EP2207920A1 - Method for preparing polyurethaneurea elastic fiber with improved heat settability and polyurethaneurea elastic fiber prepared by the same - Google Patents
Method for preparing polyurethaneurea elastic fiber with improved heat settability and polyurethaneurea elastic fiber prepared by the sameInfo
- Publication number
- EP2207920A1 EP2207920A1 EP07851459A EP07851459A EP2207920A1 EP 2207920 A1 EP2207920 A1 EP 2207920A1 EP 07851459 A EP07851459 A EP 07851459A EP 07851459 A EP07851459 A EP 07851459A EP 2207920 A1 EP2207920 A1 EP 2207920A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- elastic fiber
- polyurethaneurea
- prepolymer
- diphenylmethanediisocyanate
- polyurethaneurea elastic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 229920003226 polyurethane urea Polymers 0.000 title claims abstract description 65
- 210000004177 elastic tissue Anatomy 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 24
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000009987 spinning Methods 0.000 claims abstract description 17
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 13
- 229920005862 polyol Polymers 0.000 claims abstract description 12
- 150000003077 polyols Chemical class 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000004970 Chain extender Substances 0.000 claims description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 7
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 7
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 7
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 6
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 6
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 6
- 150000002009 diols Chemical class 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- 239000005700 Putrescine Substances 0.000 claims description 3
- GHWVXCQZPNWFRO-UHFFFAOYSA-N butane-2,3-diamine Chemical compound CC(N)C(C)N GHWVXCQZPNWFRO-UHFFFAOYSA-N 0.000 claims description 3
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 239000004744 fabric Substances 0.000 description 19
- 239000000835 fiber Substances 0.000 description 10
- 238000009998 heat setting Methods 0.000 description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 8
- 229940113088 dimethylacetamide Drugs 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000004677 Nylon Substances 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 229920001778 nylon Polymers 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000009940 knitting Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 229920002334 Spandex Polymers 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004759 spandex Substances 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- ACZGCWSMSTYWDQ-UHFFFAOYSA-N 3h-1-benzofuran-2-one Chemical compound C1=CC=C2OC(=O)CC2=C1 ACZGCWSMSTYWDQ-UHFFFAOYSA-N 0.000 description 1
- CYHYIIFODCKQNP-UHFFFAOYSA-N 5,7-ditert-butyl-3-(3,4-dimethylphenyl)-3h-1-benzofuran-2-one Chemical compound C1=C(C)C(C)=CC=C1C1C(C=C(C=C2C(C)(C)C)C(C)(C)C)=C2OC1=O CYHYIIFODCKQNP-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000000578 dry spinning Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- -1 polyol compound Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical compound NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
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
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
Definitions
- the present invention relates to a method for preparing polyurethaneurea elastic fiber with improved heat-set efficiency and polyurethaneurea elastic fiber prepared by the same, and more particularly to a method for preparing polyurethaneurea elastic fiber with improved heat-set efficiency, in which a prepolymer is prepared from a mixture of at least one of diisocyanate of polyurethaneurea comprising 4,4'-diphenylmethanediisocyanate and 2,4'-diphenylmethanediisocyanate, and polyurethaneurea elastic fiber prepared by the same.
- polyurethaneurea elastic fiber is prepared as follows. First, a polyol compound with a large molecular weight is reacted with excessive amount of diisocyanate to prepare a prepolymer having isocyanate groups at both ends of the polyol. Then, after dissolving the prepolymer in an adequate solvent, a diamine- or diol-based chain extender and a chain terminator such as monoalcohol, monoamine, etc. are added to the resulting solution to produce a polyurethaneurea spinning solution. Subsequently, polyurethaneurea elastic fiber is prepared by dry- or wet- spinning the polyurethaneurea spinning solution.
- Such prepared polyurethaneurea fiber is characterized by its high elasticity, and widely used in a variety of areas such as functional underwear, sports wear, and the like as weaved together with polyamide, polyester or natural fibers. As its usage has expanded, there is a growing demand for developing extra features of conventional fibers.
- polyurethaneurea fiber is heat-set at high temperature.
- heat-sensitive fibers such as nylon, cotton, silk, wool, etc. that is weaved together with polyurethaneurea during post-process after knitting.
- Japanese Patent Laid-Open No. Hei 7-82608 discloses a method for preparing polyurethaneurea elastic fiber having excellent stability of polymer solution, not causing knitting unevenness in processing by using diphenylmethanediisocyanate comprising 1.8 to 13 wt% fraction of 2,4'-diphenylmethanediisocyanate.
- the invention provides high strength at break and heat resistance, but insufficient heat-set efficiency.
- U.S. Patent No. 6,472,494 discloses spandex prepared from a mixture of 23 to 55 mole % of 2,4'-diphenylmethanediisocyanate and 4,4'-diphenylmethanediisocyanate, polyether glycol and a chain extender.
- the resultant polyurethaneurea elastic fiber has improved heat-set efficiency.
- it is unfavorable in spinning, because of greatly deteriorated modulus and elasticity recovery and insufficient yarn evenness.
- the present invention has been made in an effort to solve the above- described problems associated with the prior art, and it is an object of the present invention to provide a method for preparing polyurethaneurea elastic fiber with improved yarn evenness and high heat-set efficiency.
- a method for preparing polyurethaneurea elastic fiber by polymerizing polyol with excessive amount of diisocyanate to produce a prepolymer (first polymerization), and dissolving the prepolymer in an organic solvent and then adding a chain extender and a chain terminator thereto (second polymerization) to produce polyurethaneurea elastic fiber, characterized in that the prepolymer is prepared by reacting a mixture of at least one diisocyanate comprising 4,4'-diphenylmethanediisocyanate and 7 to 25 mole % of 2,4'-diphenylmethanediisocyanate with polyol.
- the diisocyanate is at least one selected from the group consisting of 4,4'-diphenylmethanediisocyanate, 1 ,5'-naphthalenediisocyanate, 1 ,4'-phenylenediisocyanate, hexamethylenediisocyanate, 1 ,4'-cyclohexanediisocyanate, 4,4'-dicyclohexylmethanediisocyanate and isophoronediisocyanate
- the polyol of the prepolymer is one selected from the group consisting of polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol and a combination thereof
- the chain extender is at least one selected from the group consisting of ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 2,3-diaminobutane, 1,5-d
- weight proportion of isocyanate of the prepolymer is from 1.75 % to 4.13 %.
- Segmented polyurethaneurea used to prepare the elastic fiber of the present invention is prepared by reacting organic diisocyanate with polymer diol to produce a p repolymer, and dissolving the prepolymer in an organic solvent and then reacting with diamine and monoamine.
- Examples of the diisocyanate used to prepare the polyurethaneurea elastic fiber of the present invention may include at least one selected from the group consisting of 4,4'-diphenylmethanediisocyanate, 2,4'-diphenylmethanediisocyanate, 1 ,5'-naphthalenediisocyanate, 1 ,4'-phenylenediisocyanate, hexamethylenediisocyanate, 1 ,4'-cyclohexanediisocyanate, 4,4'-dicyclohexylmethanediisocyanate and isophoronediisocyanate, but is not necessarily limited thereto.
- At least one diisocyanate comprising
- 4,4'-diphenylmethanediisocyanate is mixed with 2,4'-diphenylmethanediisocyanate. It is preferable that the proportion of the 2,4'-diphenylmethanediisocyanate is from 7 to 25 mole %.
- the 2,4'-diphenylmethanediisocyanate is included in an amount less than 7 mole %, selvage curling may occur during heat-setting process at low temperature because of insufficient heat-setting efficiency. And, when it is included in an amount exceeding 25 mole %, modulus may decrease abruptly. Hence, it is preferable that the 2,4'-diphenylmethanediisocyanate is included in an amount within the aforesaid range.
- the polyol used in the present invention may be one selected from the group consisting of polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol and a combination thereof, but is not necessarily limited thereto.
- the chain extender used in the present invention may be a diamine.
- the chain extender may be at least one selected from the group consisting of ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 2,3-diaminobutane, 1,5-diaminopentane, 1,6-hexamethylenediamine, 1,4-cyclohexanediamine and a combination thereof, but is not necessarily limited thereto.
- Examples of the chain terminator used to control the molecular weight of polyurethaneurea may include amine having one functional group such as di- ethylamine, monoethanolamine, dimethylamine and so on.
- sterically hindered phenolic compounds in order to prevent discoloration or property impairment of polyurethaneurea that may be caused by UV, smog or heat-setting process for spandex, sterically hindered phenolic compounds, benzofuranone based compounds, semi- carbazide based compounds, benzotriazole based compounds, or polymeric tertiary amine stabilizers may be added in combination into a spinning solution.
- polyurethaneurea elastic fiber of the present invention may further comprise additives such as titanium dioxide, magnesium stearate, etc.
- the weight proportion of isocyanate of the prepolymer is maintained from
- Heat-set efficiency (%) [(heat-set length - original length) / (stretched length - original length)] x 100
- NCO% [100 x 2 x formula weight of NCO x (CR-I)] / [(molecular weight of di- isocyanate x CR) + molecular weight of polyol]
- CR (capping ratio) molar ratio of diisocyanate / molar ratio of polyol
- the produced yarns were mounted on a U% measurement apparatus (Keisokki Co.) and winded. After 20 seconds of unwinding, the thickness of yarns is measured with an evenness sensor and averaged. Average value is depicted as 0 % line in the chart. When the yarns are thicker than the average, points are marked over the 0 % line. And, when the yarns are thinner, they are marked below the 0 % line. U% is the deviation from the reference line as calculated from the area ratio. A smaller U% means superior yarn evenness.
- Polyurethaneurea elastic fiber was prepared in the same manner as in Example 1, except for changing the proportion of 2,4'-diphenylmethanediisocyanate to 4,4'-diphenylmethanediisocyanate. Physical properties thereof were evaluated in the same way, and the results were shown in Table 1.
- Polyurethaneurea elastic fiber was prepared in the same manner as in Example 1, except for changing the proportion of 2,4'-diphenylmethanediisocyanate to 4,4'-diphenylmethanediisocyanate. Physical properties thereof were evaluated in the same way, and the results were shown in Table 1.
- the polyurethaneurea elastic fiber of the present invention has high heat-set efficiency at low temperature. Therefore, thermal degradation of the fiber that is weaved together with polyurethaneurea can be prevented with the heat-set process at low temperature, which resulted in superior hand-feel of the resulting fabric available in various areas.
Abstract
The present invention relates to a method for preparing polyurethaneurea elastic fiber, the method comprising reacting a mixture of at least one diisocyanate comprising 4,4'-diphenylmethanediisocyanate and 7 to 25 mole % of 2,4'-diphenylmethanediisocyanate with polyol to produce a prepolymer, and polyurethaneurea elastic fiber prepared by the same. The polyurethaneurea elastic fiber of the present invention has superior spinning workability, improved yarn evenness, and high heat-set efficiency even at low temperature.
Description
Description METHOD FOR PREPARING POLYURETHANEUREA ELASTIC
FIBER WITH IMPROVED HEAT SETTABILITY AND POLYURETHANEUREA ELASTIC FIBER PREPARED BY THE
SAME Technical Field
[1] The present invention relates to a method for preparing polyurethaneurea elastic fiber with improved heat-set efficiency and polyurethaneurea elastic fiber prepared by the same, and more particularly to a method for preparing polyurethaneurea elastic fiber with improved heat-set efficiency, in which a prepolymer is prepared from a mixture of at least one of diisocyanate of polyurethaneurea comprising 4,4'-diphenylmethanediisocyanate and 2,4'-diphenylmethanediisocyanate, and polyurethaneurea elastic fiber prepared by the same. Background Art
[2] In general, polyurethaneurea elastic fiber is prepared as follows. First, a polyol compound with a large molecular weight is reacted with excessive amount of diisocyanate to prepare a prepolymer having isocyanate groups at both ends of the polyol. Then, after dissolving the prepolymer in an adequate solvent, a diamine- or diol-based chain extender and a chain terminator such as monoalcohol, monoamine, etc. are added to the resulting solution to produce a polyurethaneurea spinning solution. Subsequently, polyurethaneurea elastic fiber is prepared by dry- or wet- spinning the polyurethaneurea spinning solution.
[3] Such prepared polyurethaneurea fiber is characterized by its high elasticity, and widely used in a variety of areas such as functional underwear, sports wear, and the like as weaved together with polyamide, polyester or natural fibers. As its usage has expanded, there is a growing demand for developing extra features of conventional fibers.
[4] In general, polyurethaneurea fiber is heat-set at high temperature. As a result, there is thermal degradation of heat-sensitive fibers such as nylon, cotton, silk, wool, etc. that is weaved together with polyurethaneurea during post-process after knitting. In order to prevent such thermal degradation and improve dimensional stability of the fabric, it is increasingly necessary to develop a polyurethaneurea fiber to be heat-set at low temperature.
[5] Japanese Patent Laid-Open No. Hei 7-82608 discloses a method for preparing polyurethaneurea elastic fiber having excellent stability of polymer solution, not
causing knitting unevenness in processing by using diphenylmethanediisocyanate comprising 1.8 to 13 wt% fraction of 2,4'-diphenylmethanediisocyanate. The invention provides high strength at break and heat resistance, but insufficient heat-set efficiency. U.S. Patent No. 6,472,494 discloses spandex prepared from a mixture of 23 to 55 mole % of 2,4'-diphenylmethanediisocyanate and 4,4'-diphenylmethanediisocyanate, polyether glycol and a chain extender. By significantly increasing the content of the 2,4'-diphenylmethanediisocyanate to 23 to 55 mole %, the resultant polyurethaneurea elastic fiber has improved heat-set efficiency. However, it is unfavorable in spinning, because of greatly deteriorated modulus and elasticity recovery and insufficient yarn evenness.
Disclosure of Invention Technical Problem
[6] Therefore, the present invention has been made in an effort to solve the above- described problems associated with the prior art, and it is an object of the present invention to provide a method for preparing polyurethaneurea elastic fiber with improved yarn evenness and high heat-set efficiency.
[7] It is an another object of the present invention to provide polyurethaneurea elastic fiber which is prepared by the method of the present invention and has superior spinning workability, improved yarn evenness, and high heat-set efficiency at low temperature. Technical Solution
[8] In accordance with an aspect of the present invention, there is provided a method for preparing polyurethaneurea elastic fiber by polymerizing polyol with excessive amount of diisocyanate to produce a prepolymer (first polymerization), and dissolving the prepolymer in an organic solvent and then adding a chain extender and a chain terminator thereto (second polymerization) to produce polyurethaneurea elastic fiber, characterized in that the prepolymer is prepared by reacting a mixture of at least one diisocyanate comprising 4,4'-diphenylmethanediisocyanate and 7 to 25 mole % of 2,4'-diphenylmethanediisocyanate with polyol. Preferably, the diisocyanate is at least one selected from the group consisting of 4,4'-diphenylmethanediisocyanate, 1 ,5'-naphthalenediisocyanate, 1 ,4'-phenylenediisocyanate, hexamethylenediisocyanate, 1 ,4'-cyclohexanediisocyanate, 4,4'-dicyclohexylmethanediisocyanate and isophoronediisocyanate, the polyol of the prepolymer is one selected from the group consisting of polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol and a combination thereof, and the chain extender is at least one selected from the group consisting of ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 2,3-diaminobutane, 1,5-diaminopentane,
1,6-hexamethylenediamine, 1,4-cyclohexanediamine and a combination thereof. Also, preferably, weight proportion of isocyanate of the prepolymer is from 1.75 % to 4.13 %. [9] According to another aspect of the present invention, there is provide polyurethaneurea elastic fiber prepared by the method described above, which has superior spinning workability, improved yarn evenness, and high heat-set efficiency at low temperature.
Advantageous Effects
[10] According to the present invention, it is possible to produce polyurethaneurea elastic fiber with superior spinning workability, improved yarn evenness, and high heat-set efficiency. Since heat-setting can be performed at low temperature, thermal degradation of the fiber that is weaved together with polyurethaneurea can be prevented, hand- feel of the fabric can be improved, and selvage curling of knitted fabric during processing after heat-setting can be prevented. Mode for the Invention
[11] Hereinafter, a method for preparing polyurethaneurea elastic fiber according to the present invention will be described in detail.
[12] Segmented polyurethaneurea used to prepare the elastic fiber of the present invention is prepared by reacting organic diisocyanate with polymer diol to produce a p repolymer, and dissolving the prepolymer in an organic solvent and then reacting with diamine and monoamine.
[13] Examples of the diisocyanate used to prepare the polyurethaneurea elastic fiber of the present invention may include at least one selected from the group consisting of 4,4'-diphenylmethanediisocyanate, 2,4'-diphenylmethanediisocyanate, 1 ,5'-naphthalenediisocyanate, 1 ,4'-phenylenediisocyanate, hexamethylenediisocyanate, 1 ,4'-cyclohexanediisocyanate, 4,4'-dicyclohexylmethanediisocyanate and isophoronediisocyanate, but is not necessarily limited thereto.
[14] In the method of the present invention, at least one diisocyanate comprising
4,4'-diphenylmethanediisocyanate is mixed with 2,4'-diphenylmethanediisocyanate. It is preferable that the proportion of the 2,4'-diphenylmethanediisocyanate is from 7 to 25 mole %. When the 2,4'-diphenylmethanediisocyanate is included in an amount less than 7 mole %, selvage curling may occur during heat-setting process at low temperature because of insufficient heat-setting efficiency. And, when it is included in an amount exceeding 25 mole %, modulus may decrease abruptly. Hence, it is preferable that the 2,4'-diphenylmethanediisocyanate is included in an amount within the aforesaid range.
[15] The polyol used in the present invention may be one selected from the group
consisting of polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol and a combination thereof, but is not necessarily limited thereto.
[16] The chain extender used in the present invention may be a diamine. For example, the chain extender may be at least one selected from the group consisting of ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 2,3-diaminobutane, 1,5-diaminopentane, 1,6-hexamethylenediamine, 1,4-cyclohexanediamine and a combination thereof, but is not necessarily limited thereto.
[17] Examples of the chain terminator used to control the molecular weight of polyurethaneurea may include amine having one functional group such as di- ethylamine, monoethanolamine, dimethylamine and so on.
[18] Furthermore, in order to prevent discoloration or property impairment of polyurethaneurea that may be caused by UV, smog or heat-setting process for spandex, sterically hindered phenolic compounds, benzofuranone based compounds, semi- carbazide based compounds, benzotriazole based compounds, or polymeric tertiary amine stabilizers may be added in combination into a spinning solution.
[19] In addition, the polyurethaneurea elastic fiber of the present invention may further comprise additives such as titanium dioxide, magnesium stearate, etc.
[20] Preferably, the weight proportion of isocyanate of the prepolymer is maintained from
1.75 % to 4.13 % so as to have the properties of polyurethaneurea elastic fiber.
[21]
[22] Hereinafter, the present invention will be described in detail with reference to the following non-limiting examples. It should nevertheless be understood that the same is considered as illustrative and no limitation of the scope of the present invention is thereby intended.
[23]
[24] In the following Examples and Comparative Examples, heat-set efficiency, NCO%,
U%, workability, selvage curling and hand- feel of polyurethaneurea fiber were evaluated as follows.
[25]
[26] Heat- set efficiency of polyurethaneurea yarns
[27] The produced yarns were stretched 100 % as exposed in the air, and were heated at
170 0C for 1 minute in an oven. After cooling to room temperature, the length of the yarns was measured and heat-set efficiency was calculated according to the following formula:
[28] Heat-set efficiency (%) = [(heat-set length - original length) / (stretched length - original length)] x 100
[29]
[30] NCO%
[31] NCO% = [100 x 2 x formula weight of NCO x (CR-I)] / [(molecular weight of di- isocyanate x CR) + molecular weight of polyol]
[32] Note) CR (capping ratio) = molar ratio of diisocyanate / molar ratio of polyol
[33]
[34] U%
[35] The produced yarns were mounted on a U% measurement apparatus (Keisokki Co.) and winded. After 20 seconds of unwinding, the thickness of yarns is measured with an evenness sensor and averaged. Average value is depicted as 0 % line in the chart. When the yarns are thicker than the average, points are marked over the 0 % line. And, when the yarns are thinner, they are marked below the 0 % line. U% is the deviation from the reference line as calculated from the area ratio. A smaller U% means superior yarn evenness.
[36]
[37] Workability
[38] Workability means the proportion of yarns with no defects of the total yarns produced a day. A higher workability means that good yarns with no defects such as cutting or twisting are produced.
[39]
[40] Selvage curling
[41] On circular knitted fabric made of nylon/polyurethaneurea elastic fiber, a regular triangle with one side being 5 cm is drawn. After scissoring two sides and spraying water, the fabric is dried. After drying the ratio of the curled area to the initial area is calculated.
[42] Selvage curling (%) = (area of curled triangle / area of original triangle) x 100
[43]
[44] Hand-feel of fabric
[45] Hand- feel of fabric is evaluated depending on sensual judgment. The inventors evaluated hardness, flexibility, elasticity, softness, drape, warmth or coolness, luster, etc. with eyes and hands in view that the articles are judged by experience.
[46]
[47] Example 1
[48] 32 g of 2,4'-diphenylmethanediisocyanate, 427 g of
4,4'-diphenylmethanediisocyanate and 2000 g of polytetramethylene ether glycol (molecular weight = 1800) were reacted with agitation at 90 0C for 180 minutes in nitrogen gas flow to produce a polyurethaneurea prepolymer having isocyanate groups on both ends thereof. The prepolymer was cooled to room temperature, and 3614 g of dimethylacetamide was added to produce a polyurethaneurea prepolymer solution.
Subsequently, 33.6 g (0.56 mol) of ethylenediamine, 10.4 g (0.14 mol) of 1,2-diaminopropane and 5.14 g of diethylamine were dissolved in 656 g of dimethy- lacetamide, and added to the prepolymer solution at 10 0C or below to produce a polyurethaneurea solution.
[49] Based on the solid content of the resultant polymer, 1.5 wt% of ethylenebis(oxyethylene)bis-(3-(5-?-butyl-4-hydroxy-m-toyl)-propionate), 0.5 wt% of 5,7-di-?-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one, 1 wt% of l,l,l,l-tetramethyl-4,4'-(methylene-di-/7-phenylene)disemicarbazide, 1 wt% of poly (N, JV-diethyl-2-aminoethyl methacrylate), and 0.1 wt% of titanium dioxide were added as a additive and mixed to produce a polyurethaneurea spinning solution.
[50] The spinning solution was then dry-spun (spinning temperature: 253 0C) to produce
40 denier polyurethaneurea elastic fiber. Physical properties thereof were evaluated, and the results were shown in Table 1.
[51]
[52] Example 2
[53] 46 g of 2,4'-diphenylmethanediisocyanate, 413 g of
4,4'-diphenylmethanediisocyanate and 2000 g of polytetramethylene ether glycol (molecular weight = 1800) were reacted with agitation at 90 0C for 180 minutes in nitrogen gas flow to produce a polyurethaneurea prepolymer having isocyanate groups on both ends thereof. The prepolymer was cooled to room temperature, and 3614 g of dimethylacetamide was added to produce a polyurethaneurea prepolymer solution. Subsequently, 33.6 g (0.56 mol) of ethylenediamine, 10.4 g (0.14 mol) of 1,2-diaminopropane and 5.14 g of diethylamine were dissolved in 656 g of dimethylacetamide, and added to the prepolymer solution at 10 0C or below to produce a polyurethaneurea solution.
[54] Based on the solid content of the resultant polymer, 1.5 wt% of ethylenebis(oxyethylene)bis-(3-(5-?-butyl-4-hydroxy-m-toyl)-propionate), 0.5 wt% of 5,7-di-t-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one, 1 wt% of l,l,l,l-tetramethyl-4,4'-(methylene-di-/7-phenylene)disemicarbazide, 1 wt% of poly (N, JV-diethyl-2-aminoethyl methacrylate), and 0.1 wt% of titanium dioxide were added as a additive and mixed to produce a polyurethaneurea spinning solution.
[55] The spinning solution was then dry-spun (spinning temperature: 253 0C) to produce
40 denier polyurethaneurea elastic fiber. Physical properties thereof were evaluated, and the results were shown in Table 1.
[56]
[57] Examples 3 and 4
[58] Polyurethaneurea elastic fiber was prepared in the same manner as in Example 1, except for changing the proportion of 2,4'-diphenylmethanediisocyanate to
4,4'-diphenylmethanediisocyanate. Physical properties thereof were evaluated in the same way, and the results were shown in Table 1.
[59]
[60] Example 5
[61] 80 g of 2,4'-diphenylmethanediisocyanate, 453 g of
4,4'-diphenylmethanediisocyanate and 2000 g of polytetramethylene ether glycol (molecular weight = 1800) were reacted with agitation at 90 0C for 180 minutes in nitrogen gas flow to produce a polyurethaneurea prepolymer having isocyanate groups on both ends thereof. The prepolymer was cooled to room temperature, and 3512 g of dimethylacetamide was added to produce a polyurethaneurea prepolymer solution. Subsequently, 46.6 g (0.78 mol) of ethylenediamine, 14.44 g (0.19 mol) of 1,2-diaminopropane and 7.5 g of diethylamine were dissolved in 909 g of dimethylacetamide, and added to the prepolymer solution at 10 0C or below to produce a polyurethaneurea solution. Addition of additives and spinning were performed in the same manner as in Example 1 to produce polyurethaneurea elastic fiber. Physical properties thereof were evaluated, and the results were shown in Table 1.
[62]
[63] Comparative Example 1
[64] 459 g of 4,4'-diphenylmethanediisocyanate and 2000 g of polytetramethylene ether glycol (molecular weight = 1800) were reacted with agitation at 90 0C for 180 minutes in nitrogen gas flow to produce a polyurethaneurea prepolymer having isocyanate groups on both ends thereof. The prepolymer was cooled to room temperature, and 3614 g of dimethylacetamide was added to produce a polyurethaneurea prepolymer solution. Subsequently, 33.6 g (0.56 mol) of ethylenediamine, 10.4 g (0.14 mol) of 1,2-diaminopropane and 5.14 g of diethylamine were dissolved in 656 g of dimethylacetamide, and added to the prepolymer solution at 10 0C or below to produce a polyurethaneurea solution. Addition of additives and spinning were performed in the same manner as in Example 1 to produce polyurethaneurea elastic fiber. Physical properties thereof were evaluated in the same way, and the results were shown in Table 1.
[65]
[66] Comparative Examples 2 and 3
[67] Polyurethaneurea elastic fiber was prepared in the same manner as in Example 1, except for changing the proportion of 2,4'-diphenylmethanediisocyanate to 4,4'-diphenylmethanediisocyanate. Physical properties thereof were evaluated in the same way, and the results were shown in Table 1.
[68]
[69] Table 1
[Table 1] [Table ]
[70] [71] As shown in Table 1, the polyurethaneurea elastic fiber comprising less than 7 mole % of 2,4'-diphenylmethanediisocyanate exhibited slightly lower heat-set efficiency. When the content of 2,4'-diphenylmethanediisocyanate was in excess of 25 mole %, heat-set efficiency was improved significantly, but yarn evenness reduced significantly and workability was poor.
[72] [73] Examples 6 and 7 [74] Circular knitted fabrics were made from the elastic fiber prepared in Example 3 and nylon yarn, using a circular knitting machine (Mayer Co.) with 38 inches cylinder diameter, 28 gauge, 120 feeder. They were then treated under heat-setting conditions shown in Table 2. The selvage curling (%) and hand-feel of the resulting fabrics were evaluated, and the results were shown in Table 2. 70 denier nylon and 40 denier elastic fiber were used in preparing the circular knitted fabric. The content of the elastic fiber was 8 wt%, based on the total weight of the fabric.
[75] [76] Comparative Examples 4 and 5 [77] Circular knitted fabrics were made in the same manner as in Example 6, except for using the elastic fiber prepared in Comparative Example 1 and changing heat-setting conditions as shown in Table 2. The selvage curling (%) and hand-feel of the resulting fabrics were evaluated in the same manner, and the results were shown in Table 2.
[79] Table 2 [Table 2] [Table ]
Pre- setting Finish setting Selvage Hand-feel of temperature (0C) temperature (0C) curling (%) fabric
Ex. 6 170 165 0 Superior
Ex. 7 175 160 0 Superior
Comp. Ex. 4 190 180 0 Poor
Comp. Ex. 5 180 170 100 Superior
[80] [81] As shown in Table 2, in the process of preparing circular knitted nylon fabric, the fabric of Example 6 prepared with elastic fiber in Example 3 do not cause selvage curling even at about 20 0C lower heat-setting temperature, compared to the fabric in Comparative Example 4 prepared with elastic fiber in Comparative Example 1. Thus, a superior fabric with good hand- feel can be attained, without thermal degradation of nylon. Further, cost reduction can be attained by lowering the heat-setting temperature.
[82] [83] The present invention has been described in detail with reference to preferred embodiments thereof. However, it will be appreciated by those skilled in the art that changes may be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents. Industrial Applicability
[84] The polyurethaneurea elastic fiber of the present invention has high heat-set efficiency at low temperature. Therefore, thermal degradation of the fiber that is weaved together with polyurethaneurea can be prevented with the heat-set process at low temperature, which resulted in superior hand-feel of the resulting fabric available in various areas.
Claims
[1] A method for preparing polyurethaneurea elastic fiber by polymerizing polyol with excessive amount of diisocyanate to produce a prepolymer (first polymerization), and dissolving the prepolymer in an organic solvent and then adding a chain extender and a chain terminator thereto (second polymerization) to produce polyurethaneurea elastic fiber, characterized in that the prepolymer is prepared by reacting a mixture of at least one diisocyanate comprising 4,4'-diphenylmethanediisocyanate and 7 to 25 mole % of 2,4'-diphenylmethanediisocyanate with polyol.
[2] The method according to claim 1, wherein the diisocyanate is at least one selected from the group consisting of 4,4'-diphenylmethanediisocyanate, 1 ,5'-naphthalenediisocyanate, 1 ,4'-phenylenediisocyanate, hexamethylenedi- isocyanate, 1 ,4'-cyclohexanediisocyanate, 4,4'-dicyclohexylmethanediisocyanate and isophoronediisocyanate.
[3] The method according to claim 1, wherein the polyol of the prepolymer is one selected from the group consisting of polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol and a combination thereof.
[4] The method according to claim 1, wherein the chain extender is at least one selected from the group consisting of ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 2,3-diaminobutane, 1,5-diaminopentane, 10,6-hexamethylenediamine, 1,4-cyclohexanediamine and a combination thereof.
[5] The method according to claim 1, wherein weight proportion of isocyanate of the prepolymer is from 1.75 % to 4.13 %.
[6] Polyurethaneurea elastic fiber prepared by the method of claim 1, which has superior spinning workability, improved yarn evenness, and high heat-set efficiency at low temperature.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20070112524A KR100942359B1 (en) | 2007-11-06 | 2007-11-06 | Method for preparing polyurethaneurea elastic fiber with improved heat settability |
| PCT/KR2007/006488 WO2009061020A1 (en) | 2007-11-06 | 2007-12-13 | Method for preparing polyurethaneurea elastic fiber with improved heat settability and polyurethaneurea elastic fiber prepared by the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP2207920A1 true EP2207920A1 (en) | 2010-07-21 |
| EP2207920A4 EP2207920A4 (en) | 2011-10-05 |
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| Application Number | Title | Priority Date | Filing Date |
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| EP07851459A Withdrawn EP2207920A4 (en) | 2007-11-06 | 2007-12-13 | Method for preparing polyurethaneurea elastic fiber with improved heat settability and polyurethaneurea elastic fiber prepared by the same |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP2207920A4 (en) |
| KR (1) | KR100942359B1 (en) |
| CN (1) | CN101849048A (en) |
| BR (1) | BRPI0722274A2 (en) |
| WO (1) | WO2009061020A1 (en) |
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| CN102002317A (en) * | 2009-08-31 | 2011-04-06 | 日立卷线株式会社 | Polyamide-imide resin based insulating varnish and insulated wire covered with same |
| KR101167377B1 (en) * | 2009-12-31 | 2012-07-19 | 주식회사 효성 | Process for Preparing polyurethaneurea elastic fiber with improved heat settable properties |
| EP2524072B1 (en) | 2010-01-14 | 2017-09-27 | Invista Technologies S.à.r.l. | Spandex with high uniformity |
| KR101238557B1 (en) * | 2010-12-31 | 2013-02-28 | 주식회사 효성 | Manufacturing method of polyurethaneurea elastic fiber by high speed spinning method |
| CN102517688B (en) * | 2011-12-08 | 2014-04-16 | 烟台泰和新材料股份有限公司 | Preparation method of polyurethane elastomeric fiber possessing excellent heat setting performance |
| KR101526931B1 (en) * | 2012-10-15 | 2015-06-11 | 한국생산기술연구원 | Treatment agent with excellentelasticity recovery and the the knitting textile treated therewith |
| CN103255500B (en) * | 2013-05-30 | 2015-03-25 | 浙江华峰氨纶股份有限公司 | Preparation method of polyurethane elastic fiber suitable for low-temperature setting |
| CN103526331B (en) * | 2013-09-25 | 2015-06-10 | 浙江华峰氨纶股份有限公司 | Efficient production method of polyurethane elastic fiber |
| CN104726960A (en) * | 2013-12-20 | 2015-06-24 | 浙江华峰氨纶股份有限公司 | Polyurethane elastic fiber with improved heat-setting performance, and preparation method thereof |
| CN103924321A (en) * | 2014-05-06 | 2014-07-16 | 浙江华峰氨纶股份有限公司 | Preparation method of elastic polyurethane fiber with polycarbonate diols added |
| CN107663670B8 (en) * | 2017-08-16 | 2019-10-15 | 东华大学 | A kind of polyurethane elastomeric fiber and preparation method thereof |
| CN109487361B (en) * | 2018-11-23 | 2021-07-23 | 万华化学集团股份有限公司 | Spandex fiber with good heat resistance and low-temperature setting property and preparation method thereof |
| CN109610039B (en) * | 2018-12-04 | 2021-05-25 | 华峰化学股份有限公司 | Preparation method of polyurethane urea elastic fiber with high heat setting efficiency |
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| KR100514456B1 (en) * | 2003-11-25 | 2005-09-13 | 태광산업주식회사 | Polyurethaneurea Elastic Fiber Having Stable Viscosity and Good Heat-resistant Properties and Its Preparation Method |
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- 2007-11-06 KR KR20070112524A patent/KR100942359B1/en active IP Right Grant
- 2007-12-13 CN CN200780101439A patent/CN101849048A/en active Pending
- 2007-12-13 BR BRPI0722274-2A patent/BRPI0722274A2/en not_active Application Discontinuation
- 2007-12-13 EP EP07851459A patent/EP2207920A4/en not_active Withdrawn
- 2007-12-13 WO PCT/KR2007/006488 patent/WO2009061020A1/en active Application Filing
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| US20050165200A1 (en) * | 2003-05-05 | 2005-07-28 | Invista North America S.A.R.L. | Dyeable spandex |
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Also Published As
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| EP2207920A4 (en) | 2011-10-05 |
| KR20090046401A (en) | 2009-05-11 |
| BRPI0722274A2 (en) | 2014-04-22 |
| KR100942359B1 (en) | 2010-02-12 |
| WO2009061020A1 (en) | 2009-05-14 |
| CN101849048A (en) | 2010-09-29 |
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