-mentioned copolyester fiber, comprises following steps:
A 50 parts of poly terephthalic acids/adipic acid fourth diester, 1-5 part polyethylene glycol, 2-10 part phosphorus flame retardant and 0.1-4 part inorganic nanometer powder are extruded through double screw extruder by (), granulation, obtain polyethylene glycol/poly terephthalic acid adipic acid fourth two ester blend;
B polyethylene glycol that poly terephthalic acid/adipic acid fourth diester, step (1) obtain by ()/poly terephthalic acid adipic acid fourth two ester blend carries out vacuumize, and after dry, moisture is less than 200ppm;
Get dry poly terephthalic acid/adipic acid fourth diester 50 parts, polyethylene glycol/poly terephthalic acid/adipic acid fourth two ester blend, anionic antistatic agents 0.2-1.3 part carries out blended 3-10min, melt spinning is carried out through screw type spinning machine, after cooling, carry out oiling, preliminary draft, winding process, obtain the copolyester fiber that even structure, fiber number are controlled;
C the fiber obtained in step (b) is carried out drawing-off processing by (), obtain antistatic-fire retardation copolyester fiber.
In described step (a), the extrusion temperature of double screw extruder is 120-170 DEG C.
The spinning temperature of described step (b) is 250-290 DEG C, and spinning speed is 800-1200m/min.
In described step (c), the multiplying power of traction processing is 1.5-3.5, and volume speed is 300-800m/min, and drawing-off processing temperature is 60-90 DEG C.
Compared with prior art, the present invention has the following advantages:
The antistatic behaviour fire-retardant polyester fibre obtained in the present invention has elasticity, the fabric processed has the advantages such as good antistatic property, anti-flammability, heat resistance, washing resistance, soft, can with cotton, wool fibre blending, and there is good biological degradability.This preparation method is pollution-free, flow process is short, efficiency is high, quality is good, method is simple, is easy to suitability for industrialized production; By lengthening cooling distance, effectively improving the problem of strand bonding in spinning process, obtaining fibrous material of good performance; Nano material simultaneously in polyester and fire retardant produce cooperative effect, reduce polyester fiber when burning because of injury that molten drop causes.
Accompanying drawing explanation
Fig. 1 is the structural representation implementing spinning machine of the present invention
Accompanying drawing marks:
1 hopper, 2 screw rods,
3 casings, 4 measuring pumps,
5 spinneretss, 6 lengthen distance cooling,
7 boundling oiling devices, 8 take up rolls.
specific implementation method
Below in conjunction with specific embodiment, further illustrate the present invention.The structural formula of the poly terephthalic acid in the following example/adipic acid fourth diester is:
poly-adipic acid/butylene terephthalate is random copolymerization, is made up of above-mentioned two repetitives, wherein, and 1≤x≤50,1≤y≤50; Molecular weight polyethylene glycol is 5000-20000.
Embodiment 1
(1) poly terephthalic acid/adipic acid fourth diester, polyethylene glycol (molecular weight is 5000) are carried out vacuumize respectively, moisture is less than 200ppm;
(2) by the 100 parts of poly terephthalic acids/adipic acid fourth diester after step (1) drying process, 1 part of polyethylene glycol, 0.2 part of neopelex, 2 parts of 2-hydroxyethylbenzene phosphoric acid, 0.1 part of silica carries out blended 3min, double screw extruder is entered successively by hopper 1, enter the casing 3 of filament spinning component through melt pipe after melt extruding under the effect of screw rod 2, measured by measuring pump 4, extruded by spinnerets 5 successively, cooling zone 6 cools, boundling oiling device 7 oils, take up roll 8 carries out preliminary draft and winding process, obtain even structure, the copolyester fiber that fiber number is controlled.Wherein, spinning temperature is 250 DEG C, and spinning speed is 800m/min; Its fibre strength is 1.53cN/dtex, and degree of stretching is 140.6%, soft;
(3) fiber obtained in step (2) is carried out drawing-off processing, obtain antistatic-fire retardation copolyester fiber.Wherein, processing multiplying power is 1.5, and volume speed is 300m/min, and drawing-off processing temperature is 60 DEG C.
The copolyester fiber good spinnability that the present embodiment is obtained, the volume resistivity of fiber about 10 after drawing-off
9Ω cm, limited oxygen index is 27.5, and intensity is 2.62cN/dtex, and feel is more soft.
Embodiment 2
(1) poly terephthalic acid/adipic acid fourth diester, polyethylene glycol (molecular weight is 10000) are carried out vacuumize, moisture is less than 200ppm;
(2) by the 100 parts of poly terephthalic acids/adipic acid fourth diester after step (1) drying process, 2 parts of polyethylene glycol, 0.8 part of pentadecyl sulfonic acid sodium, 5 parts of 2-hydroxyethyl methyl phosphates, 1 part of calcium carbonate carries out blended 5min, double screw extruder is entered successively by hopper 1, enter the casing 3 of filament spinning component through melt pipe after melt extruding under the effect of screw rod 2, measured by measuring pump 4, extruded by spinnerets 5 successively, cooling zone 6 cools, boundling oiling device 7 oils, take up roll 8 carries out preliminary draft and winding process, obtain even structure, the biodegradable polyester fiber that fiber number is controlled.Wherein, spinning temperature is 260 DEG C, and spinning speed is 1000m/min.Its fibre strength is 1.41cN/dtex, and degree of stretching is 152.3%, soft.
(3) fiber obtained in step (2) is carried out drawing-off processing, obtain antistatic-fire retardation copolyester fiber.Wherein processing multiplying power is 1.8, and volume speed is 400m/min, and drawing-off processing temperature is 75 DEG C.
The copolyester fiber good spinnability that the present embodiment is obtained, the volume resistivity of fiber about 10 after drawing-off
9Ω cm, limited oxygen index is 29, and intensity is 2.84cN/dtex, and feel is more soft.
Embodiment 3
(1) 50 parts of poly terephthalic acids/adipic acid fourth diester, 3 parts of polyethylene glycol (molecular weight is 15000), 4 parts of 2-hydroxyethyl methyl phosphoric acid and 2 parts of barium sulfate are extruded through double screw extruder, granulation, obtain polyethylene glycol/poly terephthalic acid/adipic acid fourth two ester blend, processing temperature is 140 DEG C;
(2) polyethylene glycol/poly terephthalic acid/adipic acid fourth two ester blend that 50 parts of poly terephthalic acids/adipic acid fourth diester, step (1) obtain is carried out vacuumize, moisture is less than 200ppm.Get dried 50 parts of poly terephthalic acids/adipic acid fourth diester and polyethylene glycol/poly terephthalic acid adipic acid fourth two ester blend, 1.0 parts of neopelexes carry out blended 8min, double screw extruder is entered successively by hopper 1, enter the casing 3 of filament spinning component through melt pipe after melt extruding under the effect of screw rod 2, measured by measuring pump 4, extruded by spinnerets 5 successively, cooling zone 6 cools, boundling oiling device 7 carries out oiling, take up roll 8 carries out preliminary draft and winding process, obtain the copolyester fiber that even structure, fiber number are controlled.Wherein, spinning temperature is 270 DEG C, and spinning speed is 1200m/min.Its fibre strength is 1.48cN/dtex, and degree of stretching is 161.5%, soft.
(3) fiber obtained in step (2) is carried out drawing-off processing, obtain antistatic-fire retardation copolyester fiber.Wherein, processing multiplying power is 2.0, and volume speed is 600m/min, and drawing-off processing temperature is 70 DEG C.
The copolyester fiber good spinnability that the present embodiment is obtained, the volume resistivity of fiber about 10 after drawing-off
9Ω cm, limited oxygen index is 30.5, and intensity is 3.10cN/dtex, and feel is more soft.
Embodiment 4
(1) 50 parts of poly terephthalic acids/adipic acid fourth diester, 5 parts of polyethylene glycol (molecular weight is 20000), 7 parts of two (p-carboxy phenyl) phenyl phosphine oxides and 2 parts of calcium carbonate, 2 parts of magnesium carbonate are extruded through double screw extruder, granulation, obtain polyethylene glycol/poly terephthalic acid adipic acid fourth two ester blend, processing temperature is 120 DEG C;
(2) polyethylene glycol/poly terephthalic acid/adipic acid fourth two ester blend that 50 parts of poly terephthalic acids/adipic acid fourth diester, step (1) obtain is carried out vacuumize respectively, moisture is less than 200ppm; Get dried 50 parts of poly terephthalic acids/adipic acid fourth diester and polyethylene glycol/poly terephthalic acid/adipic acid fourth two ester blend, 0.6 part of neopelex carry out blended 10min, double screw extruder is entered successively by hopper 1, enter the casing 3 of filament spinning component through melt pipe after melt extruding under the effect of screw rod 2, measured by measuring pump 4, extruded by spinnerets 5 successively, cooling zone 6 cools, boundling oiling device 7 carries out oiling, take up roll 8 carries out preliminary draft and winding process, obtain the copolyester fiber that even structure, fiber number are controlled.Wherein, spinning temperature is 280 DEG C, and spinning speed is 1100m/min.Its fibre strength is 1.85cN/dtex, and degree of stretching is 146.4%, soft.
(3) fiber obtained in step (2) is carried out drawing-off processing, obtain antistatic-fire retardation copolyester fiber.Wherein, processing multiplying power is 2.2, and volume speed is 700m/min, and drawing-off processing temperature is 80 DEG C.
The copolyester fiber good spinnability that the present embodiment is obtained, the volume resistivity of fiber about 10 after drawing-off
9Ω cm, limited oxygen index is 31, and intensity is 3.49cN/dtex, and feel is more soft.
Embodiment 5
(1) 50 parts of poly terephthalic acids/adipic acid fourth diester, 4 parts of polyethylene glycol (molecular weight is 18000), 4 parts of 2-hydroxyethylbenzene phosphoric acid, 6 parts of 2-hydroxyethyl methyl phosphates and 2.5 parts of silica are extruded through double screw extruder, granulation, obtain polyethylene glycol/poly terephthalic acid/adipic acid fourth two ester blend, processing temperature is 170 DEG C;
(2) polyethylene glycol/poly terephthalic acid/adipic acid fourth two ester blend that 50 parts of poly terephthalic acids/adipic acid fourth diester, step (1) obtain is carried out vacuumize respectively, moisture is less than 200ppm; Get dried 50 parts of poly terephthalic acids/adipic acid fourth diester and polyethylene glycol/poly terephthalic acid/adipic acid fourth two ester blend, 1.3 parts of sodium stearyl sulfonate carry out blended 6min, double screw extruder is entered successively by hopper 1, enter the casing 3 of filament spinning component through melt pipe after melt extruding under the effect of screw rod 2, measured by measuring pump 4, extruded by spinnerets 5 successively, cooling zone 6 cools, boundling oiling device 7 carries out oiling, take up roll 8 carries out preliminary draft and winding process, obtain the biodegradable polyester fiber that even structure, fiber number are controlled.Wherein, spinning temperature is 290 DEG C, and spinning speed is 900m/min.Its fibre strength is 1.50cN/dtex, and degree of stretching is 155.2%, soft.
(3) fiber obtained in step (2) is carried out drawing-off processing, obtain antistatic-fire retardation copolyester fiber.Wherein, processing multiplying power is 3.5, and volume speed is 800m/min, and drawing-off processing temperature is 90 DEG C.
The copolyester fiber good spinnability that the present embodiment is obtained, the volume resistivity of fiber about 10 after drawing-off
9Ω cm, limited oxygen index is 32, and intensity is 3.35cN/dtex, and feel is more soft.
Known by above embodiment result, the present invention obtain antistatic-fire retardation copolyester fiber, its volume resistivity is all 10
9Ω about cm, limited oxygen index is all more than 27, and intensity>=2.58cN/dtex, and soft, has good antistatic behaviour, fire resistance and mechanical property, be with a wide range of applications.
Above-mentioned is can understand and apply the invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.
Claims (10)
1. a copolyester fiber, is characterized in that: be made up of the component comprising following weight portion:
2. copolyester fiber according to claim 1, is characterized in that: the structural formula of described poly terephthalic acid/adipic acid fourth diester is:
Described poly-adipic acid/butylene terephthalate is random copolymerization, is made up of above-mentioned two repetitives, wherein, and 1≤x≤50,1≤y≤50.
3. copolyester fiber according to claim 1, is characterized in that: described molecular weight polyethylene glycol is 5000-20000.
4. copolyester fiber according to claim 1, is characterized in that: described antistatic additive is anionic antistatic agents, and be preferably the antistatic additive containing organic sulfonic acid salt, general formula is (R-SO
3)
nm, wherein R is C
8-C
18straight chained alkyl or alkyl phenyl, M is alkali metal or alkaline-earth metal ions, be preferably Na, K or Mg etc., n is 1 or 2.
5. the copolyester fiber according to claim 1 or 4, is characterized in that: described antistatic additive is neopelex, pentadecyl sulfonic acid sodium or sodium stearyl sulfonate.
6. the copolyester fiber according to claim 1 or 4, is characterized in that: described fire retardant be selected from 2-hydroxyethylbenzene phosphoric acid, 2-hydroxyethyl methyl phosphate, 2-hydroxyethyl methyl phosphoric acid or two (p-carboxy phenyl) phenyl phosphine oxide one or more;
Or described inorganic nanometer powder is one or more in nano level silica, calcium carbonate or magnesium carbonate or barium sulfate.
7. the preparation method of arbitrary described copolyester fiber in claim 1-6, is characterized in that: comprise the following steps:
(1) poly terephthalic acid/adipic acid fourth diester, polyethylene glycol are carried out vacuumize respectively, make its moisture content be less than 200ppm;
(2) 100 parts of poly terephthalic acids/adipic acid fourth diester, 1-5 part polyethylene glycol, 0.2-1.3 part anionic antistatic agents 2-10 part phosphorus flame retardant, 0.1-4 part inorganic nanometer powder are carried out blended 3-10min, melt spinning is carried out through screw type spinning machine, after cooling, carry out oiling, preliminary draft, winding process, obtain the copolyester fiber that even structure, fiber number are controlled;
(3) copolyester fiber obtained in step (2) is carried out drawing-off processing, obtain antistatic-fire retardation copolyester fiber.
8. preparation method according to claim 7, is characterized in that: the spinning temperature of described step (2) is 250-290 DEG C, and spinning speed is 800-1200m/min;
Or the processing multiplying power of traction processing in described step (3) is 1.5-3.5, volume speed is 300-800m/min, and processing temperature is 60-90 DEG C, wherein processes multiplying power and refers to draft ratio.
9. the preparation method of arbitrary described copolyester fiber in claim 1-6, is characterized in that: comprise following steps:
A 50 parts of poly terephthalic acids/adipic acid fourth diester, 1-5 part polyethylene glycol, 2-10 part phosphorus flame retardant and 0.1-4 part inorganic nanometer powder are extruded through double screw extruder by (), granulation, obtain polyethylene glycol/poly terephthalic acid adipic acid fourth two ester blend;
B polyethylene glycol that poly terephthalic acid/adipic acid fourth diester, step (1) obtain by ()/poly terephthalic acid adipic acid fourth two ester blend carries out vacuumize, and after dry, moisture is less than 200ppm;
Get dry poly terephthalic acid/adipic acid fourth diester 50 parts, polyethylene glycol/poly terephthalic acid/adipic acid fourth two ester blend, anionic antistatic agents 0.2-1.3 part carries out blended 3-10min, melt spinning is carried out through screw type spinning machine, after cooling, carry out oiling, preliminary draft, winding process, obtain the copolyester fiber that even structure, fiber number are controlled;
C the fiber obtained in step (b) is carried out drawing-off processing by (), obtain antistatic-fire retardation copolyester fiber.
10. preparation method according to claim 9, is characterized in that: in described step (a), the extrusion temperature of double screw extruder is 120-170 DEG C;
Or the spinning temperature of described step (b) is 250-290 DEG C, spinning speed is 800-1200m/min;
Or the multiplying power of traction processing in described step (c) is 1.5-3.5, volume speed is 300-800m/min, and drawing-off processing temperature is 60-90 DEG C.
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CN105239189A (en) * | 2015-11-13 | 2016-01-13 | 深圳市名仕度服饰有限公司 | Phosphamide fiber and preparation method thereof through solution method |
CN105350109A (en) * | 2015-11-13 | 2016-02-24 | 深圳市名仕度服饰有限公司 | Polyphosphamide fiber and melting-process preparation method thereof |
CN105780260A (en) * | 2016-04-29 | 2016-07-20 | 王斐芬 | Flame-retardant polysulfonamide blended fabric |
CN106087101A (en) * | 2016-06-13 | 2016-11-09 | 常熟市欧西依织造有限公司 | A kind of fire-resistant antistatic polyester fiber |
CN106521691A (en) * | 2016-11-16 | 2017-03-22 | 揭阳市腾晟科技咨询有限公司 | Polyester fiber with flame resistance and antibacterial properties, and applications thereof |
CN107119341A (en) * | 2017-04-21 | 2017-09-01 | 常熟涤纶有限公司 | A kind of fire-retardant Biodegradable fibers |
CN112127005A (en) * | 2020-10-10 | 2020-12-25 | 杭州成江纺织有限公司 | Polyester filament yarn and preparation process thereof |
CN112760982A (en) * | 2020-12-28 | 2021-05-07 | 安徽省天助纺织科技集团股份有限公司 | High-flame-retardant antistatic yarn and processing method thereof |
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CN105239189A (en) * | 2015-11-13 | 2016-01-13 | 深圳市名仕度服饰有限公司 | Phosphamide fiber and preparation method thereof through solution method |
CN105350109A (en) * | 2015-11-13 | 2016-02-24 | 深圳市名仕度服饰有限公司 | Polyphosphamide fiber and melting-process preparation method thereof |
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TWI744305B (en) * | 2016-04-06 | 2021-11-01 | 美商阿散德性能材料營運公司 | Light color/low resistance anti-static fiber and textiles incorporating the fiber |
CN105780260A (en) * | 2016-04-29 | 2016-07-20 | 王斐芬 | Flame-retardant polysulfonamide blended fabric |
CN106087101A (en) * | 2016-06-13 | 2016-11-09 | 常熟市欧西依织造有限公司 | A kind of fire-resistant antistatic polyester fiber |
CN106521691A (en) * | 2016-11-16 | 2017-03-22 | 揭阳市腾晟科技咨询有限公司 | Polyester fiber with flame resistance and antibacterial properties, and applications thereof |
CN107119341A (en) * | 2017-04-21 | 2017-09-01 | 常熟涤纶有限公司 | A kind of fire-retardant Biodegradable fibers |
CN112127005A (en) * | 2020-10-10 | 2020-12-25 | 杭州成江纺织有限公司 | Polyester filament yarn and preparation process thereof |
CN112760982A (en) * | 2020-12-28 | 2021-05-07 | 安徽省天助纺织科技集团股份有限公司 | High-flame-retardant antistatic yarn and processing method thereof |
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Denomination of invention: Antistatic and flame retardant copolyester fiber and preparation method thereof Effective date of registration: 20191202 Granted publication date: 20180918 Pledgee: Chuzhou economic and Technological Development Corporation Pledgor: Shanghai Jieshijie New Materials (Group) Co., Ltd. Registration number: Y2019980000815 |