CN100445438C - Process of producing polyacrylic fiber dyeable with both cationic dye and acid dye - Google Patents
Process of producing polyacrylic fiber dyeable with both cationic dye and acid dye Download PDFInfo
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Abstract
The process of producing polyacrylic fiber dyeable with both cationic dye and acid dye includes dissolving polyacrylonitrile resin A and polyacrylonitrile resin B in the weight ratio of 1 to (0.6-1.6) in solvent of water solution of NaSCN in the 35- 58 wt% concentration to form raw spinning liquor with total solid content of 8-20 %; spinning the raw spinning liquor through the 8-15 wt% concentration water solution of NaSCN inside the coagulating bath to form nascent fiber; and post-treatment of the nascent fiber to produce polyacrylic fiber product. The third monomer for resin A is sodium methyl acryl sulfonate or 2-acrylamido-2-methyl propyl sulfonic acid and accounts for 0.8-5.0 wt%; and that for resin B is one of N, N-dimethyl amido ethyl methyl acrylate nitrate, N-dimethyl amido ethyl methyl acrylate hydrochloride or N-dimethyl amido ethyl methyl acrylate sulfate and accounts for 3.3-12.5 wt%.
Description
Technical field
The present invention relates to a kind of method of making acrylic fiber, particularly a kind of is the method that the solvent wet spinning process is made acrylic fiber with the NaSCN aqueous solution.
Background technology
Acrylic fiber has good bulkiness and warmth retention property, and is soft, and performance exactly likes wool, and very superior light resistance and radiation resistance are arranged.The application surface of acrylic fibers is very wide, take, field such as bedding and soft decoration all is desirable textile raw material.The spinning material of acrylic fibers is a polyacrylonitrile resin, simple polyacrylonitrile resin dyeability is very poor, so improve the second flexible comonomer except adding in the resin, also must add the 3rd comonomer that is used for dyeing, modifying, so that the seat that dyes that dyes on the dyestuff to be provided to polymer molecule.In the prior art, the 3rd monomer of plain polypropylene nitrile resin only is fit to cationic dyeing.Because the performance of acrylic fibers exactly likes wool, acrylic fibers and wool blended, the mixed fabric of knitting occupy very big ratio in the converted products behind acrylic fibers.But wool should adopt ACID DYES to dye, and therefore hair-nitrile blending, mixes the fabric of knitting and requires acrylic fibers and wool can carry out " with bath " to dye, and promptly requires the 3rd comonomer in the polyacrylonitrile resin can be fit to the dyeing of ACID DYES.The manufacturing technology of acid-dyeable acrylic fibers has been seen more report, opens clear 56-21842, spy as the Japan Patent spy and opens the content that clear 55-8604 and the clear 48-7888 of Te Kai have all related to this respect.Although still there is obvious defects in these existing acid-dyeable acrylic fibers, reactivity ratio is on the low side in the copolymerization system that is constituted as the 3rd monomer of dyeing, modifying and acrylonitrile and flexible modification second monomer commonly used, so that easily cause dyeing saturation value can't reach desirable numerical value, but realized the acid-dyeable of acrylic fiber after all.
But existing acrylic fiber only has the dye accessible performance of single kind, or cationic dye capable of dyeing or acid-dyeable, can't accomplish that two kinds of dyestuffs all can dye.This obviously gives in the production of product sales management, the weaving processing of road, back and dyeing and finishing process of acrylic fiber and has increased difficulty in the management.
Summary of the invention
Technical problem to be solved by this invention provides the manufacture method of the acrylic fibers that a kind of cation dyes and ACID DYES all can dye, and no matter the acrylic fiber that this method makes all has desirable dyeing saturation value to cation dyes or ACID DYES.
Below be the technical scheme that the present invention solves the problems of the technologies described above:
The manufacture method of the acrylic fibers that a kind of cation dyes and ACID DYES all can be dyed, this method comprises process:
1) polyacrylonitrile resin A and B are dissolved in solvent and make spinning solution, A or B are terpolymer, and viscosity average molecular weigh is 4～70,000.Both first monomers are that acrylonitrile, second monomer are methyl acrylate or vinylacetate, wherein the 3rd monomer of A is methylpropene sodium sulfonate or 2-acrylamido-2-methyl propane sulfonic acid, and the 3rd monomer of B is a kind of in methacrylic acid N, N dimethylaminoethyl nitrate, methacrylic acid N, N dimethylaminoethyl hydrochloride or methacrylic acid N, the N dimethylaminoethyl sulfate.In the total amount of three kinds of comonomers, second content of monomer of A or B is 5.5～1 6.5wt%, and the 3rd content of monomer of A is 0.8～5.0wt%, and the 3rd content of monomer of B is 3.3～1 2.5wt%.The weight ratio of A and B is A: B=1 in the spinning solution: (0.6～1.6), total solid content are 8～20%, and solvent is that concentration is the NaSCN aqueous solution of 35～58wt%;
2) spinning solution is configured as as-spun fibre by coagulating bath behind the spray silk, and the shower nozzle degree of draft is-70～-85%, and coagulating bath is that concentration is the NaSCN aqueous solution of 8～15wt%, and coagulation bath temperature is-5～8 ℃;
3) as-spun fibre is made the acrylic fiber product through last handling process.
The 3rd monomer of above-mentioned A is preferably methylpropene sodium sulfonate, and the 3rd monomer of B is preferably methacrylic acid N, N dimethylaminoethyl nitrate or methacrylic acid N, N dimethylaminoethyl hydrochloride;
The 3rd content of monomer of B is preferably 6.0～10.0wt%;
Total solid content is preferably 10～18wt% in the spinning solution;
A and B are preferably the powdery polymer that obtains by aqueous polymerization.
Above-mentioned as-spun fibre the last handling process of process generally comprise cold drawing-off, washing, hot drawing-off, oil, compacting by drying, curl and HEAT SETTING.
Key of the present invention is that the polyacrylonitrile resin raw material that is used for spinning has comprised two kinds of polyacrylonitrile copolymers, and wherein A is a cationic dye capable of dyeing polyacrylonitrile resin conventional in the prior art, and B then is a kind of polyacrylonitrile resin of acid-dyeable.This makes that the fiber of making still is that ACID DYES all has good stainability to cation dyes.Be understood that after comprising these two kinds of copolymers of A and B in the spinning material simultaneously, for a certain dyestuff (cation dyes or ACID DYES), what combine with dye molecule in the fiber dyes seat with corresponding minimizing in proportion.Therefore no matter be A or B, should be with the wherein corresponding raising of the 3rd content of monomer of dyeing, modifying, could guarantee like this in the fiber at a certain dye molecule to dye a content constant.By prior art as can be known, these known cationic dye capable of dyeing the 3rd monomers have very high reactivity ratio in the copolymerization system that constitutes with second monomer by acrylonitrile and flexible modification, so the raising of the 3rd content of monomer is not difficult in the copolymer.But as use those acid-dyeable the 3rd monomers of existing report can't guarantee that because of reactivity ratio is too low the 3rd monomer can be brought up to enough content in the copolymer.And the 3rd monomer that the acrylic resin B of the selected acid-dyeable of the present invention adopts has higher reactivity ratio in above-described copolymerization system, this has just guaranteed that the 3rd monomer can be brought up to enough content in resin under general polymerizing condition, thereby finally makes the acrylic fiber that has comprised A, B two kinds of copolymers in the spinning material that ACID DYES is had desirable dyeing saturation value equally.
It is that the process for suspension polymerization of medium is made that A and B preferably adopt water, and the resin that obtains like this is pulverous, and this will help, and both are mixed fully when the preparation spinning solution.
In the present invention, the last handling process of as-spun fibre is not distinct with existing conventional NaSCN wet spinning process, generally includes cold drawing-off, washing, hot drawing-off, oils, compacting by drying, curls and HEAT SETTING etc.
Wherein cold drawing-off is generally carried out in concentration is the NaSCN solution of 5～10wt%, and bathing temperature is 30～40 ℃, and drafting multiple is 1.0～4.0 times; The coolant-temperature gage of washing is 45～65 ℃, and NaSCN content is less than 0.002wt% in the fiber after requiring to wash; Tow after the washing enters hot drafting process after with the hot water preheating, and tow is carried out high drafting, and hot drafting multiple is controlled at 2～10 times.
Tow after the drawing-off enters oil groove and oils, to eliminate fiber electrostatic; The back tow that oils enters drying machine, carries out the compacting by drying of fiber, dry built-in temperature subregion control, and temperature controlling range is 95～140 ℃; The processing of curling is then curled and can be adopted hot water heating or Steam Heating; Tow through curling carries out HEAT SETTING to be handled, and the temperature of HEAT SETTING is generally 100～140 ℃.
Fiber after the typing according to after spin processing request and cut off, make the acrylic staple fibre product of different length.
Compared with prior art, the invention has the advantages that the acrylic fiber that makes all has desirable dye-uptake to cation dyes and ACID DYES, dyeing saturation value is all very high, and fibrous physical property index and conventional acrylic fibers do not have any difference.This gives in the production of product sales management, the weaving processing of road, back and dyeing and finishing process of acrylic fiber and has brought very big convenience in the management.
Below will the invention will be further described by specific embodiment.With respect to prior art, the present invention is that mainly the 3rd monomer changes to some extent in the spinning material polyacrylonitrile resin, because the amount of the 3rd monomer is less at the polyacrylonitrile resin proportion, obviously such variation can't bring tangible influence to its spinning properties.So the spinning of technical solution of the present invention and last handling process are identical with general NaSCN wet spinning process, are also known by those of ordinary skill in the art, so in an embodiment the process conditions of spinning and post processing are exceeded for example.
In addition, also same as the prior art as the A in the spinning material polyacrylonitrile resin, by what technical solution of the present invention comprised,, the A of other kind of not enumerating in an embodiment has identical effect and can predicting it for those of ordinary skill in the art.Because dyeing and finishing add man-hour CATION or acid two kinds of dyestuffs can not use simultaneously, and those A are known to the dyeability of cation dyes, so embodiment does not enumerate selecting for use too much of A yet.
The specific embodiment
In an embodiment:
Fiber cationic dye dye-uptake (dye-uptake I) assay method:
Adopt cation dyes (peacock green, maximum absorption wavelength are 618nm), bath raio is 1: 100, PH=4～5 (regulating with acetic acid and sodium acetate).Dyeing is that initial temperature is 70 ℃, and programming rate is 1 ℃/min, to 100 ℃ of constant temperature 1 hour, and cool to room temperature then, washing.Measure the dyeing absorbance and the absorbance of raffinate afterwards that dyes of stoste before respectively with spectrophotometer, and obtain dye-uptake according to the dye-uptake formula.
Fiber ACID DYES dye-uptake (dye-uptake II) assay method:
Adopt that ACID DYES vapour crust Tectlion is red, maximum absorption wavelength is that 510nm, bath raio are 1: 100, PH=2～4 (acetic acid adjusting).30 ℃ of dyeing initial temperatures, 1.0 ℃/min of programming rate to 100 ℃ of constant temperature dyeings 1 hour, naturally cools to room temperature then, washing.Measure the dyeing absorbance and the absorbance of raffinate afterwards that dyes of stoste before respectively with spectrophotometer, and obtain dye-uptake according to the dye-uptake formula.
The dye-uptake formula:
Dye-uptake=[(A1-A2)/A1] * 100
A1: the absorbance of dye liquor before the dyeing
A2: the absorbance of raffinate after the dyeing
[embodiment 1～3]
Polyacrylonitrile copolymer A, B are dissolved in the NaSCN aqueous solution that concentration is 51.3wt% in required ratio, are mixed with stoste and always are the spinning solution of 11.8wt% admittedly.Spinning solution filters the back by spinning head spray silk with measuring pump through candle filter, and the shower nozzle degree of draft is controlled to be-75%, and tow is that-2.5 ℃, concentration are that solidification forming is an as-spun fibre in the NaSCN aqueous coagulation bath of 12wt% in temperature.The as-spun fibre tow enters cold drawing machine and carries out preliminary draft, and drafting multiple is 1.8.Be 45～65 ℃ water washing again with temperature, enter preheating machine then and enter hot drawing machine again after with heat water-spraying's preheating of 85 ℃ that tow is carried out high drafting, and drafting multiple is 4.3.Oil, oil concentration is controlled to be 3.0wt% again.The back tow that oils enters drying machine and carries out compacting by drying, and drying machine one district, two districts, three districts, four district's temperature are respectively 105 ℃, 115 ℃, 110 ℃, 100 ℃.Curl and HEAT SETTING, curling temperature is 83 ℃ again, and setting temperature is 125 ℃.Make 1.67dtex cotton acrylic fiber at last.
First monomer of A, B is an acrylonitrile in the spinning material polyacrylonitrile resin, and second, third monomer and the content in copolymer molecule thereof see Table 1 (copolymer A) and table 2 (copolymer B), and the viscosity average molecular weigh of A and B all is 6.2 ten thousand, and the weight ratio of A and B sees Table 3.
The dyeability index of fiber sees Table 3, and the physical index of fiber sees Table 4.
[embodiment 4～6]
Polyacrylonitrile copolymer A, B are dissolved in the NaSCN aqueous solution that concentration is 51.3wt% in required ratio, are mixed with stoste and always are the spinning solution of 11.8wt% admittedly.Spinning solution filters the back by spinning head spray silk with measuring pump through candle filter, and the shower nozzle degree of draft is controlled to be-76%, and tow is that-2.4 ℃, concentration are that solidification forming is an as-spun fibre in the NaSCN aqueous coagulation bath of 12wt% in temperature.The as-spun fibre tow enters cold drawing machine and carries out preliminary draft, and drafting multiple is 1.9.Be 45～65 ℃ water washing again with temperature, enter preheating machine then and enter hot drawing machine again after with heat water-spraying's preheating of 85 ℃ that tow is carried out high drafting, and drafting multiple is 4.1.Oil, oil concentration is controlled to be 2.9wt% again.The back tow that oils enters drying machine and carries out compacting by drying, and drying machine one district, two districts, three districts, four district's temperature are respectively 105 ℃, 115 ℃, 110 ℃, 100 ℃.Curl and HEAT SETTING, curling temperature is 85 ℃ again, and setting temperature is 129 ℃.Make 5.55dtex wool type acrylic fiber at last.
First monomer of A, B is an acrylonitrile in the spinning material polyacrylonitrile resin, and second, third monomer and the content in copolymer molecule thereof see Table 1 (copolymer A) and table 2 (copolymer B), and the viscosity average molecular weigh of A and B all is 6.4 ten thousand, and the weight ratio of A and B sees Table 3.
The dyeability index of fiber sees Table 3, and the physical index of fiber sees Table 4.
[embodiment 7～9]
Polyacrylonitrile copolymer A, B are dissolved in the NaSCN aqueous solution that concentration is 51.3wt% in required ratio, are mixed with stoste and always are the spinning solution of 12.0wt% admittedly.Spinning solution filters the back by spinning head spray silk with measuring pump through candle filter, and the shower nozzle degree of draft is controlled to be-75%, and tow is that-2.4 ℃, concentration are that solidification forming is an as-spun fibre in the NaSCN aqueous coagulation bath of 12wt% in temperature.The as-spun fibre tow enters cold drawing machine, carries out preliminary draft, and drafting multiple is 2.0.Be 45～65 ℃ water washing again with temperature, enter preheating machine then and enter hot drawing machine again after with heat water-spraying's preheating of 85 ℃ that tow is carried out high drafting, and drafting multiple is 4.3.Oil, oil concentration is controlled to be 3.2wt% again.The back tow that oils enters drying machine and carries out compacting by drying, and drying machine one district, two districts, three districts, four district's temperature are respectively 105 ℃, 115 ℃, 110 ℃, 100 ℃.Curl and HEAT SETTING, curling temperature is 85 ℃ again, and setting temperature is 125 ℃.Make 2.22dtex cotton acrylic fiber at last.
First monomer of A, B is an acrylonitrile in the spinning material polyacrylonitrile resin, and second, third monomer and the content in copolymer molecule thereof see Table 1 (copolymer A) and table 2 (copolymer B), and the viscosity average molecular weigh of A and B all is 6.4 ten thousand, and the weight ratio of A and B sees Table 3.
The dyeability index of fiber sees Table 3, and the physical index of fiber sees Table 4.
Table 1
| Second monomer | Second content of monomer (wt%) | The 3rd monomer | The 3rd content of monomer (wt%) | |
| Embodiment 1 | Methyl acrylate | 8.2 | 2-acrylamido-2-methyl propane sulfonic acid | 1.21 |
| Embodiment 2 | Methyl acrylate | 8.2 | 2-acrylamido-2-methyl propane sulfonic acid | 1.06 |
| Embodiment 3 | Methyl acrylate | 8.2 | 2-acrylamido-2-methyl propane sulfonic acid | 0.85 |
| Embodiment 4 | Vinylacetate | 12 | Methylpropene sodium sulfonate | 5.0 |
| Embodiment 5 | Vinylacetate | 12 | Methylpropene sodium sulfonate | 1.38 |
| Embodiment 6 | Vinylacetate | 16.5 | Methylpropene sodium sulfonate | 1.38 |
| Embodiment 7 | Methyl acrylate | 8 | Methylpropene sodium sulfonate | 5.0 |
| Embodiment 8 | Methyl acrylate | 5.5 | Methylpropene sodium sulfonate | 1.51 |
| Embodiment 9 | Methyl acrylate | 8 | Methylpropene sodium sulfonate | 0.89 |
Table 2
| Second monomer | Second content of monomer (wt%) | The 3rd monomer | The 3rd content of monomer (wt%) | |
| Embodiment 1 | Vinylacetate | 12.2 | Methacrylic acid N, N dimethylaminoethyl sulfate | 3.5 |
| Embodiment 2 | Vinylacetate | 12.5 | Methacrylic acid N, N dimethylaminoethyl sulfate | 4.6 |
| Embodiment 3 | Vinylacetate | 12.1 | Methacrylic acid N, N dimethylaminoethyl sulfate | 10.0 |
| Embodiment 4 | Methyl acrylate | 8.5 | Methacrylic acid N, N dimethylaminoethyl hydrochloride | 6.0 |
| Embodiment 5 | Methyl acrylate | 5.5 | Methacrylic acid N, N dimethylaminoethyl hydrochloride | 8.7 |
| Embodiment 6 | Methyl acrylate | 8.0 | Methacrylic acid N, N dimethylaminoethyl hydrochloride | 10.0 |
| Embodiment 7 | Vinylacetate | 12.0 | Methacrylic acid N, N dimethylaminoethyl nitrate | 5.9 |
| Embodiment 8 | Vinylacetate | 16.2 | Methacrylic acid N, N dimethylaminoethyl nitrate | 7.6 |
| Embodiment 9 | Vinylacetate | 12.0 | Methacrylic acid N, N dimethylaminoethyl nitrate | 12.5 |
Table 3.
| A/B (weight ratio) | Dye-uptake I (%) | Dye-uptake II (%) | |
| Embodiment 1 | 1/0.60 | 88.9 | 84.6 |
| Embodiment 2 | 1/0.78 | 88.4 | 88.4 |
| Embodiment 3 | 1/1.12 | 86.3 | 93.1 |
| Embodiment 4 | 1/0.82 | 92.5 | 90.8 |
| Embodiment 5 | 1/0.95 | 88.7 | 92.4 |
| Embodiment 6 | 1/1.60 | 87.6 | 97.2 |
| Embodiment 7 | 1/0.75 | 93.2 | 90.0 |
| Embodiment 8 | 1/0.97 | 90.1 | 91.6 |
| Embodiment 9 | 1/1.23 | 85.8 | 97.8 |
Table 4.
| Fracture strength (CN/dtex) | Extension at break (%) | Fault (mg/100g) | Crimpness (%) | |
| Embodiment 1 | 3.2 | 44 | 28 | 11 |
| Embodiment 2 | 3.1 | 43 | 25 | 12 |
| Embodiment 3 | 3.1 | 43 | 24 | 11 |
| Embodiment 4 | 2.8 | 48 | 40 | 15 |
| Embodiment 5 | 2.7 | 47 | 41 | 13 |
| Embodiment 6 | 2.5 | 48 | 44 | 13 |
| Embodiment 7 | 3.0 | 45 | 22 | 12 |
| Embodiment 8 | 2.9 | 46 | 25 | 11 |
| Embodiment 9 | 3.1 | 44 | 23 | 12 |
Claims (7)
1, the manufacture method of a kind of cation dyes and the ACID DYES acrylic fibers that all can dye, this method comprises process:
1) polyacrylonitrile resin A and B are dissolved in solvent and make spinning solution, A or B are terpolymer, viscosity average molecular weigh is 4～70,000, both first monomers are acrylonitrile, second monomer is methyl acrylate or vinylacetate, wherein the 3rd monomer of A is methylpropene sodium sulfonate or 2-acrylamido-2-methyl propane sulfonic acid, the 3rd monomer of B is methacrylic acid N, N dimethylaminoethyl nitrate, methacrylic acid N, N dimethylaminoethyl hydrochloride or methacrylic acid N, a kind of in the N dimethylaminoethyl sulfate, total amount in three kinds of comonomers, second content of monomer of A or B is 5.5～16.5wt%, the 3rd content of monomer of A is 0.8～5.0wt%, the 3rd content of monomer of B is 3.3～12.5wt%, the weight ratio of A and B is A: B=1 in the spinning solution: (0.6～1.6), total solid content is 8～20%, and solvent is that concentration is the NaSCN aqueous solution of 35～58wt%;
2) spinning solution is configured as as-spun fibre by coagulating bath behind the spray silk, and the shower nozzle degree of draft is-70～-85%, and coagulating bath is that concentration is the NaSCN aqueous solution of 8～15wt%, and coagulation bath temperature is-5～8 ℃;
3) as-spun fibre is made the acrylic fiber product through last handling process.
2, the manufacture method of acrylic fibers according to claim 1, the 3rd monomer that it is characterized in that described A is a methylpropene sodium sulfonate.
3, the manufacture method of acrylic fibers according to claim 1, the 3rd monomer that it is characterized in that described B are methacrylic acid N, N dimethylaminoethyl nitrate or methacrylic acid N, N dimethylaminoethyl hydrochloride.
4, the manufacture method of acrylic fibers according to claim 1, the 3rd content of monomer that it is characterized in that described B is 6.0～10.0wt%.
5, the manufacture method of acrylic fibers according to claim 1 is characterized in that total solid content is 10～18wt% in the described spinning solution.
6, the manufacture method of acrylic fibers according to claim 1 is characterized in that described A and the B powdery polymer for obtaining by aqueous polymerization.
7, the manufacture method of acrylic fibers according to claim 1, it is characterized in that described as-spun fibre the last handling process of process comprise cold drawing-off, washing, hot drawing-off, oil, compacting by drying, curl and HEAT SETTING.
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101450981B (en) * | 2007-12-07 | 2011-01-26 | 中国石化上海石油化工股份有限公司 | Method for preparing acrylonitrile copolymer |
| CN101450978B (en) * | 2007-12-07 | 2011-01-26 | 中国石化上海石油化工股份有限公司 | Method for preparing acrylonitrile copolymer for producing acrylic fiber |
| CN102400234B (en) * | 2010-09-17 | 2013-10-23 | 中国石油化工股份有限公司 | Method for preparing polyacrylonitrile-based carbon fiber protofilament spinning stock solution |
| CN102102234B (en) * | 2010-12-22 | 2013-08-14 | 中国科学院山西煤炭化学研究所 | Ternary copolymerization highly hydrophilic polyacrylonitrile-based carbon fiber spinning solution and preparation method thereof |
| CN103668531B (en) * | 2012-09-25 | 2017-01-18 | 中国石油化工股份有限公司 | Method for preparing anti-pilling acrylic fibers from acrylonitrile and vinyl chloride |
| CN103668532B (en) * | 2012-09-25 | 2016-12-21 | 中国石油化工股份有限公司 | Utilize the method that acrylonitrile and vinylacetate prepare anti-pilling acrylic fiber |
| CN103668530B (en) * | 2012-09-25 | 2016-05-25 | 中国石油化工股份有限公司 | Utilize acrylonitrile and methyl methacrylate to prepare the method for anti-pilling acrylic fiber |
| CN103409838B (en) * | 2013-08-12 | 2016-08-17 | 常州大学 | A kind of method improving the liquid-solid body burden of acrylic spinning |
| CN104562270A (en) * | 2013-10-11 | 2015-04-29 | 中国石油化工股份有限公司 | Wet spinning method for improving acrylic fiber glossiness |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4955922A (en) * | 1972-10-03 | 1974-05-30 | ||
| CN1143985A (en) * | 1994-01-26 | 1997-02-26 | 孟山都公司 | Fibre bundles including reversible crimp filaments having improved dyeability |
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2005
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4955922A (en) * | 1972-10-03 | 1974-05-30 | ||
| CN1143985A (en) * | 1994-01-26 | 1997-02-26 | 孟山都公司 | Fibre bundles including reversible crimp filaments having improved dyeability |
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