CN101421445A - Process for the production of acrylic fibre for fabrics with a low pilling formation and acrylic fibres thus obtained - Google Patents
Process for the production of acrylic fibre for fabrics with a low pilling formation and acrylic fibres thus obtained Download PDFInfo
- Publication number
- CN101421445A CN101421445A CNA200680053558XA CN200680053558A CN101421445A CN 101421445 A CN101421445 A CN 101421445A CN A200680053558X A CNA200680053558X A CN A200680053558XA CN 200680053558 A CN200680053558 A CN 200680053558A CN 101421445 A CN101421445 A CN 101421445A
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- CN
- China
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- weight
- comonomer
- acrylic
- acid
- fibre
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Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/06—Washing or drying
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D10B2321/10—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/14—Dyeability
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2501/00—Wearing apparel
- D10B2501/02—Underwear
- D10B2501/021—Hosiery; Panti-hose
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2505/00—Industrial
- D10B2505/18—Outdoor fabrics, e.g. tents, tarpaulins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/30—Woven fabric [i.e., woven strand or strip material]
- Y10T442/3065—Including strand which is of specific structural definition
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Chemical & Material Sciences (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Artificial Filaments (AREA)
- Woven Fabrics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
Abstract
Process for the production of acrylic fibre, for fabrics with a low pilling formation, having a titer within the range of 1.0 to 5.6 dtex, which comprises the wet spinning in a solvent of a copolymer essentially consisting of acrylonitrile, in a quantity within the range of 97 to 99.99% by weight, and a comonomer with a strong acid group of the sulfonic type having the general formula: CH2=C(R) -CH2SO3-M wherein R represents a hydrogen atom or the CH3 radical whereas M represents a hydrogen atom or an alkaline metal in a quantity ranging from 0.01 to 3% by weight.
Description
The present invention relates to the preparation method of a kind of low balling-up fabric with acrylic fibre (acrylic fibre).
More specifically, the present invention relates to preparation method and the thus obtained fiber of a kind of low balling-up fabric with acrylic fibre.
As everyone knows, acrylic fibre since its imitate and usually surmount natural fabric for example wool and cotton special nature and in synthetic and artificial fibre, have very high status greatly.
The machinability of acrylic fibre in cotton or wool textile series beyond doubt excellent and be higher than above-mentioned natural fabric far away.Simultaneously, the chromatophilia of acrylic fibre can keep bright and sun-proof for a long time, makes its performance be better than natural fabric.
Acrylic fibre can also be used for a large amount of final uses, and it usually is better than natural fabric in some fields, knitwear for example, and hosiery, sportswear, family is spun, fluffy account cloth, cement reinforcing material etc.
The main application fields of acrylic fibre be undoubtedly pure or with wool blended knitwear.But along with use, these type of final products can produce stubborn problem, occur along with the inaesthetic bobbles that uses and the time increases as meeting.
The phenomenon that bobbles occurs is formation and the increase that causes them owing to the reason of machinery as everyone knows.In the past, the applicant, for example, utilization reach the bobbles of acrylic fibre index formation, increase and the formation of the kinetic model that drops research bobbles (Doria G., Trevisan E. " Textile Asia ", 64,1989), this acrylic fibre is Leacril NP known for everyone on the market, has to be used for delaying the high surface waviness that filament is extracted out from yarn, with the low toughness of the fiber that is used to impel the filament breakage that is connected bobbles and final products.
According to above-mentioned model by applicant's research and development, promptly have the fiber of low toughness and low elongation at vertical and node, other producers have proposed the acrylic fibre of " not balling-up " type.
These commercial fibres of a part are not have the method for the fiber of balling-up or low balling-up to obtain with preparation " naturally ".The method of using aqueous solvent is arranged in these methods, and wherein, because the low concentration of polymer in spinning solution, the fiber of acquisition has hide " space " of weakening fiber in a large number.On the other hand, most wet method and dry spinning method relaxed fibre immediately rather than in the autoclave with pressurization saturated vapor helps having the natural production of the fiber of low node thus.
All commercial fibres of Chu Xianing comprise Leacril NP in the market, although not balling-up and be the pattern of improving with respect to traditional acrylic fibres can not solve the problem that occurs influence bobbles attractive in appearance on the final products fully.
All commercial acrylic fibre in fact, all are subjected to " physical-chemical " restriction relevant with the composition of polymer, that is, and and in damp and hot lower DIMENSIONAL STABILITY down.The damp and hot down unsettled reason of commercial acrylic fibre is must " dilution " to be incorporated into for example CN group in vinylacetate or the methyl acrylate polymeric chain of comonomer, they have, and bigger molecule hinders and the ion neutralization, its objective is that improvement especially uses the dissolubility and the processability of the polymer with the solvent that hangs down solvability.
The polyacrylonitrile homopolymers in fact has structure very closely, and this structure is insensitive to hot water and steam, because the strong interaction of dipole-dipole type between the CN group makes polymer be difficult to dissolve and be difficult to change into fiber.In fact, the polyacrylonitrile homopolymer fibre that except applicant's Ricem, is not fit to industrial use on the market.
Traditional acrylic fibres for textile use, the comonomer that adopts is vinylacetate, methyl acrylate system etc., the degree scope is 5-10%, successfully penetrate into the hydrone capable " solvation " of fiber CN group as real plasticizer, reduce to be configured to the fragility of the fiber of low degree of molecular orientation (stretching) and low malleableize, make the easier extension of fiber itself and delay the formation of bobbles thus.
Occur in dyeing stage of fiber by means of the solvation of the acrylic fibre of hydrone, in temperature is equal to or higher than 100 ℃ water, or occur in operational phase, it is by the moisture of human body.
Provided the suggestion of the solution selected of foregoing in the literature.For example, utilize and introduce inert material such as kaolin, the particle reduction fiber (Japan Patent 3,174 of silica or titanium dioxide, 012), on long filament, introduce surface cuts (United States Patent (USP) 3,928,528), push final products (United States Patent (USP) 3 between two plates of irregular surface having, 894,318) or reduce toughness and node elongation, keep polymer concentration≤20% of spinning solution so that the value of product is lower than 2.0g/den (Japanese patent application 4057909).
It all is invalid that the solution of all these suggestions has been proved to be, and this is because the deterioration that they are had low stretch value or had the outward appearance and the spinning process of final products by the fiber of copolymer.Should remember that particularly, the long stapled production of flatness negatively influences the potentiality of fiber production system.
The applicant, be used to filter the producer of the polyacrylonitrile homopolymer fibre of the hot cigarette that coal power generation factory produces, have been found that now a kind of polyacrylonitrile homopolymer fibre of special modification shows the unexpected performance aspect balling-up that any commercial acrylic fibre all can't compare.This result who describes in detail in appended claim is especially astonishing and unexpected, and this is because well-known polyacrylonitrile homopolymer fibre is not to be suitable for traditional weaving purposes.The applicant has overcome this defective by introducing than the dyed group with the conventional more a large amount that obtains of persulfate-bisulfites oxidation reduction catalyst.
Sulfonic acid and the sulfate (sulphate) by the oxidation reduction catalyst preparation that are used to comprise the commercial acrylic fibre that surpasses 6% comonomer such as vinylacetate or methyl acrylate are enough to the dull fiber that dyes usually, this be because, because the plasticization of water and steam, the easy infiltration of dyestuff can be used all sulfonic acid and the fiber of sulfate group.
With regard to the polyacrylonitrile homopolymer fibre, sulfonic group is incorporated in the polymerization with some are extra (with respect to coming from those of oxidation reduction catalyst) fully by adding unsaturated sulfonation and copolymerization monomer of ethylene linkage such as sodium methallyl sulfonate, to obtain and the similar result of result who uses the copolymer based on acrylonitrile to obtain who is used for commercial fibres.
Along with introducing the sulfonation and copolymerization monomer until maximum 3.0 weight %, 0.01-3.0 weight % for example, preferred 0.1-3 weight %, the polyacrylonitrile homopolymer fibre remains unchanged and the fiber maintenance has " fragility " that makes up of special pilling tendency in spinning process in the DIMENSIONAL STABILITY damp and hot under.
Especially, the wet spinning that purpose of the present invention relates to by copolymer prepares not balling-up acrylic fibre, and described copolymer mainly comprises the acrylonitrile of at least 97 weight % and maximum 3% the comonomer with sulfonic acid class strong acid that is selected from following general formula:
CH
2＝C(R)-CH
2SO
3-M
Wherein R represent hydrogen atom or-CH
3Base, and M represents hydrogen atom or alkali metal, as methallylsulfonic acid or allyl sulphonic acid or their sodium salt.
According to the present invention, be used to prepare acrylic fibre acrylic copolymer can also, but not necessarily, comprise the vinyl-based neutral comonomer of maximum 1.5 weight %, for example C
1-C
4The vinyl esters of acid, as vinylacetate, or (methyl) acrylic acid C
1-C
4Arrcostab is as methacrylate or methyl methacrylate.
The object of the present invention is to provide a kind of copolymer that uses in process of production, its polymerization in the water slurry of persulfate-bisulfites redox-catalyst system obtains, and have many end of the chains that dye, the latter for example is used for guaranteeing that the final fiber in common weaving purposes has excellent stainability.
By the solid content weight percentage ranges is that the spinning solution of 17-23% makes fiber in coagulating bath, wet then drawing-off, and in dry on the hot-rolling and heat treatment in steam, this fiber has the minimum fracture strength of 26cN/tex and 18% minimum extension at break.The standard of coil mechanical property has indicated the sound response of the ANTIPILLING test (test of ICI case method or Martindale's test) to the pure fabric of described fiber and BLENDED FABRIC, described standard is: coil intensity≤4.0cN/tex, the product of coil elongation≤1.5% and intensity * elongation, perhaps coil merit≤6.0cN/tex
Provide the following examples to be used for illustrating without limitation the present invention.
Embodiment
Present embodiment has been described the method that makes acrylic fibre of the present invention with wet spinning.
The copolymer that contains the methallylsulfonic acid sodium of 98% acrylonitrile and 2% is polymerized by continuing in water slurry, the pH=2.8-3.0 of this water slurry and temperature are 50 ℃, have potassium peroxydisulfate catalyst and sodium hydrogensulfite activator with the ratio adding of 1.30-1.90, this ratio is represented with respect to the mass flowrate of catalyst with the mass flowrate of activator.Remove unreacted monomer, filter and dried particles after the copolymer that obtains have the interior specific viscosity of 0.240-0.290 scope, this specific viscosity is to measure in the dimethylacetylamide in 25 ℃ of temperature, 1g/l solution.Copolymer has maximum dissolving peak (use rotary viscosity measuring) in the dimethylacetylamide of 90 ± 2 ℃ of temperature, begin and heating rate is 1 ℃/min from the solvent/polymer slurry of room temperature.
It is in the dimethylacetylamide of 18 ± 2 weight % that thus obtained polymer is dissolved in respect to dissolvent solid content, then extrudes the stoste through filtering under 85 ℃ temperature.
The final fiber number of fiber is 2.2dtex.Using capillary diameter is 52 microns spinning nozzle, and the concentration that immerses temperature and be dimethylacetamide solvent in 42 ℃ and the water is in 45% the coagulating bath.
Leave the fibre bundle of coagulating bath and be to compress on the roller of 9.0atm in internal vapor pressure with the total draft rate drawing-off that equals 6x.Behind the hot rolling song, under the pressure of 2.0-3.0atm,, keep its residue shrinkage factor simultaneously less than 1% by in annealer, directly introducing the steam stable fibre bundle.
The fracture strength of the fiber that obtains thus is that 28cN/tex and extension at break are 23%.The coil intensity of measuring is verified as 2.2cN/tex and the coil elongation is 1%, and the product of intensity * elongation simultaneously is 2.2cN/tex (a coil merit).
The final cross section of the fiber that makes is for circular.The fiber of bundle form is opened, and is converted into the blended yarn (23 microns) that wool top is spun into 100% acrylic fibre yarn and 50% acrylic fibre and 50% wool then, fiber number Nm2/28-twist 400z-240s-.
Next use two knit goodss of these yarn weaving,, carry out the ANTIPILLING test after the dyeing in the above according to standard method BS-5811/86 (test of ICI case method).According to estimate the grade that forms balling-up from 1 (poor) to 5 (good), the fabric of being made by the yarn that comprises above-mentioned 100% acrylic fibre after 14,400 commentaries on classics and the grade of wool blends all are 4 and 5.
Claims (13)
1. the low balling-up fabric of a 1.0-5.6dtex fiber number is with the preparation method of acrylic fibre, be included in the copolymer of being made up of acrylonitrile basically of wet spinning 97-99.99 weight % in the solvent and the comonomer with sulfonic acid class strong acid of 3 weight % at the most, the general formula of this comonomer is:
CH
2＝C(R)-CH
2SO
3-M
Wherein R represent hydrogen atom or-CH
3Base, and M represents hydrogen atom or alkali metal.
2. preparation method as claimed in claim 1, the solvent of wherein said wet spinning is a dimethylacetylamide.
3. preparation method as claimed in claim 1 or 2, wherein said copolymer comprises the vinyl-based neutral comonomer of 1.5 weight %, for example C at the most
1-C
4Vinyl esters or (methyl) acrylic acid C of acid
1-C
4Arrcostab.
4. as the described preparation method of above-mentioned arbitrary claim, wherein said have strong sulfonic ion-type unsaturated comonomer and be selected from methallylsulfonic acid, allyl sulphonic acid and corresponding sodium and potash salt.
5. as the described preparation method of above-mentioned arbitrary claim, wherein the copolymer of being made up of acrylonitrile basically obtains by polymerization in the water slurry that has persulfate-bisulfites catalytic oxidation-reduction idol, with respect to the monomer that adds, the concentration of persulfate is 0.4-0.6% (as potassium peroxydisulfate or sodium peroxydisulfate or ammonium persulfate), and the concentration of bisulfites is 0.6-1.4%.
6. as the described preparation method of above-mentioned arbitrary claim, wherein under being 45-65 ℃ condition, temperature obtains the described copolymer formed by acrylonitrile basically.
7. as the described preparation method of above-mentioned arbitrary claim, wherein make the described copolymer of forming by acrylonitrile basically in the water slurry of 2.6-3.0 in the pH value.
8. the acrylic fibre of a 1.0-5.6dtex fiber number, it comprises the acrylonitrile of 97-99.9 weight %, the comonomer with sulfonic acid class strong acid of 0.01-3 weight % and the vinyl-based neutral comonomer of 0-1.5 weight %, for example C
1-C
4The vinyl esters such as the vinylacetate of acid, or (methyl) acrylic acid C
1-C
4Arrcostab, described neutral comonomer is selected from the comonomer with following general formula:
CH
2＝C(R)-CH
2SO
3-M
Wherein R represent hydrogen atom or-CH
3Base, and M represents hydrogen atom or alkali metal.
9. acrylic fibre as claimed in claim 8, it comprises the titanium dioxide that accounts for polymer weight 0-0.4 weight %.
10. acrylic fibre as claimed in claim 8 or 9, its boiling water residue shrinkage factor is less than 1%.
11. as each described polypropylene fibre of claim 8-10, its coil intensity is not higher than 4cN/tex, coil elongation be not higher than 1.5% and the product of coil intensity * coil elongation be not higher than 6cN/tex.
12. contain the fabric just like each described acrylic fibre of claim 8-11, according to standard method BS-5811/86, it has the minimum balling-up value that obtains with the test of ICI case method, in 1 to 5 grade, this value is 4/5.
13. contain fabric just like each described acrylic fibre of claim 8-11 and 1-50 weight % natural fabric such as wool, according to standard method BS-5811/86, it has the minimum balling-up value that obtains with the test of ICI case method, and in 1 to 5 grade, this value is 4/5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITMI20060386 ITMI20060386A1 (en) | 2006-03-03 | 2006-03-03 | PROCEDURE FOR THE PRODUCTION OF ACRYLIC FIBER FOR LOW-FORM PILLING FABRICS AND ACUTE ACRYLIC FIBERS |
| ITMI2006A000386 | 2006-03-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101421445A true CN101421445A (en) | 2009-04-29 |
Family
ID=37776508
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA200680053558XA Pending CN101421445A (en) | 2006-03-03 | 2006-11-21 | Process for the production of acrylic fibre for fabrics with a low pilling formation and acrylic fibres thus obtained |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20090053953A1 (en) |
| EP (1) | EP1991722A1 (en) |
| JP (1) | JP2009528453A (en) |
| KR (1) | KR20080096814A (en) |
| CN (1) | CN101421445A (en) |
| IT (1) | ITMI20060386A1 (en) |
| WO (1) | WO2007098796A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102677290A (en) * | 2012-05-29 | 2012-09-19 | 蔡紫林 | Shell fabric |
| CN106661771A (en) * | 2014-08-27 | 2017-05-10 | 三菱丽阳株式会社 | Glossy pilling-resistant acrylic fiber, method for producing same, and spun yarn and knitted fabric including said acrylic fiber |
| US11594732B2 (en) | 2018-03-01 | 2023-02-28 | Adeka Corporation | Organo sulfur-based electrode active material |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101186860B1 (en) * | 2012-05-29 | 2012-10-02 | 안영훈 | Knitwear and knitting method for preventing fluff |
| KR101938487B1 (en) * | 2017-07-31 | 2019-01-14 | 서울대학교산학협력단 | Electrical parameters-assisted wet-spinning method |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB911341A (en) * | 1960-06-08 | 1962-11-28 | Du Pont | Polyacrylonitrile fiber |
| JP2908046B2 (en) * | 1991-02-21 | 1999-06-21 | 三菱レイヨン株式会社 | Anti-pilling acrylic fiber and method for producing the same |
| JPH0559608A (en) * | 1991-08-30 | 1993-03-09 | Mitsubishi Rayon Co Ltd | Anti-pilling acrylic fiber and its production |
| JP3656311B2 (en) * | 1996-03-14 | 2005-06-08 | 東レ株式会社 | Anti-pill ultrafine acrylic fiber and method for producing the same |
| US6268450B1 (en) * | 1998-05-11 | 2001-07-31 | Solutia Inc. | Acrylic fiber polymer precursor and fiber |
-
2006
- 2006-03-03 IT ITMI20060386 patent/ITMI20060386A1/en unknown
- 2006-11-21 EP EP20060829105 patent/EP1991722A1/en not_active Withdrawn
- 2006-11-21 JP JP2008556664A patent/JP2009528453A/en active Pending
- 2006-11-21 WO PCT/EP2006/011213 patent/WO2007098796A1/en active Application Filing
- 2006-11-21 US US12/281,386 patent/US20090053953A1/en not_active Abandoned
- 2006-11-21 CN CNA200680053558XA patent/CN101421445A/en active Pending
- 2006-11-21 KR KR1020087021578A patent/KR20080096814A/en not_active Application Discontinuation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102677290A (en) * | 2012-05-29 | 2012-09-19 | 蔡紫林 | Shell fabric |
| CN106661771A (en) * | 2014-08-27 | 2017-05-10 | 三菱丽阳株式会社 | Glossy pilling-resistant acrylic fiber, method for producing same, and spun yarn and knitted fabric including said acrylic fiber |
| CN106661771B (en) * | 2014-08-27 | 2020-05-19 | 三菱化学株式会社 | Gloss pilling-resistant acrylic fiber, process for producing the same, and yarn and knitted fabric comprising the same |
| US11594732B2 (en) | 2018-03-01 | 2023-02-28 | Adeka Corporation | Organo sulfur-based electrode active material |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2007098796A8 (en) | 2007-11-29 |
| KR20080096814A (en) | 2008-11-03 |
| JP2009528453A (en) | 2009-08-06 |
| EP1991722A1 (en) | 2008-11-19 |
| ITMI20060386A1 (en) | 2007-09-04 |
| WO2007098796A1 (en) | 2007-09-07 |
| US20090053953A1 (en) | 2009-02-26 |
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