EP1643019B1 - Polyether ester elastic fiber and fabrics and clothes made by using the same - Google Patents
Polyether ester elastic fiber and fabrics and clothes made by using the same Download PDFInfo
- Publication number
- EP1643019B1 EP1643019B1 EP04746409A EP04746409A EP1643019B1 EP 1643019 B1 EP1643019 B1 EP 1643019B1 EP 04746409 A EP04746409 A EP 04746409A EP 04746409 A EP04746409 A EP 04746409A EP 1643019 B1 EP1643019 B1 EP 1643019B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polyether ester
- elastic fiber
- weight
- fiber
- percent
- 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.)
- Expired - Lifetime
Links
- 210000004177 elastic tissue Anatomy 0.000 title claims description 88
- 150000002148 esters Chemical class 0.000 title claims description 76
- 239000004721 Polyphenylene oxide Substances 0.000 title claims description 59
- 229920000570 polyether Polymers 0.000 title claims description 59
- 239000004744 fabric Substances 0.000 title claims description 30
- 238000010521 absorption reaction Methods 0.000 claims description 49
- 239000000835 fiber Substances 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- -1 polybutylene terephthalate Polymers 0.000 claims description 39
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 38
- 229920001971 elastomer Polymers 0.000 claims description 23
- 239000000806 elastomer Substances 0.000 claims description 23
- 125000001931 aliphatic group Chemical group 0.000 claims description 22
- 239000003921 oil Substances 0.000 claims description 21
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- 238000007334 copolymerization reaction Methods 0.000 claims description 14
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 13
- 239000002480 mineral oil Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000002736 nonionic surfactant Substances 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 8
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 8
- 125000000524 functional group Chemical group 0.000 claims description 8
- 239000000314 lubricant Substances 0.000 claims description 8
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 7
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 7
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 238000000034 method Methods 0.000 description 17
- 239000011734 sodium Substances 0.000 description 11
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 9
- 229940077388 benzenesulfonate Drugs 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 238000006068 polycondensation reaction Methods 0.000 description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 229920001515 polyalkylene glycol Polymers 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 238000009987 spinning Methods 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- YZTJKOLMWJNVFH-UHFFFAOYSA-N 2-sulfobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1S(O)(=O)=O YZTJKOLMWJNVFH-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 238000009940 knitting Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical group O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- VIBDJEWPNNCFQO-UHFFFAOYSA-N ethane-1,1,2-triol Chemical group OCC(O)O VIBDJEWPNNCFQO-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000003578 releasing effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- IOGGBUVFUGPCLQ-UHFFFAOYSA-N 1-[4-(2-oxoazepane-1-carbonyl)benzoyl]azepan-2-one Chemical compound C=1C=C(C(=O)N2C(CCCCC2)=O)C=CC=1C(=O)N1CCCCCC1=O IOGGBUVFUGPCLQ-UHFFFAOYSA-N 0.000 description 1
- IZTHTNFCHNNDAQ-QXMHVHEDSA-N 11-methyldodecyl (Z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCCCCCCCCCC(C)C IZTHTNFCHNNDAQ-QXMHVHEDSA-N 0.000 description 1
- YTPNTTUPPCGZPJ-UHFFFAOYSA-N 11-methyldodecyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCCCCCCCCCCC(C)C YTPNTTUPPCGZPJ-UHFFFAOYSA-N 0.000 description 1
- HFWHTGSLDKKCMD-UHFFFAOYSA-N 2,2-bis(octanoyloxymethyl)butyl octanoate Chemical compound CCCCCCCC(=O)OCC(CC)(COC(=O)CCCCCCC)COC(=O)CCCCCCC HFWHTGSLDKKCMD-UHFFFAOYSA-N 0.000 description 1
- ZRPKEUVFESZUKX-UHFFFAOYSA-N 2-(2-hydroxyethoxy)benzoic acid Chemical compound OCCOC1=CC=CC=C1C(O)=O ZRPKEUVFESZUKX-UHFFFAOYSA-N 0.000 description 1
- KKKKCPPTESQGQH-UHFFFAOYSA-N 2-(4,5-dihydro-1,3-oxazol-2-yl)-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=NCCO1 KKKKCPPTESQGQH-UHFFFAOYSA-N 0.000 description 1
- XCSGHNKDXGYELG-UHFFFAOYSA-N 2-phenoxyethoxybenzene Chemical compound C=1C=CC=CC=1OCCOC1=CC=CC=C1 XCSGHNKDXGYELG-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004129 EU approved improving agent Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- OXPCWUWUWIWSGI-MSUUIHNZSA-N Lauryl oleate Chemical compound CCCCCCCCCCCCOC(=O)CCCCCCC\C=C/CCCCCCCC OXPCWUWUWIWSGI-MSUUIHNZSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- DJNTZVRUYMHBTD-UHFFFAOYSA-N Octyl octanoate Chemical compound CCCCCCCCOC(=O)CCCCCCC DJNTZVRUYMHBTD-UHFFFAOYSA-N 0.000 description 1
- 229920001283 Polyalkylene terephthalate Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- CJFLBOQMPJCWLR-UHFFFAOYSA-N bis(6-methylheptyl) hexanedioate Chemical compound CC(C)CCCCCOC(=O)CCCCC(=O)OCCCCCC(C)C CJFLBOQMPJCWLR-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- QICYQWTZZBCCIA-UHFFFAOYSA-L disodium;3,7-bis(methoxycarbonyl)naphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].C1=C(C(=O)OC)C=C(S([O-])(=O)=O)C2=CC(C(=O)OC)=CC(S([O-])(=O)=O)=C21 QICYQWTZZBCCIA-UHFFFAOYSA-L 0.000 description 1
- OGTMSWHHHRTOEF-UHFFFAOYSA-L disodium;3,7-dicarboxynaphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].C1=C(C(O)=O)C=C(S([O-])(=O)=O)C2=CC(C(=O)O)=CC(S([O-])(=O)=O)=C21 OGTMSWHHHRTOEF-UHFFFAOYSA-L 0.000 description 1
- 238000000578 dry spinning Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- AVPYUFDQTKOBNG-UHFFFAOYSA-M lithium;3,5-bis(methoxycarbonyl)benzenesulfonate Chemical compound [Li+].COC(=O)C1=CC(C(=O)OC)=CC(S([O-])(=O)=O)=C1 AVPYUFDQTKOBNG-UHFFFAOYSA-M 0.000 description 1
- ZERIVMMUDSPYOZ-UHFFFAOYSA-M lithium;3,7-bis(methoxycarbonyl)naphthalene-1-sulfonate Chemical compound [Li+].C1=C(C(=O)OC)C=C(S([O-])(=O)=O)C2=CC(C(=O)OC)=CC=C21 ZERIVMMUDSPYOZ-UHFFFAOYSA-M 0.000 description 1
- GGKPBCOOXDBLLG-UHFFFAOYSA-M lithium;3-carboxy-5-sulfobenzoate Chemical compound [Li+].OC(=O)C1=CC(C(O)=O)=CC(S([O-])(=O)=O)=C1 GGKPBCOOXDBLLG-UHFFFAOYSA-M 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- IIGMITQLXAGZTL-UHFFFAOYSA-N octyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCCCCCCC IIGMITQLXAGZTL-UHFFFAOYSA-N 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- FJIZBDJKYXYPAE-UHFFFAOYSA-M potassium;3,5-bis(methoxycarbonyl)benzenesulfonate Chemical compound [K+].COC(=O)C1=CC(C(=O)OC)=CC(S([O-])(=O)=O)=C1 FJIZBDJKYXYPAE-UHFFFAOYSA-M 0.000 description 1
- DVBBBJFTGOHNHC-UHFFFAOYSA-M potassium;3,5-dicarboxybenzenesulfonate Chemical compound [K+].OC(=O)C1=CC(C(O)=O)=CC(S([O-])(=O)=O)=C1 DVBBBJFTGOHNHC-UHFFFAOYSA-M 0.000 description 1
- KJNLNBUCZYHGPG-UHFFFAOYSA-M potassium;3,7-bis(methoxycarbonyl)naphthalene-1-sulfonate Chemical compound [K+].C1=C(C(=O)OC)C=C(S([O-])(=O)=O)C2=CC(C(=O)OC)=CC=C21 KJNLNBUCZYHGPG-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- SLOMLIJJTAEWQA-UHFFFAOYSA-M sodium;2,6-bis(methoxycarbonyl)naphthalene-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=C(C(=O)OC)C=CC2=CC(C(=O)OC)=CC=C21 SLOMLIJJTAEWQA-UHFFFAOYSA-M 0.000 description 1
- LLHSEQCZSNZLRI-UHFFFAOYSA-M sodium;3,5-bis(methoxycarbonyl)benzenesulfonate Chemical compound [Na+].COC(=O)C1=CC(C(=O)OC)=CC(S([O-])(=O)=O)=C1 LLHSEQCZSNZLRI-UHFFFAOYSA-M 0.000 description 1
- YXTFRJVQOWZDPP-UHFFFAOYSA-M sodium;3,5-dicarboxybenzenesulfonate Chemical compound [Na+].OC(=O)C1=CC(C(O)=O)=CC(S([O-])(=O)=O)=C1 YXTFRJVQOWZDPP-UHFFFAOYSA-M 0.000 description 1
- PKAZXAJFBXZMAY-UHFFFAOYSA-M sodium;3,7-bis(methoxycarbonyl)naphthalene-1-sulfonate Chemical compound [Na+].C1=C(C(=O)OC)C=C(S([O-])(=O)=O)C2=CC(C(=O)OC)=CC=C21 PKAZXAJFBXZMAY-UHFFFAOYSA-M 0.000 description 1
- YGCFNVDNEPLPGM-UHFFFAOYSA-M sodium;3,7-bis(methoxycarbonyl)naphthalene-2-sulfonate Chemical compound [Na+].C1=C(C(=O)OC)C(S([O-])(=O)=O)=CC2=CC(C(=O)OC)=CC=C21 YGCFNVDNEPLPGM-UHFFFAOYSA-M 0.000 description 1
- PXMZGQMCKRIHHE-UHFFFAOYSA-M sodium;3,7-dicarboxynaphthalene-1-sulfonate Chemical compound [Na+].C1=C(C(O)=O)C=C(S([O-])(=O)=O)C2=CC(C(=O)O)=CC=C21 PXMZGQMCKRIHHE-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 239000011701 zinc Substances 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
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/86—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from polyetheresters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
Definitions
- the present invention relates to a polyether ester elastic fiber giving a fabric which has a good moisture-absorbing or releasing property, is reversibly expanded or contracted by the absorption or release of water, and especially gives non-conventional comfortableness for sports uses, inner wear uses and the like.
- polyurethane elastic fibers have mainly been used as elastic fibers for clothes and industrial materials, but have defects that heat resistance, chemical resistance and weather (light) resistance are inferior.
- the polyurethane elastic fibers need a dry spinning process on their production, and the recovery of a solvent is therefore needed.
- the polyurethane elastic fibers have problems of low productivity and large energy consumption.
- the polyurethane elastic fibers have many problems directed to the coming of a future recycling-oriented society, such as the difficulty of recycling and the production of harmful gases on combustion.
- polyether ester elastic fibers containing a highly crystalline polyester such as a polyalkylene terephthalate as a hard segment and a polyalkylene glycol as a soft segment and capable of being melt-spun have been put to practical uses, while utilizing advantages such as high productivity, excellent heat resistance and excellent heat set resistance.
- polyether ester elastic fibers using polybutylene terephthalate as a hard segment and polyoxybutylene glycol as a soft segment, or the like, have been used as elastic fibers having elastic performances comparable to those of polyurethane elastic fibers.
- both these hard segment and soft segment are generally hydrophobic, and polyether ester elastic fibers having hydrophilic properties such as a moisture-absorbing property or a water-absorbing property have little been put to a practical use.
- the present invention has been completed on the basis of the above-mentioned conventional techniques as the background, and the object of the present invention is to provide the recyclable polyether ester elastic fibers giving fabrics which have a good moisture-absorbing property and is reversibly largely expanded or contracted by the absorption or release of water to give excellent comfortableness, and to provide a fabric, clothing using the elastic fibers.
- the polyether ester elastomer is an elastic fiber comprising a polyether ester elastomer containing polybutylene terephthalate as a hard segment and polyoxyethylene glycol as a soft segment.
- the polybutylene terephthalate as the hard segment contains butylene terephthalate units in an amount of at least 70 percent by mole.
- the content of the butylene terephthalate is more preferably not less than 80 percent by mole, furthermore preferably not less than 90 percent by mole.
- the above-mentioned polybutylene terephthalate may be copolymerized with one or more other components within a range substantially not affecting the achievement of the object of the present invention.
- the dicarboxylic acid component used as the one or more other copolymerization components includes aromatic, aliphatic and alicyclic dicarboxylic acid components such as naphthalene dicarboxylic acid, isophthalic acid, diphenyl dicarboxylic acid, diphenoxyethane dicarboxylic acid, ⁇ -hydroxyethoxybenzoic acid, p-hydroxybenzoic acid, adipic acid, sebacic acid and 1,4-cyclohexane dicarboxylic acid.
- a trifunctional or more functional polycarboxylic acid such as trimellitic acid or pyromellitic acid may be used as a copolymerization component.
- the diol component includes aliphatic, alicyclic and aromatic diol components such as trimethylene glycol, ethylene glycol, cyclohexane-1,4-dimethanol, and neopentyl glycol.
- a trifunctional or more functional polyol such as glycerol, trimethylolpropane or pentaerythritol may be used as a copolymerization component.
- the polyoxyethylene glycol as the soft segment contains oxyethylene glycol units in an amount of not less than at least 70 percent by mole.
- the content of the oxyethylene glycol is more preferably not less than 80 percent by mole, furthermore preferably not less than 90 percent by mole.
- the above-mentioned polyoxyethylene glycol may be copolymerized with, for example, propylene glycol, tetramethylene glycol, glycerol or the like within a range substantially not affecting the achievement of the object of the present invention.
- the number-average molecular weight of the above-mentioned polyoxyethylene glycol is preferably 400 to 8,000, especially preferably 1,000 to 6,000.
- the weight ratio of the hard segment : the soft segment is preferably in a range of 70 : 30 to 30 : 70, more preferably in a range of 60 : 40 to 40 : 60.
- the weight ratio of the hard segment exceeds 70 %, the elongation of the elastic fiber is lowered, and it becomes difficult to use the elastic fiber for high stretch uses.
- the moisture-absorbing property is liable to be lowered.
- the weight ratio of the hard segment is less than 30 %, the strength is liable to be lowered, because the rate of the crystal portion of the polybutylene terephthalate is lowered, and it is difficult to copolymerize all of the added polyoxyethylene glycol. Washing fastness is therefore liable to be deteriorated in post-processing processes such as scouring and dyeing processes or when the elastic fiber is used as a product.
- the elastic fiber has a coefficient of moisture absorption of not less than 5 % at 35°C and at a RH of 95 % and a coefficient of water absorption extension of not less than 10 %.
- a woven or knitted fabric comprising such the elastic fibers is a fabric giving excellent comfortableness and having the so-called self-adjusting function wherein, when the woven or knitted fabric absorbs sweat or the like, the fibers are extended to open the stitches of the woven or knitted fabric to release moisture in the clothing, and when the woven or knitted fabric is dried, the fibers are contracted into the original lengths, thereby clogging the stitches of the woven or knitted fabric to prevent the release of temperature in the clothing.
- the woven or knitted fabric gives a sticky sense or stuffy sense
- the coefficient of water absorption extension is less than 10 %
- the reversibly extending or contracting characteristic due to the absorption or release of water is insufficient.
- the stitches of the woven or knitted fabric are sufficiently not opened or closed, and the fabric giving excellent comfortableness is not obtained.
- the coefficient of moisture absorption or the coefficient of water absorption extension in the elastic fibers of the present invention comprising the above-mentioned polyether ester is excessively large, elastic performance, heat resistance, weather (light) resistance, chemical resistance, and the like are liable to be deteriorated.
- the coefficient of moisture absorption is preferably in a range of 5 to 45 %, more preferably in a range of 10 to 40 %.
- the coefficient of water absorption extension is preferably in a range of 10 to 100 %, more preferably in a range of 10 to 80 %, furthermore preferably in a range of 15 to 60 %.
- the finishing oil is adhered to the surface of the elastic fiber in an amount of 0.5 to 5.0 percent by weight based on the weight of said fiber, and it is preferable in said finishing oil that at least one lubricant selected from the group consisting of mineral oils, silicones, and aliphatic esters occupies 70 to 100 percent by weight of said finishing oil.
- the above-mentioned lubricant selected from the mineral oils, the silicones, and the aliphatic esters little swells the elastic fiber, does not cause the increase of friction and the deterioration of dynamical characteristics due to the swelling, and improves process stability in a fiber-producing process and in post-processing processes.
- the content (the total content of the lubricants, when the lubricants are used) of the lubricant is controlled to 70 to 100 percent by weight. Thereby, the traveling stability of the fiber on the production of the fiber can be improved, and the abnormal elongation of the fiber and the production of scum can be prevented.
- the mineral oils having viscosities in the range of 5 ⁇ 10 -6 to 4 ⁇ 10 -5 m 2 /s at 30°C are preferable.
- the mineral oils having the viscosities in such the viscosity range little evaporate during storage. Thereby, the composition ratio of the finishing oil on the elastic fiber is little changed, and the high smoothness can be maintained.
- the silicone is polydimethylsiloxane, and has a viscosity of 5 ⁇ 10 -6 to 4 ⁇ 10 -5 m 2 /s at 30°C for the same reason as in the case of the mineral oils.
- aliphatic esters are compounds such as aliphatic acid monoalkyl esters, dialkyl aliphatic dicarboxylates, and the mono- or multi-fatty acid esters of aliphatic polyhydric alcohols, and preferably have the molecular weights in a range of 250 to 550. High smoothness can be maintained by controlling the molecular weights to such the range of the molecular weight.
- the fatty acid monoalkyl esters in the aliphatic esters preferably used include octyl octanoate, octyl stearate, isotridecyl laurate, isotridecyl oleate, and lauryl oleate.
- the dialkyl aliphatic dicarboxylates include diisooctyl adipate.
- the mono- or multi-fatty acid esters of the aliphatic polyhydric alcohols include trimethylol propane trioctanoate. Especially, the aliphatic acid monoalkyl esters are preferable.
- the ether-based or ester-based nonionic surfactant is the nonionic surfactant having a viscosity of 8 ⁇ 10 6 to 5 ⁇ 10 -5 m 2 /s at 30°C.
- the ether-based nonionic surfactant preferably used includes polyalkylene glycol alkyl ethers and polyalkylene glycol aryl ethers.
- the ester-based nonionic surfactant includes the alkylene oxide adducts of polyhydric alcohol partial esters, and polyalkylene glycol alkyl ethers are especially preferable.
- the alkyl group has the carbon atoms within a range of 8 to 20 carbon atoms, the elastic fiber is hardly swollen, and high smoothness can also simultaneously be achieved.
- the alkylene group of the polyalkylene glycol chain has two or three carbon atoms, especially two carbon atoms, and it is suitable that the number of the chains (the molar number of ethylene oxide added to the alcohol) is within a range of 3 to 20. When the number of the chains is within the range, compatibility with the lubricants comprising the above-mentioned mineral oils, the silicones or the aliphatic esters is not deteriorated.
- the above-mentioned mineral oils, the silicones, and the like have viscosities of 5 ⁇ 10 -6 to 2 ⁇ 10 -5 m 2 /s at 30 °C
- the above-mentioned ether-based or ester-based nonionic surfactant is not necessarily contained in the finishing oil, but it is preferable at the point of handleability, that said nonionic surfactant is contained in an amount of not more than 30 percent by weight, when the above-mentioned viscosity exceeds 2 ⁇ 10 -5 m 2 /s.
- the finishing oil used in the present invention is comprised of the above-mentioned components, but one or more other components may, if necessary, be added in small amounts within a range not affecting the object of the present invention.
- Lubricating auxiliaries for example, another nonionic surfactant, an anionic or cationic surfactant, stability-improving agents such as an antioxidant and an ultraviolet absorber, may be added in small amounts.
- the above-mentioned finishing oil used in the present invention has a viscosity in a range of 5 ⁇ 10 -6 to 4 ⁇ 10 -5 m 2 /s at 30°C.
- the viscosity is controlled to such the range, the components in the finishing oil are hardly evaporated during the storage of the elastic fiber, and the high smoothness can be maintained.
- the finishing oil has a high viscosity in a range of 2 ⁇ 10 -5 to 4 ⁇ 10 -5 m 2 /s at 30°C, and is imparted as a neat finishing oil in a spinning process
- the finishing oil is, for example, heated to lower the viscosity to not more than 2 X 10 -5 m 2 /s.
- the temperature is controlled to at most 60°C.
- the amount of the above-mentioned finishing oil adhered to the elastic fiber is preferably 0.5 to 5.0 percent by weight, more preferably 1.0 to 4.0 percent by weight, based on the weight of said fiber.
- the above-mentioned high coefficient of moisture absorption and the above-mentioned high coefficient of water absorption extension is easily achieved by copolymerizing the above-mentioned polyether ester elastomer with a metal organic sulfonate represented by the following general formula (1) and controlling the intrinsic viscosity of the elastic fiber to not less than 0.9.
- R1 represents an aromatic hydrocarbon group or an aliphatic hydrocarbon group, preferably an aromatic hydrocarbon group having 6 to 15 carbon atoms or an aliphatic hydrocarbon group having not more than 10 carbon atoms. Particularly preferable R1 represents an aromatic hydrocarbon group having 6 to 12 carbon atoms, especially a benzene ring.
- M1 represents an alkali metal or an alkaline earth metal, and j represents 1 or 2. Especially, M1 represents preferably an alkali metal (for example, lithium, sodium or potassium), and j represents preferably 1.
- X1 represents an ester-forming functional group
- X2 represents an ester-forming functional group identical to or different from X1 or a hydrogen atom, but represents preferably the ester-forming functional group.
- the ester-forming functional group may be a group for reacting and binding to the main chain or terminal of the polyether ester, and include concretely by the following groups. (wherein, R' represents a lower alkyl group or a phenyl group; a and d represent each an integer of 1 to 10; b represents an integer of 2 to 6).
- the preferably concrete examples of the metal organic sulfonate represented by the above-mentioned general formula (1) include sodium 3,5-dicarbomethoxybenzenesulfonate, potassium 3,5-dicarbomethoxybenzenesulfonate, lithium 3,5-dicarbomethoxybenzenesulfonate, sodium 3,5-dicarboxybenzenesulfonate, potassium 3,5-dicarboxybenzenesulfonate, lithium 3,5-dicarboxybenzenesulfonate, sodium 3,5-di( ⁇ -hydroxyethoxycarbonyl)benzenesulfonate, potassium 3,5-di( ⁇ -hydroxyethoxycarbonyl)benzenesulfonate, lithium 3,5-di( ⁇ -hydroxyethoxycarbonyl)benzenesulfonate, sodium 2,6-dicarbomethoxynaphthalene-4-sulfonate, potassium 2,6-dicarbomethoxynaphthalene-4-sulf
- the copolymerization of the metal organic sulfonate represented by the following general formula (2) is preferable at a point capable of easily increasing the intrinsic viscosity of the polyether ester elastomer to not less than 0.9 and further at a point capable of remarkably enhancing the coefficient of moisture absorption and the coefficient of water absorption extension of the obtained elastic fiber.
- a point capable of easily increasing the intrinsic viscosity of the polyether ester elastomer to not less than 0.9
- a point capable of remarkably enhancing the coefficient of moisture absorption and the coefficient of water absorption extension of the obtained elastic fiber According to our researches, it has been found by the copolymerization of such the metal organic sulfonate that an extremely high level coefficient of water absorption extension of not less than 20 % can be achieved to easily give a fabric giving excellent comfortableness.
- R2 represents an aromatic hydrocarbon group or an aliphatic hydrocarbon group which is the same as the definition of R1 in the above-mentioned general formula (1)
- M2 represents an alkali metal or an alkaline earth metal which is the same as the definition of M1 in the above-mentioned general formula (1).
- the preferable concrete examples of such the metal organic sulfonate includes sodium 3,5-di( ⁇ -hydroxyethoxycarbonyl)benzenesulfonate, potassium 3,5-di( ⁇ -hydroxyethoxycarbonyl)benzenesulfonate, and lithium 3,5-di( ⁇ -hydroxyethoxycarbonyl)benzenesulfonate.
- the copolymerization quantity of the above-mentioned metal organic sulfonate is too much, the melting point of the elastic fiber tends to be lowered to deteriorate heat resistance, weather (light) resistance, chemical resistance, and the like. Therefore, it is preferable that the copolymerization quantity is in the range of 0.1 to 20 percent by mole based on all the acid components constituting the polyether ester elastomer. To the contrary, when the above-mentioned copolymerization quantity is too little, the coefficient of moisture absorption and the coefficient of water absorption extension trends to be lowered. Therefore, it is more preferable that the copolymerization quantity is in the range of 0.5 to 15 percent by mole.
- the polyether ester elastomer used in the present invention can be obtained, for example, by subjecting raw materials comprising dimethyl terephthalate, tetramethylene glycol and polyoxyethylene glycol to an ester interchange reaction in the presence of an ester interchange catalyst to form the bis( ⁇ -hydroxybutyl) terephthalate and/or the oligomer and then melt-polycondensing the bis( ⁇ -hydroxybutyl) terephthalate and/or the oligomer in the presence of a polycondensation catalyst and a stabilizer at high temperature under reduced pressures.
- the salt of an alkali metal such as sodium the salt of an alkaline earth metal such as magnesium or calcium, or the compound of a metal such as titanium, zinc or manganese as the above-mentioned ester interchange catalyst.
- the amount of the used catalyst is especially not limited. A plurality of the catalysts can also together be used.
- a hindered phenol-based compound or a hindered amine-based compound described later is added to the above-mentioned polyether ester, because of having effects for not only preventing the lowering in the intrinsic viscosity of the polymer, when melt-molded, but also controlling the thermal deterioration, oxidation deterioration, photo-deterioration and the like of said obtained elastic fiber .
- the employment of a hindered phenol-based compound having a double bond in the molecule and represented by the general formula (3) described below is more preferable at a point that the elastic fiber having a high intrinsic viscosity is easily obtained and at a point that the polyether ester elastic fiber having the high coefficient of moisture absorption and the high coefficient of water absorption extension can easily be produced, because the hindered phenol-based compound represented by the general formula (3) has an effect for promoting the polycondensation reaction of the polyether ester elastomer of the present invention.
- the substituents R3 and R4 represent each independently a monovalent organic group having one to six carbon atoms, wherein when there are a plurality of the substitutents R3 and /or a plurality of the substitutents R4, the substituents may be identical or different each other; m and n represent each independently an integer of 0 to 4; and R5 represents a hydrogen atom or an organic group having one to five carbon atoms.
- the concrete examples of such the hindered phenol-based compound having the double bond in the molecule include the compounds represented by the following formulas (4) to (7).
- the hindered phenol-based compound represented by the following formula (4) is especially preferable, because of giving the above-mentioned elastic fiber having the high coefficient of moisture absorption and the high coefficient of water absorption extension.
- the ester interchange catalyst can be supplied at the early stage of the ester interchange reaction in addition to the time for the preparation of raw materials. Also, the stabilizer can be supplied until the early time of the polycondensation reaction, but it is preferable to add the stabilizer at the finish of the ester interchange reaction. Further, the polycondensation catalyst can be supplied until the early time of the polycondensation reaction process.
- a method for enhancing the intrinsic viscosity of the elastic fiber to not less than 0.9 can be a method for polymerizing the polyether ester elastomer in a solid phase, a method for using a chain extender at a stage for synthesizing the polyester ether elastomer and at a stage for melt-spinning the polyester ether elastomer, and the like, in addition to the above-mentioned method.
- the preferable concrete examples of the chain extender used herein include oxazoline compounds such as 2,2'-bis(2-oxazoline), and N,N'-terephthaloylbiscaprolactam.
- the elastic fiber comprises the above-mentioned polyether ester elastomer, and has an intrinsic viscosity of not less than 0.9.
- the above-mentioned intrinsic viscosity is not less than 0.9, the extremely high coefficient of moisture absorption and the extremely high coefficient of water absorption extension can be realized, and a fabric giving excellent comfortableness can easily be obtained.
- the intrinsic viscosity is too large, the fiber productivity of the polymer is not only deteriorated, but the cost for producing the fiber is also enhanced. Therefore, it is more preferable that the intrinsic viscosity is in a range of 0.9 to 1.2.
- a breaking elongation of not less than 400 % is preferable at a point that the coefficient of moisture absorption and the coefficient of water absorption extension can be enhanced to not less than 5 % and not less than 10 %, respectively, and as a point that the breakage of the elastic fiber caused by the slight changes of conditions in a process on weaving or knitting can be reduced.
- the above-mentioned breaking elongation is more preferably in a range of 400 to 900 %, furthermore preferably in a range of 400 to 800 %.
- the shrinkage percentage of the elastic fiber in boiling water is not less than 10 %.
- the elastic fiber of the present invention can be produced, for example, by melt-extruding the polyether ester in a pellet-like state from a spinneret, thermally insulating a space ranging from a place just under the spinneret to a place apart from the spinneret at a distance of at least 10 cm, preferably at least 15 cm, imparting a finishing oil to the spun fiber at a place within 5 m, preferably 4 m, from the place just under the spinneret, taking off the fiber at a take-off speed of 300 to 1,200 m / minute, preferably 400 to 980 m / minute, and then winding up the fiber at a wind-up draft ratio of 1.3 to 1.6, preferably 1.4 to 1.5, based on said take-off speed.
- the wind-up draft rate of less than 1.3 is not preferable, because tensions added to the fiber between Godet rollers and between the Godet roller and a winder are insufficient to cause the winding of the fiber on the Godet roller and the subsequent breakage of the fiber.
- the coefficient of moisture absorption and the coefficient of water absorption extension it is preferable for controlling the coefficient of moisture absorption and the coefficient of water absorption extension to not less than 5 % and not less than 10 %, respectively, to thermally insulate the space under the spinneret, control the spinning speed to a low value as much as possible, shorten a distance to an oiling device to stop an advance in the orientation of the fiber, and further wind up the taken elastic fiber at a small wind-up draft ratio as much as possible within a range in which the elastic fiber can be wound up without being drawn as much as possible. From such the viewpoint, it is not preferable to wind up or take off the elastic fiber and then continuously draw or further thermally treat the elastic fiber.
- a sample was subjected to the control of humidity in an air-conditioned room controlled to prescribed conditions for 24 hours, and then the coefficient of moisture absorption was determined from the weight of the absolutely dried sample and the weight of the humidity-controlled sample according to the following expression.
- Coefficient of moisture absorption (weight of humidity-controlled sample - weight of absolutely dried sample) ⁇ 100 / weight of absolutely dried sample.
- a fiber was reeled, treated in boiling water under non-tension for 30 minutes, subjected to an air-drying and humidity-controlling treatment at 20°C and at 65 % RH, and then subjected to a dry thermal treatment under an environment of 160°C under non-tension for two minutes.
- the treated fiber was left under an environment of 20°C and 65 % RH for 24 hours, and a load of 0.88 ⁇ 10 -3 cN / dtex was hung on the fiber.
- the length of the fiber was measured as "length of fiber when dried".
- the fiber was immersed in softened water controlled at 20°C for one minute, lifted from the water, nipped with filter paper which have been air-dried at 20°C and at 65% RH, placed on a horizontal base, subjected to the putting of a weight of 1.5 g/cm 2 on the fiber, and then left for two seconds to wipe off excessive water on the surface of the fiber. After ten seconds, a load of 0.88 ⁇ 10 -3 cN / dtex was hung on the fiber, and the length of the fiber was measured as "length of fiber when absorbing water".
- the coefficient of water absorption extension was calculated according to the following expression. All the measurements were carried out under an environment of 20°C and 65 % RH.
- Coefficient of water absorption extension (length of fiber when absorbing water - length of fiber when dried) ⁇ length of fiber when dried ⁇ 100%.
- Coefficient of moisture absorption extension (length of fiber when absorbing moisture - length of fiber when dried ⁇ length of fiber when dried ⁇ 100 %.
- the breaking strength and the breaking elongation were measured by carrying out a tension test with a Tensilon RTM-100 tension tester manufactured by Toyo Baldwin Co. in an air-conditioned room controlled to 20°C ⁇ 65 % RH.
- the elastic fibers were knitted into the 132 g/m 2 knitted fabrics with a cylindrical knitting machine.
- the fabrics were used to cover the elbows and knees of arbitrarily selected five persons for one day, and then the sticky senses and the stuffy senses were evaluated. The results were shown as (little) wherein the sticky senses and the stuffy senses are little, respectively, or (large) wherein the sticky senses and the stuffy senses are large, respectively.
- the polycondensation reaction was carried by reducing the inner pressure to 30 mmHg over about 30 minutes, further reducing to 3 mmHg over 30 minutes, then reacting at an inner temperature of 250°C under a vacuum of 1 mmHg for 200 minutes, adding 1 part by weight of the following hindered phenol-based compound (8) and 2 parts by weight of the following hindered amine-based compound (9) at the time, and then further reacting at 250°C under a vacuum of not more than 1 mmHg for 20 minutes.
- the produced polyether ester elastomer had an intrinsic viscosity of 1.10, and a polybutylene terephthalate (hard segment) / polyoxyethylene glycol (soft segment) weight ratio of 50 / 50.
- the obtained polyether ester elastomer was melted at 230°C, and extruded from a spinneret at an extrusion rate of 3.05 g / minute. At this time, a space ranged from a place just under the spinneret to a place apart from the spinneret at a distance of 9 cm was thermally insulated.
- a finishing oil comprising 100 % polydimethyl siloxane having a viscosity of 1 ⁇ 10 -5 m 2 /s at 30°C was imparted to the melted and extruded polymer in an amount of 3.0 percent by weight based on the weigh of the fibers at a place of 3 m below the spinneret, and the oiled fibers were taken off on a Godet roller at a speed of 510 m / minute, and further wound up at a speed of 750 m / minute (winding draft ratio : 1.47) to obtain the polyether ester elastic fibers of 44 dtex / filament.
- the results are shown in Table 1.
- the above-mentioned elastic fibers were knitted with a cylindrical knitting machine to form the knitted fabric of 132 g / m 2 .
- the knitted fabric was left under an environment of 20°C and 65 % RH for 24 hours, immersed in 20°C softened water for one minute, taken out from the water, and then nipped with filter paper to remove the water adhered to the surface of the knitted fabric. Then, the stitch openings of the treated knitted fabric were observed. Consequently, it was confirmed that the stitch openings of the knitted fabric were enlarged, after the knitted fabric was immersed in the softened water.
- Example 1 The operations were carried out similarly as in Example 1 except that the copolymerization ratio of the polyoxyethylene glycol (number-average molecular weight : 4,000) was changed to a hard segment / soft segment weight ratio of 60 / 40 percent by weight, and the polyether ester elastic filaments having an intrinsic viscosity of 1.12 were consequently obtained.
- the results are shown in Table 1.
- Example 1 The operations were carried out similarly as in Example 1 except that the copolymerization quantity of dihydroxyethyl 5-Na sulfoisophthalate (the same as sodium 3,5-di( ⁇ -hydroxyethoxycarbonyl)benzenesulfonate) was changed to 2.0 percent by mole based on all the acid components constituting the polyether ester elastomer, and the polyether ester elastic filaments having an intrinsic viscosity of 1.18 were consequently obtained. The results are shown in Table 1.
- dihydroxyethyl 5-Na sulfoisophthalate the same as sodium 3,5-di( ⁇ -hydroxyethoxycarbonyl)benzenesulfonate
- Example 1 The operations were carried out similarly as in Example 1 except that dimethyl 5-Na sulfoisophthalate was used instead of the dihydroxyethyl 5-Na sulfoisophthalate (the same as sodium 3,5-di( ⁇ -hydroxyethoxycarbonyl)benzenesulfonate), and the polyether ester elastomer having an intrinsic viscosity of 1.10 was consequently obtained.
- the polyether ester elastomer was used to melt-spin the elastomer similarly as in Example 1. The results are shown in Table 1.
- the elastic fibers obtained in Example 1 were knitted into a circular knitted fabric (smooth) having an end spacing of 52 warps / 2.54 cm and a pick spacing of 60 wefts / 2.54 cm, and male underwear (upper half portion) and sportswear (upper half portion) in whose armpits and chest portions the pieces of the knitted fabric were used were formed.
- the underwear and the sportswear were worn by five persons and then subjected to their physical exercises for two hours, respectively. Consequently, the sticky senses and stuffy senses of the used underwear and the sportswear were less than those of underwear and sportswear not using the above-mentioned elastic fibers, and the comfortableness was excellent.
- the elastic fibers of the present invention have excellent recyclability, because of comprising the polyether ester. Additionally, the elastic fibers of the present invention exhibit a self-adjusting function for changing the stitch openings of the fabric by the absorption or release of water, because of having the good moisture-absorbing or releasing property and being reversibly expanded or contracted by the absorption or release of the water, and can give a fabric having excellent comfortableness. Therefore, the above-mentioned elastic fibers exhibit excellent performances in the uses of clothes, especially sportswear, inner wear, linings, stockings, socks and the like.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
- Woven Fabrics (AREA)
- Undergarments, Swaddling Clothes, Handkerchiefs Or Underwear Materials (AREA)
- Knitting Of Fabric (AREA)
- Chemical Treatment Of Fibers During Manufacturing Processes (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003175788 | 2003-06-20 | ||
JP2003329584 | 2003-09-22 | ||
PCT/JP2004/008940 WO2004113599A1 (ja) | 2003-06-20 | 2004-06-18 | ポリエーテルエステル弾性繊維及びこれを用いた布帛、衣料 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1643019A1 EP1643019A1 (en) | 2006-04-05 |
EP1643019A4 EP1643019A4 (en) | 2007-09-05 |
EP1643019B1 true EP1643019B1 (en) | 2010-09-22 |
Family
ID=33543484
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP04746409A Expired - Lifetime EP1643019B1 (en) | 2003-06-20 | 2004-06-18 | Polyether ester elastic fiber and fabrics and clothes made by using the same |
Country Status (9)
Country | Link |
---|---|
US (1) | US20060177655A1 (ja) |
EP (1) | EP1643019B1 (ja) |
JP (1) | JP4202361B2 (ja) |
KR (1) | KR101183498B1 (ja) |
CA (1) | CA2529842C (ja) |
DE (1) | DE602004029254D1 (ja) |
HK (1) | HK1116520A1 (ja) |
TW (2) | TWI285688B (ja) |
WO (1) | WO2004113599A1 (ja) |
Families Citing this family (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050208857A1 (en) | 2004-03-19 | 2005-09-22 | Nike, Inc. | Article of apparel incorporating a modifiable textile structure |
US7437774B2 (en) | 2004-03-19 | 2008-10-21 | Nike, Inc. | Article of apparel incorporating a zoned modifiable textile structure |
US9700077B2 (en) | 2004-03-19 | 2017-07-11 | Nike, Inc. | Article of apparel with variable air permeability |
JP2007023417A (ja) * | 2005-07-15 | 2007-02-01 | Teijin Fibers Ltd | 嵩高吸湿弾性糸及びその製造方法 |
US8187984B2 (en) | 2006-06-09 | 2012-05-29 | Malden Mills Industries, Inc. | Temperature responsive smart textile |
JP4983138B2 (ja) * | 2006-08-03 | 2012-07-25 | パナソニック株式会社 | 高分子発熱体 |
US8389100B2 (en) | 2006-08-29 | 2013-03-05 | Mmi-Ipco, Llc | Temperature responsive smart textile |
JP2008057099A (ja) | 2006-08-29 | 2008-03-13 | Mmi-Ipco Llc | 感温性スマートテキスタイル |
JP2008069124A (ja) * | 2006-09-15 | 2008-03-27 | Teijin Fibers Ltd | 化粧料 |
JP4947796B2 (ja) * | 2007-06-08 | 2012-06-06 | 竹本油脂株式会社 | 合成繊維用ストレート型処理剤、これを用いる合成繊維仮撚加工糸の処理方法及び合成繊維仮撚加工糸 |
JP2009235242A (ja) * | 2008-03-27 | 2009-10-15 | Teijin Fibers Ltd | 共重合ポリエステル及びポリエステル繊維 |
JP2009235243A (ja) * | 2008-03-27 | 2009-10-15 | Teijin Fibers Ltd | 共重合ポリエステル及びポリエステル繊維 |
US10039610B2 (en) | 2008-08-08 | 2018-08-07 | Medline Industries, Inc. | Zip strip draping system and methods of manufacturing same |
US9334608B2 (en) | 2009-10-20 | 2016-05-10 | Teijin Frontier Co., Ltd. | Polyester fiber, method for producing the same, cloth, textile product, and polyester formed article |
WO2012086563A1 (ja) * | 2010-12-20 | 2012-06-28 | 東レ・オペロンテックス株式会社 | 弾性繊維を有する編地とその製造方法及びその編地を用いた伸縮性衣料と伸縮性衣料資材 |
JP5748475B2 (ja) * | 2010-12-24 | 2015-07-15 | 株式会社ムツミテキスタイル | ポリウレタン系弾性繊維からなる丸編地とその製造方法及びその丸編地を用いた伸縮性衣料と伸縮性衣料資材 |
US10441010B2 (en) | 2011-10-18 | 2019-10-15 | Medline Industries, Inc. | Disposable medical gown |
USD785284S1 (en) | 2011-10-18 | 2017-05-02 | Medline Industries, Inc. | Medical gown |
USD774729S1 (en) | 2011-10-18 | 2016-12-27 | Medline Industries, Inc. | Medical gown |
USD836297S1 (en) | 2011-10-18 | 2018-12-25 | Medline Industries, Inc. | Medical gown |
USD863727S1 (en) | 2011-10-18 | 2019-10-22 | Medline Industries, Inc. | Medical gown |
US10455872B2 (en) | 2011-10-18 | 2019-10-29 | Medline Industries, Inc. | Disposable medical gown |
USD821704S1 (en) | 2011-10-18 | 2018-07-03 | Medline Industries, Inc. | Medical gown |
CA144409S (en) | 2011-10-18 | 2013-06-18 | Medline Ind Inc | Medical gown |
USD791434S1 (en) | 2011-10-18 | 2017-07-11 | Medline Industries, Inc. | Medical gown |
USD779156S1 (en) | 2011-10-18 | 2017-02-21 | Medline Industries, Inc. | Medical gown |
KR101494319B1 (ko) | 2013-07-30 | 2015-02-23 | 주식회사 휴비스 | 영구압축 변형율이 낮은 열접착 섬유 |
US11116263B2 (en) | 2013-11-21 | 2021-09-14 | Medline Industries, Inc. | Gown for self-donning while maintaining sterility and methods therefor |
KR102291563B1 (ko) * | 2014-12-30 | 2021-08-19 | 코오롱플라스틱 주식회사 | 3d 프린팅용 조성물 및 이를 이용한 3d 프린터용 필라멘트 |
KR102400353B1 (ko) * | 2015-04-13 | 2022-05-24 | 주식회사 휴비스 | 수분전이 특성에 의한 자율 통기조절기능이 향상된 탄성섬유 |
KR101822643B1 (ko) | 2015-12-28 | 2018-01-30 | 주식회사 휴비스 | 폴리에스테르계 탄성부직포를 이용한 의류용 신축심지 |
EP3763872B1 (en) * | 2018-03-07 | 2024-01-10 | Kuraray Co., Ltd. | Melt-anisotropic aromatic polyester multifilament |
KR101970598B1 (ko) | 2018-06-15 | 2019-05-17 | (주) 정산인터내셔널 | 폴리에스테르-에테르 블록공중합체의 원사를 이용한 투명성이 강화된 원단 및 그 제조방법 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR870001132B1 (ko) * | 1983-04-14 | 1987-06-09 | 도오요오 보오세끼 가부시끼가이샤 | 제전성섬유 및 그 제조방법 |
JPH073029B2 (ja) * | 1986-03-28 | 1995-01-18 | 東レ株式会社 | 吸水性ウエツブの製造法 |
US4906729A (en) * | 1988-08-05 | 1990-03-06 | E. I. Du Pont De Nemours And Company | Thermoplastic copolyetherester elastomers |
JPH08209459A (ja) * | 1995-02-07 | 1996-08-13 | Nippon Ester Co Ltd | ポリエーテルエステル系弾性糸の製造法 |
JP3577362B2 (ja) * | 1995-06-12 | 2004-10-13 | 帝人ファイバー株式会社 | 抄紙用熱接着性繊維及び紙 |
JP3592842B2 (ja) * | 1996-07-08 | 2004-11-24 | 帝人ファイバー株式会社 | ポリエステル系弾性繊維及びそれからなる伸縮性湿式不織布 |
JPH11279883A (ja) | 1998-03-24 | 1999-10-12 | Mitsubishi Rayon Co Ltd | ポリエステル複合糸 |
JP2000073232A (ja) * | 1998-08-26 | 2000-03-07 | Nippon Ester Co Ltd | 吸湿性ポリエステル繊維 |
KR100471931B1 (ko) * | 2000-07-31 | 2005-03-10 | 산요가세이고교 가부시키가이샤 | 탄성섬유용 방사유제 |
JP4064149B2 (ja) * | 2002-05-17 | 2008-03-19 | 帝人ファイバー株式会社 | エラストマー組成物及びそれよりなる繊維 |
-
2004
- 2004-06-18 TW TW093117766A patent/TWI285688B/zh not_active IP Right Cessation
- 2004-06-18 KR KR1020057024465A patent/KR101183498B1/ko active IP Right Grant
- 2004-06-18 US US10/561,155 patent/US20060177655A1/en not_active Abandoned
- 2004-06-18 EP EP04746409A patent/EP1643019B1/en not_active Expired - Lifetime
- 2004-06-18 WO PCT/JP2004/008940 patent/WO2004113599A1/ja active Application Filing
- 2004-06-18 JP JP2005507293A patent/JP4202361B2/ja not_active Expired - Lifetime
- 2004-06-18 TW TW095148263A patent/TW200722563A/zh unknown
- 2004-06-18 DE DE602004029254T patent/DE602004029254D1/de not_active Expired - Lifetime
- 2004-06-18 CA CA2529842A patent/CA2529842C/en not_active Expired - Fee Related
-
2008
- 2008-05-19 HK HK08105508.6A patent/HK1116520A1/xx not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
WO2004113599A1 (ja) | 2004-12-29 |
JPWO2004113599A1 (ja) | 2006-07-20 |
TW200502451A (en) | 2005-01-16 |
HK1116520A1 (en) | 2008-12-24 |
KR101183498B1 (ko) | 2012-09-20 |
DE602004029254D1 (de) | 2010-11-04 |
KR20060021910A (ko) | 2006-03-08 |
TWI285688B (en) | 2007-08-21 |
EP1643019A4 (en) | 2007-09-05 |
US20060177655A1 (en) | 2006-08-10 |
CA2529842C (en) | 2011-07-12 |
JP4202361B2 (ja) | 2008-12-24 |
TW200722563A (en) | 2007-06-16 |
EP1643019A1 (en) | 2006-04-05 |
CA2529842A1 (en) | 2004-12-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1643019B1 (en) | Polyether ester elastic fiber and fabrics and clothes made by using the same | |
JP2004332166A (ja) | ポリ乳酸繊維 | |
JP5704530B2 (ja) | ポリウレタン弾性糸およびその製造方法 | |
CN114222834A (zh) | 再循环聚氨酯弹性纤维、其制法、含有该再循环聚氨酯弹性纤维的纤维结构物、褶裥构件及卫生材料 | |
JP4661266B2 (ja) | 合成繊維、およびそれからなる繊維構造体 | |
WO2020169417A1 (en) | A process for producing a thermoplastic polyurethane fiber with low shrinkage, and the use of the fiber | |
JP2008274476A (ja) | 耐光性に優れたポリエーテルエステル弾性繊維 | |
CN100404735C (zh) | 聚醚酯弹性纤维以及采用它的织物、衣料 | |
JP2009235242A (ja) | 共重合ポリエステル及びポリエステル繊維 | |
JP2009235243A (ja) | 共重合ポリエステル及びポリエステル繊維 | |
JP3694103B2 (ja) | 自然分解性複合繊維及びその応用製品 | |
JP4834858B2 (ja) | ポリウレタン糸およびその製造方法 | |
JP6383570B2 (ja) | ポリウレタン弾性繊維 | |
JP4473638B2 (ja) | 感温吸水伸長繊維 | |
JP3259840B2 (ja) | 難燃ポリエステル繊維 | |
JP3683037B2 (ja) | 自然分解性複合糸およびその製品 | |
JP4886657B2 (ja) | 吸湿捲縮複合繊維 | |
JP2005281908A (ja) | 吸放湿性ポリエーテルエステル弾性繊維を含む繊維製品 | |
JP2008274477A (ja) | ポリエーテルエステル弾性繊維の製造方法 | |
JP2019081864A (ja) | 共重合ポリエステル組成物およびそれを含む複合繊維 | |
JP3683036B2 (ja) | 自然分解性複合糸およびその製品 | |
JPH08209459A (ja) | ポリエーテルエステル系弾性糸の製造法 | |
JPH05140818A (ja) | ポリエーテルエステルブロツク共重合体弾性糸 | |
JP2005200792A (ja) | 吸湿性複合繊維 | |
JP2006176897A (ja) | ポリエーテルエステル弾性繊維およびその製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20060113 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): DE FR GB IT NL |
|
REG | Reference to a national code |
Ref country code: HK Ref legal event code: DE Ref document number: 1085772 Country of ref document: HK |
|
DAX | Request for extension of the european patent (deleted) | ||
RBV | Designated contracting states (corrected) |
Designated state(s): DE FR GB IT NL |
|
A4 | Supplementary search report drawn up and despatched |
Effective date: 20070802 |
|
17Q | First examination report despatched |
Effective date: 20090429 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE FR GB IT NL |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REF | Corresponds to: |
Ref document number: 602004029254 Country of ref document: DE Date of ref document: 20101104 Kind code of ref document: P |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: VDEP Effective date: 20100922 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100922 Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100922 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20110623 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602004029254 Country of ref document: DE Effective date: 20110623 |
|
REG | Reference to a national code |
Ref country code: HK Ref legal event code: WD Ref document number: 1085772 Country of ref document: HK |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20130620 Year of fee payment: 10 Ref country code: GB Payment date: 20130619 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20130703 Year of fee payment: 10 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 602004029254 Country of ref document: DE |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20140618 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20150227 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 602004029254 Country of ref document: DE Effective date: 20150101 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150101 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140618 Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140630 |