EP2021537A1 - Spandex fibers containing partially dehydroxylated hydrotalcite - Google Patents
Spandex fibers containing partially dehydroxylated hydrotalciteInfo
- Publication number
- EP2021537A1 EP2021537A1 EP07708702A EP07708702A EP2021537A1 EP 2021537 A1 EP2021537 A1 EP 2021537A1 EP 07708702 A EP07708702 A EP 07708702A EP 07708702 A EP07708702 A EP 07708702A EP 2021537 A1 EP2021537 A1 EP 2021537A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- hydrotalcite
- acid
- spandex
- spandex fiber
- partially dehydroxylated
- 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.)
- Granted
Links
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical class [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 title claims abstract description 140
- 229920002334 Spandex Polymers 0.000 title claims abstract description 74
- 239000004759 spandex Substances 0.000 title claims abstract description 74
- 239000000835 fiber Substances 0.000 title claims abstract description 49
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 111
- 229960001545 hydrotalcite Drugs 0.000 claims description 111
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- 238000005004 MAS NMR spectroscopy Methods 0.000 claims description 8
- 238000000862 absorption spectrum Methods 0.000 claims description 7
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- 238000001228 spectrum Methods 0.000 claims description 3
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- 238000004519 manufacturing process Methods 0.000 abstract description 2
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- 238000002360 preparation method Methods 0.000 description 37
- -1 hydroxide ions Chemical class 0.000 description 27
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- 238000000034 method Methods 0.000 description 14
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- 238000005906 dihydroxylation reaction Methods 0.000 description 10
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 10
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- 238000004566 IR spectroscopy Methods 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
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- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
- QANIADJLTJYOFI-UHFFFAOYSA-K aluminum;magnesium;carbonate;hydroxide;hydrate Chemical compound O.[OH-].[Mg+2].[Al+3].[O-]C([O-])=O QANIADJLTJYOFI-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229960004567 aminohippuric acid Drugs 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000005102 attenuated total reflection Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- CXUJOBCFZQGUGO-UHFFFAOYSA-F calcium trimagnesium tetracarbonate Chemical compound [Mg++].[Mg++].[Mg++].[Ca++].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O CXUJOBCFZQGUGO-UHFFFAOYSA-F 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- VZFUCHSFHOYXIS-UHFFFAOYSA-N cycloheptane carboxylic acid Natural products OC(=O)C1CCCCCC1 VZFUCHSFHOYXIS-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- PWZFXELTLAQOKC-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide;tetrahydrate Chemical class O.O.O.O.[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O PWZFXELTLAQOKC-UHFFFAOYSA-A 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- OSNSGMPCJPCTJZ-UHFFFAOYSA-N ethene 1,3,5-triazine-2,4,6-triamine Chemical compound C=C.C=C.C=C.C=C.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1 OSNSGMPCJPCTJZ-UHFFFAOYSA-N 0.000 description 1
- VOBXLYOWBUPHIK-UHFFFAOYSA-N ethene 1,3,5-triazine-2,4,6-triamine Chemical compound C=C.C=C.C=C.C=C.C=C.C=C.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1 VOBXLYOWBUPHIK-UHFFFAOYSA-N 0.000 description 1
- WLPKFQRBARNCNR-UHFFFAOYSA-N ethene 1,3,5-triazine-2,4,6-triamine Chemical compound C=C.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1 WLPKFQRBARNCNR-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229910000515 huntite Inorganic materials 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- YAQXGBBDJYBXKL-UHFFFAOYSA-N iron(2+);1,10-phenanthroline;dicyanide Chemical compound [Fe+2].N#[C-].N#[C-].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 YAQXGBBDJYBXKL-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229940056960 melamin Drugs 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical class CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- CZQYVJUCYIRDFR-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O CZQYVJUCYIRDFR-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 150000003349 semicarbazides Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000000371 solid-state nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 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
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
Definitions
- the present invention relates to a spandex fiber containing a partially dehydroxylated hydrotalcite which has excellent discoloration-resistance and chlorine-resistance as well as the intrinsic properties of spandex fiber.
- Spandex fibers have high rubber-like elasticity and excellent physical properties such as high tensile force and restoration force suitable for use in, e.g., underwears, socks and sports wears.
- Spandex fibers consist predominantly of polyurethane, whose physical properties deteriorate when exposed to chlorinated water, e.g., if a swimming wear manufactured by warp-knitting spandex and polyamide is exposed to swimming-pool water containing from 0.5 to 3 ppm of active chlorine.
- US Patent No. 5,447,969 discloses the use of hydrotalcite having crystallized water and being coated with a Cio- 30 fatty acid, to improve the dispersability of the hydrotalcite and thus prevent the hydrotalcite aggregation during the course of preparing spandex, thereby reducing the rise of discharge pressure and the frequency of yarn breakage while spinning, the discoloration during tannin solution-treatment, and the swelling when immersed in chlorinated water.
- the dry spinning process of a polyurethane solution is conducted at a high temperature condition of 330 °C to obtain spandex yarn.
- the use of hydrotalcite having crystallized water and being coated with a C 10 - 30 fatty acid causes the spandex yarn discoloration to yellow-brown during the dry spinning process conducted at a temperature of 250 ° C or higher.
- US Patent No. 6,692,828 discloses the use of hydrotalcite coated with a melamin-based compound having good heat-resistance as an additive to improve the chlorine-resistance of spandex fibers.
- the spandex yarn still undergoes discoloration during dry spinning conducted at 250 °C or higher.
- EP Application Publication No. 1 262 499 Al discloses the use of partially decarbonated hydrotalcite milled to an average grain size of ⁇ m or less for improving the chlorine-resistance of polyurethane spandex.
- the partially decarbonated hydrotalcite is obtained by decomposing a part of carbonic ion moieties of hydrotalcite into carbon dioxide and oxygen.
- the carbonic ion of hydrotalcite is important for imparting the chlorine-resistance to a spandex fiber. Accordingly, the resultant spandex has the hydrotalcite containing a low carbonic ion content, thereby having unsatisfactory chlorine-resistance.
- 2006-5814 discloses a method for preparing a spandex fiber having good discoloration-resistance and chlorine-resistance by using hydrotalcite which is coated with a melamine-based compound and free of crystallized water, without dehydroxylation- or decarbonation-treatment.
- said hydrotalcite only dehydrated should be carefully handled since it is high hygroscopic and tends to convert to the original form having crystallized water, during making its slurry or a mixture of the slurry and a polymer in spandex production.
- such a high hygroscopicity still leads to the discoloration of the spandex yarn during dry spinning at 250 ° C or higher.
- a spandex fiber comprising a partially dehydroxylated hydrotalcite in an amount of 0.1 to 10 % by weight.
- FIG. 1 a diagram showing the structure of hydrotalcite
- FIG. 2 an 27 Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectrum of the hydrotalcite (Mg 8 Al 4 (OH) 24 (CO 3 ) 2 ' 6H 2 O) used in Preparation 2;
- MAS NMR 27 Al magic angle spinning nuclear magnetic resonance
- FIG. 3 an 27 Al MAS NMR spectrum of the partially dehydroxylated hydrotalcite (Mg 8 Al 4 (OH) 16 O 4 (CO 3 ) 2 ) obtained in Preparation 2;
- FIG. 4 an 27 Al MAS NMR spectrum of the spandex yarn obtained in Example 2;
- FIG. 5 an 27 Al MAS NMR spectrum of the hydrotalcite extracted from the spandex yarn of Example 2;
- FIG. 6 an infrared (IR) absorption spectrum of the hydrotalcite (Mg 8 Al 4 (OH) 24 (CO 3 ) 2 ⁇ 6H 2 O) used in Preparation 2;
- FIG. 7 an IR absorption spectrum of the partially dehydroxylated hydrotalcite (Mg 8 Al 4 (OH) ⁇ ⁇ 0 4 (CO 3 ) 2 ) obtained in Preparation 2;
- FIG. 8 an IR absorption spectrum of the hydrotalcite extracted from the spandex yarn of Example 2.
- the spandex fiber of the present invention has excellent chlorine-resistance and does not undergo discoloration during spinning process conducted at 200 °C or higher, which may be prepared by heat-treating a hydrotalcite having crystallized water at a temperature of 200 to 390 ° C to induce dehydration and partial dehydroxylation and then adding a partially dehydroxylated hydrotalcite thus obtained to a polyurethane solution.
- hydrotalcite is partially dehydroxylated by heat-treatment conducted at a high temperature for a long period beyond those disclosed in Korean Patent Application Publication No. 2006-5814, and it is not decarbonated to give sufficient chlorine-resistance, other than that used in EP Application Publication No. 1 262499 Al.
- the spandex fiber according to the present invention is described in detail as follows. It should be understood that the terms used herein is defined considering the function of the present invention and the meaning will be modified according to the intent of the skill in the art, without limiting the constitution of the present invention.
- the term “spinning” or “spinning process” used herein means either melt-spinning or dry-spinning.
- the term “spinning temperature” used herein means the maximum temperature to which a spandex polymer is subjected during a spinning process, e.g., the melting temperature of a polymer chip in a melt-spinning process, or the spinning chamber temperature of a dry-spinning process.
- the term “discoloration” means that a white fiber gets colored as yellow or brown.
- the hydrotalcite used in the present invention is a type of metal hydroxide whose structure consist of two octahedral units having metal cation of 2 or 3 valences (M +2 or M +3 ) surrounded by six hydroxide ions (OH ' ) in the form of double layers, anions (A n" ) and H 2 O molecules for balancing the charged capacity between the double layers, as shown in FIG. 1.
- a hydrotalcite can be heat-treated at a high temperature to remove H 2 O molecules from between the double layers and further heat-treated at a higher temperature to induce dehydroxylation. If the hydrotalcite is heat-treated at a higher temperature than the dehydroxylation temperature, decarbonation may be induced ⁇ see Stanimirova et al., Clay Minerals, 39: 177-191, 2004).
- partially dehydroxylated hydrotalcite used herein means a hydrotalcite obtained by heat-treating a hydrotalcite having crystallized water at a high temperature to induce dehydration and dehydroxylation which may be represented by 2OH " ⁇ H 2 O + O 2" .
- the partially dehydroxylated hydrotalcite has both octahedral and tetrahedral sites, the latter containing a metal cation surrounded by four hydroxyl groups within the double-layered structure ⁇ see Stanimirova et al., Clay Minerals, 39: 177-191, 2004).
- the partially dehydroxylated hydrotalcite may be represented by formula (I):
- M is Mg 5 Ca or Zn 5 y is a value in the range of 2.4 ⁇ y ⁇ 4
- z is a value in the range of 0 ⁇ z ⁇ 8
- m is zero or a positive number.
- the partially dehydroxylated hydrotalcite is selected from the group consisting of compounds OfMg S Al 4 (OH) 16 O 4 (CO 3 ) 2 , Mg 8 Al 4 (OH) 8 O 8 (CO 3 ) 2 , Mg 9 Al 3 (OH) I8 O 3 (CO 3 ) li5 , Mg 9 Al 3 (OH) I2 O 6 (CO 3 ) li5 , Mg 9-6 Al 2-4 (OH) i 9 . 2 O 2 . 4 (CO 3 ) L2 , Mg 9-6 Al 2-4 (OH) i 4 . 4 ⁇ 4 .
- the starting hydrotalcite having crystallized water is preferably heat-treated at a temperature of 200 to 390 ° C , more preferably 250 to 300 ° C under a moisture-free atmosphere of nitrogen, helium, oxygen, hydrogen or carbon dioxide.
- the hydrotalcite having crystallized water is heat-treated at a temperature less than 200 ° C , the hydrotalcite may not be dehydroxylated. If the hydrotalcite having crystallized water is heat-treated at a temperature higher than 390 ° C , the hydrotalcite may undergo dehydroxylation and further decarbonation, leading to deteriorated chlorine-resistance. Accordingly, the partially dehydroxylated hydrotalcite obtained from the heat-treatment at about 250 to 300 ° C is useful for the improvement of chlorine-resistance.
- the partially dehydroxylated hydrotalcite of the present invention may adsorb moisture in air, but most of the moisture adsorbed is vaporized at about 100 ° C , and thus such adsorbed moisture is different from crystallized water which is present in the hydrotalcite before heat-treatment and vaporizes at about 170 to 220 ° C . Accordingly, the partially dehydroxylated hydrotalcite is believed to give no affection on the discoloration of the spandex yarn during a spinning process at 200 °C or higher since the moisture adsorbed therein is already removed at about 100 " C 5 while the hydrotalcite having crystallized water may induce the discoloration of the spandex yarn as the initial crystallized water thereof vaporizes during a spinning process at 200 °C or higher.
- the inventive spandex fiber prepared by adding the partially dehydroxylated hydrotalcite has superior chlorine-resistance than that prepared by adding hydrotalcite having crystallized water, which is considered as a result that the layered double hydroxide system of the partially dehydroxylated hydrotalcite is changed to enhance its capacity for water absorption and ion-exchange.
- the polyurethane used in the preparation of the spandex fiber according to the present invention may be prepared by a conventional method known in the art, e.g., by reacting an organic diisocyanate and a diol polymer to produce a polyurethane precursor, dissolving the precursor in an organic solvent and allowing the resulting solution to react with a diamine and monoamine.
- the organic diisocyanate which may be used in the present invention includes diphenylmethane-4,4' -diisocyanate, hexamethylenediisocyanate, toluenediisocyanate, butylenediisocyanate and hydrogenated diphenylmethane-4,4'-diisocyanate.
- examples of the diol polymer which may be used in the present invention include polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol, etc.
- the diamine is used as a chain extender and examples thereof are ethylenediamine, propylenediamine and hydrazine.
- the monoamine is used as a chain terminator and it may be diethyldiamine, monoethanolamine or dimethylamine.
- the polyurethane for preparing the spandex fiber may further comprise organic additives including hindered phenol-based compounds, benzofuranons, semicarbazides, benzotriazoles, hindered amine-based compounds, and polymeric tertiary amine stabilizers such as a tertiary nitrogen atom-containing polyurethane and polydialkyl aminoalkyl methacrylate, so as to prevent the spandex fiber from discoloration and deterioration in physical properties.
- organic additives including hindered phenol-based compounds, benzofuranons, semicarbazides, benzotriazoles, hindered amine-based compounds, and polymeric tertiary amine stabilizers such as a tertiary nitrogen atom-containing polyurethane and polydialkyl aminoalkyl methacrylate, so as to prevent the spandex fiber from discoloration and deterioration in physical properties.
- the spandex fiber of the present invention may further comprise inorganic additives such as titanium dioxide and magnesium stearate.
- the titanium dioxide may be used in an amount of 0.1 to 5 % by weight according to the whiteness of the spandex fiber desired.
- the magnesium stearate may be used in an amount of 0.1 to 2 % by weight to enhance the unwinding property of the spandex fiber.
- the partially dehydroxylated hydrotalcite is used in an amount of 0.1 to 10 % by weight based on the weight of the polyurethane used.
- the amount is less than 0.1 % by weight, the chlorine-resistance of the spandex fiber may be insufficient, and when the amount is higher than 10 % by weight, the strength, elongation and modulus of the spandex fiber deteriorate.
- the partially dehydroxylated hydrotalcite may be added to the polyurethane at any convenient time, e.g., after mixing with an additive followed by a sand-grinding or milling process, or after a sand-grinding or milling process in the absence of an additive.
- the partially dehydroxylated hydrotalcite may be further coated or not coated with a coating agent conventionally used in the art, which does not affect the chlorine-resistance and discoloration of the spandex yarn.
- the coating agent examples include aliphatic alcohols, fatty acids, fatty acid salts, fatty acid esters, phosphoric acid esters, styrene/maleic acid anhydride copolymers and derivatives thereof, silane-based coupling agents, titanate-based coupling agents, polyorganosiloxanes, polyorganohydrogensiloxanes and melamine-based compounds.
- fatty acids, fatty acid salts and/or melamine-based compounds are preferred since said two formers exhibit excellent coating efficiency and the latter can minimize discoloration upon the dehydroxylation of hydrotalcite by heat-treatment.
- the coating process for hydrotalcite may be conducted by adding a coating agent to a solvent such as water, alcohol, ether or dioxane in an amount of 0.1 to 10 % by weight based on the weight of hydrotalcite to obtain a coating agent solution, adding hydrotalcite thereto and stirring the resulting solution at an elevated temperature of 50 to 170 °C (if necày, using a high-pressure reactor) for 10 minutes to 2 hours, followed by filtering and drying.
- the coating process may be conducted by heat-melting a coating agent without solvent and mixing the melted coating agent with hydrotalcite in a high-speed mixer.
- the coating process using the melamine-based compounds in water should be conducted at a temperature of 150 ° C or higher under pressure, due to a high melting point of the melamine-based compound.
- the coating process using the fatty acids or fatty acid salts in water is preferably carried out at a temperature of 100 °C or higher.
- the coating temperature is less than 100 " C, it is difficult to achieve uniform coating and non-discoloration, and the amount of the coating agent required increases.
- the fatty acids or fatty acid salts is used in an amount of about 3 % by weight based on the hydrotalcite in the coating process at less than 100 ° C, while its amount may be reduced to 1.5 % by weight based on the hydrotalcite in the coating process at 100 ° C or higher.
- Such a reduced amount of the coating agent can reduce its discoloration during heat-treating of the hydrotalcite.
- the fatty acids which may be used as a coating agent in the present invention are preferably selected from mono- or poly-hydroxy fatty acids having linear or branched hydrocarbon chains of 3 to 40 carbon atoms, e.g., lauric acid, carproic acid, palmitic acid and stearic acid.
- the fatty acid salts which may be used as a coating agent in the present invention are formed from mono- or di-functional and saturated or unsaturated fatty acid having 6 to 30 carbon atoms, and a metal selected from metals of Groups I to III of Elementary Periodic Table and zinc.
- the fatty acid salts include lithium, magnesium, calcium, aluminum or zinc salts of oleic acid, palmitic acid or stearic acid, preferably magnesium stearate, calcium stearate and aluminum stearate, more preferably magnesium stearate.
- the melamine-based compounds which may be used as a coating agent in the present invention include melamine compounds, phosphor-containing melamine compounds and melamine cyanurate compounds, optionally substituted with an organic compound having a carboxyl group, which may be used alone or in combination.
- melamine compounds examples include methylene dimelamine, ethylene dimelamine, trimethylene dimelamine, tetramethylene dimelamine, hexamethylene dimelamine, decamethylene dimelamine, dodecamethylene dimelamine, 1,3-cyclohexylene dimelamine, p-phenylene dimelamine, /7-xylene dimelamine, diethylene trimelamine, triethylene tetramelamine, tetraethylene pentamelamine, hexaethylene heptamelamine and melamine formaldehyde.
- Examples of phosphor-containing melamine compounds include any of the above-mentioned melamine compounds coupled with phosphoric acid or a phosphate, e.g., dimelamine pyrophosphate, melamine primary phosphate, melamine secondary phosphate, melamine polyphosphate and melamine salt of bis-(pentaerythritol phosphate) phosphoric acid, etc.
- a phosphate e.g., dimelamine pyrophosphate, melamine primary phosphate, melamine secondary phosphate, melamine polyphosphate and melamine salt of bis-(pentaerythritol phosphate) phosphoric acid, etc.
- melamine cyanurate compounds include melamine cyanurates substituted with at least one substituent selected from methyl, phenyl, carboxymethyl, 2-carboxyethyl, cyanomethyl and 2-cyanoethyl.
- the above melamine-based compounds are reacted with an organic compound having a carboxyl group.
- the organic compound having a carboxyl group include aliphatic monocarboxylic acids (e.g., caprylic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, eicosanoic acid and behenic acid); aliphatic dicarboxylic acids (e.g., malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebasic acid, 1 ,9-nonanedicarboylic acid, lJO-decanedicarboxylic acid, ljl l-undecanedicarboxylic acid, 1,12-dodecane
- a coating agent enhances the dispersibility of the hydrotalcite in a spandex polymer solution and maintain the spinnability of the spandex.
- the hydrotalcite is not coated, it can exhibit excellent spinnability substantially equivalent to that of the coated hydrotalcite when sand-grinded or milled.
- the sand-grinding or milling process may be conducted by milling a mixture or slurry of the hydrotalcite, a small amount of polyurethane and a solvent using a conventional bead mill.
- the small amount of polyurethane used can enhance the dispersibility of the hydrotalcite.
- the solvent which may be used in the sand-grinding or milling process include dimethylacetamide, dimethylformamide, dimethylsulfoxide and a mixture thereof.
- the hydrotalcite when sand-grinded or milled to have secondary particles of an average size of about 15 ⁇ m or less, it can exhibit functions substantially equivalent to those of the hydrotalcite coated and sand-grinded or milled, during the preparation of the spandex fiber.
- the heat-treatment for dehydroxylation of the hydrotalcite may be conducted using various types of dryers to give heat of about 200 to 390 °C, e.g., those operated in a convection, conduction, radiation, microwaves or vacuum heating process.
- Stearic acid and hydrotalcite of formula Mg 8 Al 4 (OH) 24 (COs) 2 -OH 2 O were successively added to water.
- the amount of stearic acid was 2 wt% based on the weight of the hydrotalcite.
- the resulting mixture was stirred at 150 °C for 20 minutes, filtered and dried, to obtain hydrotalcite coated with stearic acid.
- the coated hydrotalcite was heat-treated at 250 ° C for 4 hours, to obtain hydrotalcite of formula Mg 8 Al 4 (OH) i 6 ⁇ 4 (CO 3 ) 2 coated with stearic acid.
- Mg 8 Al 4 (OH) 24 (CO 3 ) 2 -6H 2 O were successively added to water.
- the amounts of stearic acid and melamine polyphosphate were 2 wt% and 1 wt%, respectively, based on the weight of the hydrotalcite.
- the resulting mixture was stirred at 160 0 C for 30 minutes, filtered and dried, to obtain the hydrotalcite coated with stearic acid and melamine polyphosphate.
- the coated hydrotalcite was heat-treated at 250 °C for 4 hours, to obtain hydrotalcite of formula Mg 8 Al 4 (OH) I eO 4 (COs) 2 coated with stearic acid and melamine polyphosphate.
- Hydrotalcite of formula Mg 8 Al 4 (OH) 24 (CO 3 ) 2 -6H 2 O was heat-treated at 250 ° C for 4 hours, to obtain hydrotalcite of formula Mg 8 Al 4 (OH) I6 O 4 (COs) 2 .
- the resultant was immersed in water at room temperature for 5 hours and dried at 60 ° C for 48 hours, to obtain hydrotalcite of formula Mg 8 Al 4 (OH) 16 O 4 (CO 3 ) 2 -7H 2 O.
- Preparation 5 The procedure of Preparation 1 was repeated except that hydrotalcite of formula Mg 9 Al 3 (OH) 24 (CO 3 ) I 5 -T-SH 2 O was coated with 1.5 wt% of stearic acid, to obtain hydrotalcite of formula Mg 9 Al 3 (OH) 18 O 3 (CO 3 )i, 5 coated with stearic acid.
- Hydrotalcite of formula Mg 9 Al 3 (OH) 24 (CO 3 ) L5 -V-SH 2 O was heat-treated at 250 ° C for 4 hours, to obtain hydrotalcite of formula
- Hydrotalcite of formula Mg 6 Al 2 (OH) I6 CO 3 -SH 2 O was heat-treated at 180°C for 4 hours, to obtain hydrotalcite of formula Mg 6 Al 2 (OH) 16 CO 3 .
- the hydrotalcite obtained was analyzed by 27 Al magic angle spinning nuclear magnetic resonance (MAS NMR) to examine the partial dehydroxylation thereof.
- Al 2 O 3 standard 104.21 MHz transmitter frequency, 15 kHz spinning rate, scan numbers of times: 512 (hydrotalcite powder) or 8192 (hydrotalcite-contained yarn) and one pulse having 2.3 ⁇ s of pulse length.
- the 27 Al MAS NMR result obtained can be used to determine the structure surrounding Al 3+ within the hydrotalcite.
- the data from 27 Al MAS NMR for the initial hydrotalcite of Mg 8 Al 4 (OH) 24 (CO 3 ) 2 -6H 2 O used in Preparation 2 shows a peak for octahedrally coordinated Al 3+ as shown in FIG. 2, while the data for the hydrotalcite of Mg 8 Al 4 (OH) 16 O 4 (CO 3 ) 2 obtained in Preparation 2 shows peaks for both octahedrally coordinated Al and tetrahedrally coordinated Al 3+ as a result of partial dehydroxylation, as shown in FIG. 3.
- the hydrotalcite obtained in Preparation 2 was also analyzed by IR spectroscopy to examine the partial dehydroxylation thereof. If the hydrotalcite is partially dehydroxylated, an IR absorption spectrum shows a distinct peak at wave numbers of about 1500 to 1600 cm "1 .
- IR analysis was performed using IFS 88 (Bruker, German) according to ATR (attenuated total reflectance) under the conditions of: 400 to 4000 cm “1 wave number area, 4cm "1 resolution and scan numbers: 16.
- the IR absorption spectrum of the initial hydrotalcite of formula Mg 8 Al 4 (OH) 24 (CO 3 ) 2 -6H 2 O, used in Preparation 2 shows a significant absorption peak at wave numbers of about 1300 to 1400 cm “1 as shown in FIG. 6, while the spectrum for the hydrotalcite of formula Mg 8 Al 4 (OH)i 6 ⁇ 4 (CO 3 ) 2 obtained in Preparation 2 shows significant absorption peaks at wave numbers of about 1300 to 1400 cm '1 and about 1500 to 1600 cm "1 as shown in FIG. 7.
- the polyurethane spinning solution was then defoamed and dry-spinned at a spinning temperature of 250 ° C, to obtain a 4-filament 40-denier spandex fiber.
- the spandex yarn subjected to 50% stretching was treated with water (pH 4.2, 97 to 98 ° C) for 2 hours and cooled to at room temperature.
- the 5 spandex yarn was dipped in 45 t of chlorinated water (pH 7.5) containing 3.5 ppm of active chlorine for 24 hours, and its strength was measured with Instron 4301 (Instron Co., USA) by applying 1 kg cell to a sample piece of 5 cm long, at 300 mm/min of cross head speed, to calculate the strength preservation rate as follows: 0
- Strength preservation rate (%) (S/S 0 ) x 100 (wherein, So is strength before treatment, and S is strength after treatment)
- Tubular knitted fabric was prepared using a spandex alone with a tubular knitting machine (KT-400, 4 inches of diameter, 400 needles, Nagata Seiki Company, Japan), and scoured in water whose weight was 40 times as much as the weight of the fabric using a mixture of scouring agents, 2 g/L of UNITOL CT-81 (Shinyoung Chemical, Korea), 3 g/L of UNITOL-SMS (Shinyoung Chemical, Korea) and 0.5g/L of NaOH at 90 ° C for 30 minutes.
- a mixture of scouring agents 2 g/L of UNITOL CT-81 (Shinyoung Chemical, Korea), 3 g/L of UNITOL-SMS (Shinyoung Chemical, Korea) and 0.5g/L of NaOH at 90 ° C for 30 minutes.
- the spandex fibers of Examples 1 to 8 contain the partially dehydroxylated hydrotalcite and thus they did not discolor during spinning at a temperature of 200 °C or higher and were also good resistant to anti-chlorine.
- the spandex fibers containing hydrotalcites having crystallized water (Comparative Examples 2 and 3) exhibited poor resistant to both discoloration during spinning at a high temperature and chlorine.
- spandex fibers containing hydrotalcites which is not partially 5 dehydroxylated and the absence of crystallized water were more resistant to discoloration than those containing hydrotalcites having crystallized water, however, they were less resistant to discoloration and also to chlorine, as compared with the inventive spandex fibers.
- Example 2 The spandex yarn obtained in Example 2 was analyzed by 27 Al MAS NMR by the procedure of Experimental Example 1, and the result is shown 5 in FIG. 4.
- the data for the spandex fiber of Example shows peaks for both octahedrally coordinated Al 3+ and tetrahedrally coordinated Al 3+ .
- the spandex yarn obtained in Example 2 was evaluated for the presence of partially dehydroxylated hydrotalcite.
- the spandex yarn of Example 2 was de-oiled by 5 petroleum-ether treatment, the oil-free yarn was dissolved in dimethylacetamide having 100 ppm or less of moisture to a concentration of 1.3% or less, and the solution was subjected to centrifugation twice to extract hydrotalcite.
- the exracted hydrotalcite was dried at 60 °C and analyzed by 27 Al MAS NMR according to the procedure of Experimental Example 1. o The result confirmed that the exracted hydrotalcite has both octahedral and tetrahedral structures, as shown in FIG. 5.
- Experimental Example 5 IR analysis of hvdrotalcite extracted from spandex fiber
- the hydrotalcite extracted from the spandex fiber obtained in Example 2 was also analyzed by IR spectroscopy according to the procedure of Experimental Example 2.
- the IR absorption spectrum for the exracted hydrotalcite shows a significant absorption peak at wave numbers of about 1500 to 1600 cm "1 as shown in FIG. 8.
- the spandex fiber of the present invention has high resistance to both chlorine and discoloration during spinning at a temperature of 200 ° C or higher, and is therefore useful for underwear, socks, and particularly, sports apparel such as swimsuit.
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Abstract
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KR1020060041407A KR100762548B1 (en) | 2006-05-09 | 2006-05-09 | Spandex fibers containing partially dehydroxylated hydrotalcites |
PCT/KR2007/000551 WO2007129807A1 (en) | 2006-05-09 | 2007-02-01 | Spandex fibers containing partially dehydroxylated hydrotalcite |
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EP2021537A1 true EP2021537A1 (en) | 2009-02-11 |
EP2021537A4 EP2021537A4 (en) | 2009-12-09 |
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EP (1) | EP2021537B1 (en) |
JP (1) | JP4728425B2 (en) |
KR (1) | KR100762548B1 (en) |
CN (1) | CN101528993B (en) |
BR (1) | BRPI0711341B1 (en) |
TW (1) | TWI322838B (en) |
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WO2008069610A1 (en) * | 2006-12-07 | 2008-06-12 | Doobon Inc. | Oxide-like hydrotalcite and manufacturing process thereof |
KR100870533B1 (en) | 2007-06-28 | 2008-11-26 | 주식회사 효성 | Spandex fibers containing a heat-treated mineral mixture of huntite- hydromagnesite |
KR101130282B1 (en) * | 2009-10-26 | 2012-03-26 | 이화여자대학교 산학협력단 | Sepiocite Compound derived from Layered Double Hydroxide and Method for Preparing the Same |
KR101054809B1 (en) | 2010-12-22 | 2011-08-05 | (주)세창 | Synthetic fiber composition containing hydrotalcite |
KR101186818B1 (en) | 2012-02-17 | 2012-09-28 | (주)우진고분자 | A surface-treated hydrotalcite and a composition comprising the same |
KR102412143B1 (en) | 2022-01-17 | 2022-06-22 | ㈜쿨베어스 | Anti-chlorine spandex containing echinoderms-derived porous material and method for manufacturing the same |
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EP1262499A1 (en) * | 2001-05-30 | 2002-12-04 | FILLATTICE S.p.A. | Composition of an elastic fiber which can resist water containing chlorine |
WO2006006784A1 (en) * | 2004-07-14 | 2006-01-19 | Hyosung Corporation | A spandex fiber with discoloration-resistance and chlorine-resistance and a method for manufacturing the same |
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US6353049B1 (en) * | 1997-02-13 | 2002-03-05 | Asahi Kasei Kabushiki Kaisha | Elastic polyurethane fiber and process for producing the same |
JP3868097B2 (en) | 1998-02-13 | 2007-01-17 | 旭化成せんい株式会社 | Woven knitted fabric and manufacturing method thereof |
JP2000290836A (en) * | 1999-04-05 | 2000-10-17 | Asahi Chem Ind Co Ltd | Polyurethaneurea elastic fiber |
JP3922680B2 (en) * | 2000-10-11 | 2007-05-30 | 株式会社海水化学研究所 | Chlorine-based disinfectant neutralizer and method for producing the same |
KR100438005B1 (en) | 2002-04-04 | 2004-06-30 | 주식회사 두본 | Method for producing chlorine-resistant polyurethane elastic fiber and the fiber |
KR100437988B1 (en) | 2002-04-29 | 2004-06-30 | 주식회사 두본 | High chlorine and heat resistant spandex fiber and manufacturing method thereof |
KR100575374B1 (en) | 2004-10-22 | 2006-05-02 | 주식회사 효성 | Polyurethane elastic fiber having excellent chlorine-resistant and antistatic property and process for preparing the same |
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2006
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- 2007-02-01 CN CN2007800157858A patent/CN101528993B/en active Active
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EP1262499A1 (en) * | 2001-05-30 | 2002-12-04 | FILLATTICE S.p.A. | Composition of an elastic fiber which can resist water containing chlorine |
WO2006006784A1 (en) * | 2004-07-14 | 2006-01-19 | Hyosung Corporation | A spandex fiber with discoloration-resistance and chlorine-resistance and a method for manufacturing the same |
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JP2009536274A (en) | 2009-10-08 |
CN101528993A (en) | 2009-09-09 |
TW200742777A (en) | 2007-11-16 |
EP2021537A4 (en) | 2009-12-09 |
JP4728425B2 (en) | 2011-07-20 |
KR20060066689A (en) | 2006-06-16 |
KR100762548B1 (en) | 2007-10-04 |
EP2021537B1 (en) | 2010-11-24 |
BRPI0711341B1 (en) | 2017-08-01 |
CN101528993B (en) | 2011-07-13 |
TWI322838B (en) | 2010-04-01 |
BRPI0711341A2 (en) | 2011-08-30 |
WO2007129807A1 (en) | 2007-11-15 |
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