CN107313123A - A kind of polynosic fibre and preparation method thereof - Google Patents

A kind of polynosic fibre and preparation method thereof Download PDF

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Publication number
CN107313123A
CN107313123A CN201611035584.1A CN201611035584A CN107313123A CN 107313123 A CN107313123 A CN 107313123A CN 201611035584 A CN201611035584 A CN 201611035584A CN 107313123 A CN107313123 A CN 107313123A
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preparation
reinforcing agent
mass concentration
polynosic fibre
aqueous solution
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CN107313123B (en
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李文斌
徐卫林
李昌垒
李林峰
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Wuhan Textile University
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Wuhan Textile University
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    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D01F2/08Composition of the spinning solution or the bath

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

A kind of polynosic fibre and preparation method thereof, is related to textile fabric processing technique field, and the preparation method is that the first reinforcing agent is added in viscose glue stoste, is uniformly mixing to obtain mixed solution;Mixed solution is subjected to deaeration, filtering, then by spinneret, into the coagulating bath added with the second reinforcing agent, shaping obtains viscose rayon;Viscose rayon is carried out after drawing-off, silk bath is carried out into the silk body lotion added with the 3rd reinforcing agent.The preparation method is to add different reinforcing agents in the different processes that viscose rayon is produced, crosslinking between cellulosic molecule is carried out, constantly strengthen the intensity of viscose rayon, the wet strong and dry strong higher of polynosic fibre is made, therefore the preparation method and obtained polynosic fibre are adapted to popularization and application.

Description

A kind of polynosic fibre and preparation method thereof
Technical field
The present invention relates to a kind of textile fabric processing technique field, and more particularly to a kind of polynosic fibre and its system Preparation Method.
Background technology
Viscose rayon is a kind of textile fabric of current application widely, and it is given birth to by primary raw material of native cellulose The staple fibre of production, it is basic that the natural cellulosic materials such as cotton, bamboo and wood slurry are that viscose rayon provides extensive raw material.In addition, viscous Some performances of glue fiber and natural cotton fiber are very much like, are respectively provided with preferable hygroscopicity, stainability, antistatic, and dress is relaxed It is suitable, have the advantages that chemical fibre is incomparable, product wearability is good.But its shortcoming is also evident from:Viscose rayon Intensity difference, especially wet strong relatively low, generally only dry strong by 1/2nd or so, therefore, the fabric being made up of viscose rayon is not It can strongly wash by rubbing with the hands, take short life.
Over more than 100 years, the production technology of viscose rayon constantly improves, and the viscose rayon of different mechanical properties gradually emerges in large numbers, Such as:High-wet-modulus fibre, high crimped fibre, strong fiber etc..Application number CN201210183713.7 Chinese invention patent Application discloses a kind of polynosic fibre and its production method, specifically includes step:By mass percentage:Polyvinyl alcohol is molten Liquid 1~60%, the ratio blending of viscose glue stoste 40~99%, passes through stirring, deaeration, filtering, spinning, drawing-off, crosslinking process stream It is 3.4~5.8cN/dtex by force that journey, which is made dry, and wet is 1.9~4.1cN/dtex by force, and hygrometric state modulus of elasticity is 0.65~1.60cN/ Dtex viscose rayon, the intensity high 30~50% of the slight viscose rayon spun compared with traditional handicraft of gained viscose rayon with On.The characteristics of technology is using the unique polyhydroxy mafic of polyvinyl alcohol and high polymerization degree, is made spinning molten with viscose glue dope blending Liquid, so as to improve the intensity of viscose rayon.Although the addition of polyvinyl alcohol can improve the wet strong of viscose rayon, in this process Polyvinyl alcohol is not crosslinked, and the hot water resistance of fiber is poor, can not still meet the follow-up dyeing and printing process of viscose rayon product Demand;Moreover, adding the dry strong relatively low of viscose rayon made from polyvinyl alcohol, fragility is larger, easily forms filtration structures, causes The practicality of the technology is very poor.
The content of the invention
It is an object of the invention to provide a kind of preparation method of polynosic fibre, obtained viscose rayon heat-proof water Property preferably, and with higher dry, wet strength, be suitable for commercial introduction application.
Another object of the present invention is to provide a kind of polynosic fibre, its hot water resistance preferably, do it is strong, wet it is strong compared with Height, is suitable for commercial introduction application.
The present invention is solved its technical problem and realized using following technical scheme.
The present invention proposes a kind of preparation method of polynosic fibre, and it comprises the following steps:
The first reinforcing agent is added in viscose glue stoste, mixed solution is uniformly mixing to obtain;Mixed solution is subjected to deaeration, mistake Filter, then by spinneret, into the coagulating bath added with the second reinforcing agent, shaping obtains viscose rayon;To viscose rayon Drawing-off is carried out, silk bath is carried out into the silk body lotion added with the 3rd reinforcing agent.
Further, in present pre-ferred embodiments, the first reinforcing agent is the polyamides that mass concentration is 12%~13% The amine epoxychloropropane aqueous solution, mass concentration are at least one of 12%~13% aq. polyethyleneimine.
Further, in present pre-ferred embodiments, the addition of the first reinforcing agent is the 1% of the weight of viscose glue stoste ~5%.
Further, in present pre-ferred embodiments, the second reinforcing agent is the polyamides that mass concentration is 12%~13% Aq. polyethyleneimine that the amine epoxychloropropane aqueous solution, mass concentration are 12%~13%, mass concentration be 12%~ At least one of 13% urea-formaldehyde resin aqueous solution.
Further, in present pre-ferred embodiments, the addition of the second reinforcing agent is the weight of coagulating bath 0.01%~10%.
Further, in present pre-ferred embodiments, the 3rd reinforcing agent is the polyamides that mass concentration is 12%~13% The amine epoxychloropropane aqueous solution, mass concentration are at least one of 12%~13% casein-formalin.
Further, in present pre-ferred embodiments, the addition of the 3rd reinforcing agent is the weight of silk body lotion 0.01%~10%.
Further, in present pre-ferred embodiments, coagulating bath is by least 60~100g/L sulfuric acid, 200~400g/L Sodium sulphate and 10~80g/L zinc sulfate are mixed.
A kind of polynosic fibre, it uses the preparation method of above-mentioned polynosic fibre to be made.
Further, in present pre-ferred embodiments, the dry of polynosic fibre is 3.8~6cN/dtex by force, wet It is 2.6~4.8cN/dtex by force.
The beneficial effect of the polynosic fibre of the embodiment of the present invention and preparation method thereof is:
1st, the preparation method of the embodiment of the present invention is that the first reinforcing agent is added in viscose glue stoste, is uniformly mixing to obtain mixing Solution;Mixed solution is subjected to deaeration, filtering, then by spinneret, into the coagulating bath added with the second reinforcing agent, into Shape obtains viscose rayon;Drawing-off is carried out to viscose rayon, silk bath is carried out into the silk body lotion added with the 3rd reinforcing agent.Not With in process, different reinforcing agents are added, viscose rayon molecule is acted on, make progress between the cellulose macromolecule of shaped fibers Crosslinking, and then constantly strengthen the intensity of the viscose rayon of shaping.Just because of be crosslinked in fiber between molecule, then it is obtained Polynosic fibre it is wet strong and dry strong higher, therefore the preparation method and obtained polynosic fibre be adapted to promote Using.
2nd, the polynosic fibre obtained by the embodiment of the present invention has higher intensity, and it is 3.8~6cN/ by force to do Dtex, wet is by force 2.6~4.8cN/dtex, and uses conventional traditional handicraft institute spunbond glue fiber dry strong for 2.1~2.2cN/ Dtex, it is therefore, higher using fibre strength made from the preparation technology of polynosic fibre, and it has good bullet Property, hygroscopicity, stainability etc., are widely used.
3rd, the preparation method of the embodiment of the present invention directly can be adjusted in common viscose fiber production technology, without spy Different equipment, polynosic fibre can be produced in common viscose rayon production equipment;Operating process facilitates easily-controllable, easily In realizing industrialized production.
Embodiment
, below will be in the embodiment of the present invention to make the purpose, technical scheme and advantage of the embodiment of the present invention clearer Technical scheme be clearly and completely described.Unreceipted actual conditions person, builds according to normal condition or manufacturer in embodiment The condition of view is carried out.Agents useful for same or the unreceipted production firm person of instrument, are the conventional production that can be obtained by commercially available purchase Product.
Polynosic fibre of the embodiment of the present invention and preparation method thereof is specifically described below.
The embodiment of the present invention provides a kind of preparation method of polynosic fibre, and it comprises the following steps:
S1, the first reinforcing agent is added in viscose glue stoste, be uniformly mixing to obtain mixed solution.Wherein, the first reinforcing agent is The polyethyleneimine that the polyamideepichlorohydrin aqueous solution that mass concentration is 12%~13%, mass concentration are 12%~13% At least one of aqueous solution, above-mentioned solution is dissolved in viscose glue stoste, polyamideepichlorohydrin aqueous solution mass concentration Preferably 12.5%, aq. polyethyleneimine mass concentration is preferably 12.5%, and the first reinforcing agent is preferably that mass concentration is The 12.5% polyamideepichlorohydrin aqueous solution.The addition of first reinforcing agent is the 1%~5% of the weight of viscose glue stoste. The specific preparation method of mixed solution is:Viscose glue stoste and the first reinforcing agent are put into mixer and is stirred, mixing time For 0.5~2 hour, the rotating speed of mixer was 100~2000 revs/min, produces mixed solution.
After the polyamideepichlorohydrin aqueous solution is added in viscose glue stoste, viscose rayon molecule can be dispersed in It is interior, when viscose glue stoste after solidification, drawing-off, silk bath dry by obtained viscose rayon, these polyamideepichlorohydrin molecules Be crosslinked with the hydroxyl in cellulose, therefore, product it is dry strong higher, after product is placed in water, daiamid epoxy chlorine third Alkane is acted between the molecule of cross filament, keeps its network structure, therefore, Related product it is wet strong higher.
After aq. polyethyleneimine is added in viscose glue stoste, containing many in polyethyleneimine polymers strand Hydroxyl formation in individual cation group, the cation group and cellulose very strong cross-bond, therefore, Related product it is dry strong With it is wet strong higher.
S2, by mixed solution carry out deaeration, filtering, then by spinneret, into the solidification added with the second reinforcing agent In bath, shaping obtains viscose rayon.Wherein, coagulating bath by least 60~100g/L sulfuric acid, 200~400g/L sodium sulphate and 10~ 80g/L zinc sulfate is mixed.Second reinforcing agent be mass concentration be 12%~13% the polyamideepichlorohydrin aqueous solution, In the urea-formaldehyde resin aqueous solution that aq. polyethyleneimine that mass concentration is 12%~13%, mass concentration are 12%~13% At least one, dissolve in coagulating bath, and will not occur significant reaction with coagulating bath.Polyamideepichlorohydrin aqueous solution matter It is preferably 12.5% to measure concentration, and aq. polyethyleneimine mass concentration is preferably 12.5%, and urea-formaldehyde resin aqueous solution quality is dense Degree is preferably 12.5%, and the second reinforcing agent is preferably the aq. polyethyleneimine that mass concentration is 12.5%, the second reinforcing agent Addition for coagulating bath weight 0.01%~10%.In the present embodiment, defoaming method is:Mixed solution is carried out at least Twice are filtered, then are squeezed into deaeration kettle, in 20~25 DEG C of insulations, deaeration 2~6 hours.
After aq. polyethyleneimine is added in coagulating bath, containing multiple in polyethyleneimine polymers strand Cation group, the cation group forms very strong cross-bond with the hydroxyl in viscose rayon surface fiber element, therefore, is made Viscose rayon it is dry strong and wet strong higher.
After the polyamideepichlorohydrin aqueous solution is added in coagulating bath, viscose rayon intramolecular or absorption are deposited on In surface, it can not only strengthen the intramolecular structure of viscose rayon, its surface texture can also be strengthened, especially when product is placed in After in water, the polyamideepichlorohydrin molecule cross-link on surface reticulates structure, therefore, Related product it is wet strong higher.
After urea-formaldehyde resin aqueous solution is added in coagulating bath, other reinforcing agents are mainly cooperateed with, the wet of product is improved By force.
S3, to viscose rayon carry out drawing-off after, into the silk body lotion added with the 3rd reinforcing agent carry out silk bath.Wherein, 3rd reinforcing agent be mass concentration be 12%~13% the polyamideepichlorohydrin aqueous solution, mass concentration be 12%~13% At least one of casein-formalin, polyamideepichlorohydrin aqueous solution mass concentration is preferably 12.5%, junket Element-formalin mass concentration is preferably 12.5%, and the 3rd reinforcing agent is preferably that mass concentration is 12.5% daiamid epoxy The chloropropane aqueous solution.The addition of 3rd reinforcing agent is the 0.01%~10% of the weight of silk body lotion.
After the polyamideepichlorohydrin aqueous solution is added in a body lotion, viscose rayon surface is adsorbed in, works as product After being placed in water, the polyamideepichlorohydrin molecule cross-link on surface reticulates structure, therefore, product it is wet strong higher.
After casein-formalin is added in a body lotion, casein forms three-dimensional net structure after formaldehyde crosslinking, The surface of viscose rayon is attached to, the dry strong and wet strong of Related product is improved.
S4, the process such as cut off, wash, dry to obtained fiber, polynosic fibre is finally made.
In a word, reinforcing agent is added during the embodiment of the present invention prepares viscose rayon, mainly in viscose glue stoste, solidification Different intensity reinforcing agents are added respectively in bath or silk body lotion, in different processes, add different reinforcing agents, it is therefore an objective to act on It is crosslinked between viscose rayon inner cellulose molecule, and then constantly strengthens the intensity of the viscose rayon of shaping, so as to The dry and wet intensity of viscose rayon is greatly improved, the mechanism of action is:
The first reinforcing agent is added in viscose glue stoste, because the hydroxyl of cellulose in viscose rayon stoste carries negative electrical charge, It can attract each other, therefore after viscose glue stoste carries out deaeration, filtering, be entered by spinneret with the positive charge in the first reinforcing agent Enter after coagulating bath, the cellulosic molecule in viscose glue stoste is due directly to attracting each other for positive charge, can carry out intramolecular friendship Connection, this crosslinking is crosslinked in network structure, therefore obtained fiber has higher intensity.
The second reinforcing agent is added in coagulating bath, is mainly used in depositing in Forming of Viscose Rayon, permeates in viscose rayon It is interior, or the fiber surface after shaping is adsorbed in, and then structure is reticulated with molecule cross-link in fiber, increase the strong of viscose rayon Degree.
The 3rd reinforcing agent is added in silk body lotion, mainly reinforcing agent is adsorbed in viscose rayon surface or further infiltration To fibrous inside, the 3rd reinforcing agent reticulates structure with molecule cross-link in fiber, increases the intensity of viscose rayon.
The embodiment of the present invention also provides a kind of polynosic fibre, using the preparation method of above-mentioned polynosic fibre It is made, the dry of the polynosic fibre is 3.8~6cN/dtex by force, wet is 2.6~4.8cN/dtex by force.
The feature and performance to the present invention are described in further detail with reference to embodiments.
Embodiment 1
Embodiment 1 provides a kind of polynosic fibre, and it is prepared in accordance with the following methods:
By 100kg viscose glues stoste and the 1kg polyamideepichlorohydrins aqueous solution, (mass concentration is 12.5%, is by polyamides Amine epoxychloropropane, which is dissolved into water, to be formulated) it is put into mixer and is stirred, mixing time is 2 hours, mixer Rotating speed is 200 revs/min, produces mixed solution.
Mixed solution is squeezed into deaeration is carried out in deaeration kettle, then carry out three road filterings, then by spinneret, into adding The 100kg coagulating baths of 10kg urea-formaldehyde resin aqueous solutions have been added (to add 10kg urea-formaldehyde resin aqueous solutions i.e. in 100kg coagulating baths to stir Mix and uniformly form, the mass concentration of urea-formaldehyde resin aqueous solution is 12.5%, is that Lauxite is dissolved into water to be formulated) In, shaping obtains viscose rayon.
Drawing-off is carried out to viscose rayon, into the 100kg silk body lotions that with the addition of the 10kg polyamideepichlorohydrin aqueous solution In (add the 10kg polyamideepichlorohydrin aqueous solution i.e. in 100kg body lotions to stir and forms, daiamid epoxy chlorine third The mass concentration of the alkane aqueous solution is 12.5%, is that polyamideepichlorohydrin is dissolved into water to be formulated) carry out silk bath.
After testing, the dry of the polynosic fibre is 6cN/dtex by force, and wet is 4.8cN/dtex by force.
Embodiment 2
Embodiment 2 provides a kind of polynosic fibre, and it is prepared in accordance with the following methods:
By 100kg viscose glues stoste and the 5kg polyamideepichlorohydrins aqueous solution, (mass concentration is 12%, is by polyamide Epoxychloropropane is dissolved into water and is formulated) it is put into mixer and is stirred, mixing time is 2 hours, and mixer turns Speed is 1000 revs/min, produces mixed solution.
Mixed solution is squeezed into deaeration is carried out in deaeration kettle, then filtered by twice, eventually pass spinneret, into adding Having added the 0.01kg polyamideepichlorohydrins aqueous solution, (mass concentration is 12%, is that polyamideepichlorohydrin is dissolved into water In be formulated) 100kg coagulating baths (coagulating bath is mixed by 6kg sulfuric acid, 30kg sodium sulphate and 1.6kg zinc sulfate) in, Shaping obtains viscose rayon.
Drawing-off is carried out to viscose rayon, (mass concentration is 12%, is into the addition of 0.01kg caseins-formalin Casein-formaldehyde is dissolved into water and is formulated) 100kg silk body lotions in carry out silk bath.
After testing, the dry of the polynosic fibre is 5cN/dtex by force, and wet is 4cN/dtex by force.
Embodiment 3
Embodiment 3 provides a kind of polynosic fibre, and it is prepared in accordance with the following methods:
By 100kg viscose glues stoste and 1kg aq. polyethyleneimines, (mass concentration is 13%, is that polyethyleneimine is molten Solution, which enters in water, to be formulated) be put into mixer and be stirred, mixing time is 0.5 hour, the rotating speed of mixer for 2000 turns/ Point, produce mixed solution.
Mixed solution is subjected to twice filtering, then squeezed into deaeration kettle, in 20 DEG C of insulations, deaeration 3 hours, then by spray Filament plate, into the addition of 5kg aq. polyethyleneimines, (mass concentration is 12.5%, is that polyethyleneimine is dissolved into water Be formulated) 100kg coagulating baths (coagulating bath is mixed by 5kg sulfuric acid, 20kg sodium sulphate and 1.5kg zinc sulfate) in, into Shape obtains viscose rayon.
Drawing-off is carried out to viscose rayon, (mass concentration is 13%, is by junket into the addition of 5kg caseins-formalin Element-formaldehyde is dissolved into water and is formulated) 100kg silk body lotions in carry out silk bath.
After testing, the dry of the polynosic fibre is 4cN/dtex by force, and wet is 3cN/dtex by force.
Embodiment 4
Embodiment 4 provides a kind of polynosic fibre, and it is prepared in accordance with the following methods:
By 100kg viscose glues stoste and the 5kg polyamideepichlorohydrins aqueous solution, (mass concentration is 13%, is by polyamide Epoxychloropropane is dissolved into water and is formulated) it is put into mixer and is stirred, mixing time is 1 hour, and mixer turns Speed is 800 revs/min, produces mixed solution.
Mixed solution is squeezed into deaeration is carried out in deaeration kettle, then carry out twice filtering, by spinneret, into the addition of The 100kg coagulating baths of 5kg urea-formaldehyde resin aqueous solutions (mass concentration is 12%, is that Lauxite is dissolved into water to be formulated) In (coagulating bath is mixed by 8kg sulfuric acid, 30kg sodium sulphate and 10kg zinc sulfate), shaping obtains viscose rayon.
To viscose rayon carry out drawing-off, into the addition of 5kg caseins-formalin (mass concentration is 12.5%, be by Casein-formaldehyde is dissolved into water and is formulated) 100kg silk body lotions in carry out silk bath, then the work such as cut off, washed, being dried Sequence, is finally made polynosic fibre.
After testing, the dry of the polynosic fibre is 5.2cN/dtex by force, and wet is 3.8cN/dtex by force.
In summary, viscose rayon made from the preparation method of the polynosic fibre of the embodiment of the present invention dry strong and Wet strong higher, i.e. the intensity of viscose rayon is high, is adapted to popularization and application.
Embodiments described above is a part of embodiment of the invention, rather than whole embodiments.The reality of the present invention The detailed description for applying example is not intended to limit the scope of claimed invention, but is merely representative of the selected implementation of the present invention Example.Based on the embodiment in the present invention, what those of ordinary skill in the art were obtained under the premise of creative work is not made Every other embodiment, belongs to the scope of protection of the invention.

Claims (10)

1. a kind of preparation method of polynosic fibre, it is characterised in that it comprises the following steps:
The first reinforcing agent is added in viscose glue stoste, mixed solution is uniformly mixing to obtain;The mixed solution is subjected to deaeration, mistake Filter, then by spinneret, into the coagulating bath added with the second reinforcing agent, shaping obtains viscose rayon;To the viscose glue Fiber carries out drawing-off, and silk bath is carried out into the silk body lotion added with the 3rd reinforcing agent.
2. the preparation method of polynosic fibre according to claim 1, it is characterised in that first reinforcing agent is The polyethyleneimine that the polyamideepichlorohydrin aqueous solution that mass concentration is 12%~13%, mass concentration are 12%~13% At least one of aqueous solution.
3. the preparation method of polynosic fibre according to claim 1, it is characterised in that first reinforcing agent Addition is the 1%~5% of the weight of the viscose glue stoste.
4. the preparation method of polynosic fibre according to claim 1, it is characterised in that second reinforcing agent is The polyethyleneimine that the polyamideepichlorohydrin aqueous solution that mass concentration is 12%~13%, mass concentration are 12%~13% The aqueous solution, mass concentration are at least one of 12%~13% urea-formaldehyde resin aqueous solution.
5. the preparation method of polynosic fibre according to claim 1, it is characterised in that second reinforcing agent Addition is the 0.01%~10% of the weight of the coagulating bath.
6. the preparation method of polynosic fibre according to claim 1, it is characterised in that the 3rd reinforcing agent is Casein-formaldehyde that the polyamideepichlorohydrin aqueous solution that mass concentration is 12%~13%, mass concentration are 12%~13% At least one of aqueous solution.
7. the preparation method of polynosic fibre according to claim 1, it is characterised in that the 3rd reinforcing agent Addition is the 0.01%~10% of the weight of the silk body lotion.
8. the preparation method of polynosic fibre according to claim 1, it is characterised in that the coagulating bath is by least 60~100g/L sulfuric acid, 200~400g/L sodium sulphate and 10~80g/L zinc sulfate are mixed.
9. a kind of polynosic fibre, it is characterised in that it uses the high intensity any one of claim 1 to 8 to glue The preparation method of glue fiber is made.
10. polynosic fibre according to claim 9, it is characterised in that the polynosic fibre it is dry strong For 3.8~6cN/dtex, wet is 2.6~4.8cN/dtex by force.
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CN109913966A (en) * 2019-01-24 2019-06-21 盐城锦阳新材料科技有限公司 It is a kind of to prepare the filametntary method of high-strength artificial using plant cellulose
CN110559742A (en) * 2019-09-16 2019-12-13 武汉纺织大学 Preparation method of viscose-based air filtering material
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CN109913966A (en) * 2019-01-24 2019-06-21 盐城锦阳新材料科技有限公司 It is a kind of to prepare the filametntary method of high-strength artificial using plant cellulose
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CN110559742A (en) * 2019-09-16 2019-12-13 武汉纺织大学 Preparation method of viscose-based air filtering material
CN111058185A (en) * 2019-12-05 2020-04-24 湖北拓盈新材料有限公司 High-strength viscose non-woven fabric and preparation method thereof
CN111823672A (en) * 2020-07-15 2020-10-27 刁其松 Towel with cooling and refreshing functions and preparation method thereof

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