JP4202361B2 - Clothing - Google Patents
Clothing Download PDFInfo
- Publication number
- JP4202361B2 JP4202361B2 JP2005507293A JP2005507293A JP4202361B2 JP 4202361 B2 JP4202361 B2 JP 4202361B2 JP 2005507293 A JP2005507293 A JP 2005507293A JP 2005507293 A JP2005507293 A JP 2005507293A JP 4202361 B2 JP4202361 B2 JP 4202361B2
- Authority
- JP
- Japan
- Prior art keywords
- elastic fiber
- weight
- ester
- crystal melting
- clothing
- 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 claims description 77
- -1 polybutylene terephthalate Polymers 0.000 claims description 58
- 238000010521 absorption reaction Methods 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 150000002148 esters Chemical class 0.000 claims description 44
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 40
- 239000013078 crystal Substances 0.000 claims description 35
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 33
- 229920000570 polyether Polymers 0.000 claims description 33
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 238000002844 melting Methods 0.000 claims description 28
- 230000008018 melting Effects 0.000 claims description 28
- 239000003921 oil Substances 0.000 claims description 28
- 239000000835 fiber Substances 0.000 claims description 24
- 229920001971 elastomer Polymers 0.000 claims description 18
- 239000000806 elastomer Substances 0.000 claims description 18
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 17
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 14
- 125000001931 aliphatic group Chemical group 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 238000007334 copolymerization reaction Methods 0.000 claims description 10
- 239000002480 mineral oil Substances 0.000 claims description 10
- 235000010446 mineral oil Nutrition 0.000 claims description 10
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 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
- 239000002736 nonionic surfactant Substances 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 238000009499 grossing Methods 0.000 claims description 7
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 238000001938 differential scanning calorimetry curve Methods 0.000 claims description 3
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 claims description 2
- 239000011734 sodium Substances 0.000 description 13
- 239000004744 fabric Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 229910052708 sodium Inorganic materials 0.000 description 11
- 238000006068 polycondensation reaction Methods 0.000 description 10
- 238000004804 winding Methods 0.000 description 10
- 239000003054 catalyst Substances 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
- 229940077388 benzenesulfonate Drugs 0.000 description 8
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 8
- 238000005809 transesterification reaction Methods 0.000 description 8
- 239000002585 base Substances 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 208000012886 Vertigo Diseases 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229920001515 polyalkylene glycol Polymers 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 238000009987 spinning Methods 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 230000006866 deterioration 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
- 238000009940 knitting Methods 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 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
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000001143 conditioned effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 238000002074 melt spinning Methods 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000001424 substituent group Chemical group 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-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
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 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
- 230000000694 effects 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
- 235000011187 glycerol Nutrition 0.000 description 2
- 230000001771 impaired effect Effects 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
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 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
- 229920000728 polyester Polymers 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
- 238000004064 recycling Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 238000003786 synthesis reaction Methods 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
- 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
- OHPWCSKOLOZNFC-UHFFFAOYSA-N 2-phenoxy-2-(phenoxymethyl)propanedioic acid Chemical compound C=1C=CC=CC=1OC(C(O)=O)(C(=O)O)COC1=CC=CC=C1 OHPWCSKOLOZNFC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- HZAIRVWAQRURND-UHFFFAOYSA-N 3,7-bis(methoxycarbonyl)naphthalene-1-sulfonic acid;sodium Chemical compound [Na].C1=C(C(=O)OC)C=C(S(O)(=O)=O)C2=CC(C(=O)OC)=CC=C21 HZAIRVWAQRURND-UHFFFAOYSA-N 0.000 description 1
- KPRILADFLSUPOF-UHFFFAOYSA-N 3-(2,2-dihydroxyethoxycarbonyl)-2-sulfobenzoic acid Chemical compound OC(O)COC(=O)C1=CC=CC(C(O)=O)=C1S(O)(=O)=O KPRILADFLSUPOF-UHFFFAOYSA-N 0.000 description 1
- RUADKXZXMGIBSQ-UHFFFAOYSA-N C(=O)(OC)OS(=O)(=O)C1=CC=CC=C1.[Li] Chemical compound C(=O)(OC)OS(=O)(=O)C1=CC=CC=C1.[Li] RUADKXZXMGIBSQ-UHFFFAOYSA-N 0.000 description 1
- LYASCGPZFQZTOA-UHFFFAOYSA-N C1=C(C=C(C(=C1C(=O)O)S(=O)(=O)O)C(=O)OCC(O)O)O Chemical compound C1=C(C=C(C(=C1C(=O)O)S(=O)(=O)O)C(=O)OCC(O)O)O LYASCGPZFQZTOA-UHFFFAOYSA-N 0.000 description 1
- SHWDCLQRSWTSRE-UHFFFAOYSA-N CCC(CO)(CO)CO.CCCCCCCC(O)=O.CCCCCCCC(O)=O.CCCCCCCC(O)=O Chemical compound CCC(CO)(CO)CO.CCCCCCCC(O)=O.CCCCCCCC(O)=O.CCCCCCCC(O)=O SHWDCLQRSWTSRE-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001507939 Cormus domestica Species 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
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- IPLJXALXGKSNPT-UHFFFAOYSA-N benzenesulfonic acid;lithium Chemical compound [Li].OS(=O)(=O)C1=CC=CC=C1 IPLJXALXGKSNPT-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 238000011161 development Methods 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
- 238000004090 dissolution Methods 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
- 238000005516 engineering process Methods 0.000 description 1
- RZTAMFZIAATZDJ-UHFFFAOYSA-N felodipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OC)C1C1=CC=CC(Cl)=C1Cl RZTAMFZIAATZDJ-UHFFFAOYSA-N 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 210000003127 knee Anatomy 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
- 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
- 150000002736 metal compounds Chemical class 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
- 229910052757 nitrogen Inorganic materials 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
- 150000002989 phenols Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000012805 post-processing Methods 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
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery 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
- 230000002441 reversible effect Effects 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 229940077386 sodium benzenesulfonate Drugs 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
- 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
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 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
- 238000005406 washing Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
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- 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
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- 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)
Description
本発明は、吸放湿性が良好であり、吸放水により可逆に伸縮し、特にスポーツ用途やインナー用途などにおいて従来にない快適性を発現する布帛が得られるポリエーテルエステル弾性繊維に関するものである。 The present invention relates to a polyetherester elastic fiber that has good moisture absorption / release properties, reversibly expands / contracts by water absorption / release water, and can provide a fabric that exhibits unprecedented comfort especially in sports and inner applications.
背景の技術
従来、衣料用や産業資材用の弾性繊維としては、ポリウレタン弾性繊維が主に用いられているが、耐熱性、耐薬品性、耐候（光）性が劣るという欠点がある。また、製造上、乾式紡糸プロセスが必要なため、溶剤回収が必要であり、低生産性、エネルギー多消費性であるという問題がある。更に、ポリウレタン弾性繊維はリサイクルが困難であり、燃焼時には有害ガスを発生するなどといった、今後の循環型社会の到来に向けて多くの課題を有している。
BACKGROUND ART Conventionally, polyurethane elastic fibers are mainly used as elastic fibers for clothing and industrial materials, but have the disadvantages of poor heat resistance, chemical resistance, and weather resistance (light). In addition, since a dry spinning process is necessary for production, solvent recovery is required, and there is a problem of low productivity and high energy consumption. Furthermore, polyurethane elastic fibers are difficult to recycle and have many problems for the coming of a recycling society in the future, such as generation of harmful gases when burned.
このような背景のもと、溶融紡糸が可能な、ポリアルキレンテレフタレートのような高結晶性のポリエステルをハードセグメントとし、ポリアルキレングリコールをソフトセグメントとするポリエーテルエステル弾性繊維が、高生産性であること、耐熱性、耐熱セット性に優れることなどの利点を活かし実用化されている。さらに、リサイクルが可能で、有害ガスの発生もないことから、循環型社会に適した弾性繊維として今後の発展が期待されている（例えば、特公昭４７−１４０５４号公報、特開昭４８−１０３４６号公報、特開昭５７−７７３１７号公報など）。 Against this backdrop, polyether ester elastic fibers, which can be melt-spun and have a highly crystalline polyester such as polyalkylene terephthalate as a hard segment and polyalkylene glycol as a soft segment, have high productivity. It has been put to practical use by taking advantage of its excellent heat resistance and heat setability. Further, since it is recyclable and no harmful gas is generated, future development is expected as an elastic fiber suitable for a recycling society (for example, Japanese Patent Publication No. 47-14054, Japanese Patent Publication No. 48-10346). No., JP-A-57-77317, etc.).
かかるポリエーテルエステル弾性繊維としては、弾性的性能がポリウレタン弾性繊維に匹敵できるものとして、ハードセグメントとしてポリブチレンテレフタレート、ソフトセグメントとしてポリオキシブチレングリコールを用いたポリエーテルエステル弾性繊維などが使用されている。しかしながら、これらのハードセグメント及びソフトセグメントはいずれも一般的には疎水性であり、吸湿性や吸水性などの親水性を有するポリエーテルエステル弾性繊維では実用化されているものはほとんど皆無である。 As such a polyether ester elastic fiber, a polyether ester elastic fiber using polybutylene terephthalate as a hard segment and polyoxybutylene glycol as a soft segment is used as an elastic performance comparable to that of a polyurethane elastic fiber. . However, both of these hard segments and soft segments are generally hydrophobic, and almost no polyether ester elastic fiber having hydrophilic properties such as hygroscopicity and water absorption is practically used.
一方、国際公開第００／４７８０２号パンフレットには、吸湿性能を付与した弾性繊維が提案されているが、吸水率５００〜４，０００重量％の吸水性樹脂を含有したポリウレタン弾性体の具体例が記載されているに過ぎない。 On the other hand, in the pamphlet of International Publication No. 00/47802, an elastic fiber imparted with moisture absorption performance is proposed, but a specific example of a polyurethane elastic body containing a water-absorbing resin having a water absorption rate of 500 to 4,000% by weight is provided. It is only described.
また、従来提案されているように繊維自身に吸湿性を持たせるだけでは、これを布帛あるいはさらに衣服として、その快適性を向上させるのには限界があり、さらに新しい機能を持つ弾性繊維が求められている。 Moreover, there is a limit to improving the comfort of a fiber or even a garment simply by making the fiber itself hygroscopic as previously proposed, and there is a need for an elastic fiber having a new function. It has been.
本発明は、上記従来技術を背景になされたもので、その目的は、吸湿性が良好であり、吸放水により可逆的に大きく伸縮して、快適性に優れた布帛が得られる、リサイクル可能なポリエーテルエステル弾性繊維およびこれを用いた布帛、衣料を提供することにある。 The present invention has been made against the background of the above-described prior art, and its purpose is to have a good hygroscopic property and to reversibly expand and contract reversibly by absorbing and releasing water, thereby obtaining a fabric having excellent comfort and being recyclable. An object of the present invention is to provide polyetherester elastic fibers, and fabrics and clothing using the same.
本発明者らは、かかる背景の技術に鑑み検討を重ねた結果、本発明の目的は、次に示すポリエーテルエステル弾性繊維に達成できることを見出した。 As a result of repeated studies in view of the background technology, the present inventors have found that the object of the present invention can be achieved by the following polyether ester elastic fiber.
１．ポリブチレンテレフタレートをハードセグメントとしポリオキシエチレングリコールをソフトセグメントとするポリエーテルエステルエラストマーからなる弾性繊維であって、３５℃９５％ＲＨでの吸湿率が５％以上、吸水伸長率が１０％以上であるポリエーテルエステル弾性繊維を少なくとも一部に用いてなることを特徴とする衣料。 1. It is an elastic fiber made of a polyether ester elastomer having polybutylene terephthalate as a hard segment and polyoxyethylene glycol as a soft segment, and has a moisture absorption rate of 5% or more at 35 ° C. and 95% RH and a water absorption elongation rate of 10% or more. A garment comprising at least a part of a certain polyether ester elastic fiber.
２．ポリエーテルエステルエラストマーに、下記一般式（１）で表される有機スルホン酸金属塩が共重合されており、かつ弾性繊維の固有粘度が０．９以上である、１に記載の衣料。
３．弾性繊維の沸水収縮率が１０％以上である、２に記載の衣料。 3. The clothing according to 2, wherein the elastic fiber has a boiling water shrinkage of 10% or more.
４．有機スルホン酸金属塩が、下記一般式（２）で表される化合物である、２に記載の衣料。
５．有機スルホン酸金属塩の共重合量が、ポリエーテルエステルエラストマーを構成する酸成分を基準として０．１〜２０モル％の範囲である、２に記載の衣料。 5. The clothing according to 2, wherein the copolymerization amount of the organic sulfonic acid metal salt is in the range of 0.1 to 20 mol% based on the acid component constituting the polyether ester elastomer.
６．弾性繊維が示差走査型熱量計により得られるＤＳＣ曲線で２つの結晶融解ピークを有し、低温側の結晶融解ピーク高さＨｍ１と高温側の結晶融解ピーク高さＨｍ２との比Ｈｍ１／Ｈｍ２が０．６〜１．２の範囲であり、破断伸度が４００％以上である、１に記載の衣料。 6). The elastic fiber has two crystal melting peaks in a DSC curve obtained by a differential scanning calorimeter, and the ratio Hm1 / Hm2 between the crystal melting peak height Hm1 on the low temperature side and the crystal melting peak height Hm2 on the high temperature side is 0. 1. The garment according to 1, which is in the range of 6 to 1.2 and has a breaking elongation of 400% or more.
７．２つの結晶融解ピークの、低温側の結晶融解ピーク温度Ｔｍ１と高温側の結晶融解ピーク温度Ｔｍ２が、下記式を満足する、６に記載の衣料用ポリエーテルエステル弾性繊維。
２００℃≦Ｔｍ１＜Ｔｍ２≦２２５℃
7. The polyether ester elastic fiber for clothing according to 6, wherein the crystal melting peak temperature Tm1 on the low temperature side and the crystal melting peak temperature Tm2 on the high temperature side of the two crystal melting peaks satisfy the following formula.
200 ° C ≦ Tm1 <Tm2 ≦ 225 ° C
８．ハードセグメント：ソフトセグメントの比率が、重量を基準として３０：７０〜７０：３０の範囲である、１、２、６のいずれかに記載の衣料。 8). Clothing in any one of 1, 2, 6 whose ratio of a hard segment: soft segment is the range of 30: 70-70: 30 on the basis of a weight.
９．弾性繊維の表面に、該繊維重量を基準として０．５〜５．０重量％の油剤が付着しており、該油剤において、鉱物油、シリコーン、及び脂肪族エステルからなる群より選らばれる少なくとも１種の平滑剤が該油剤の７０〜１００重量％を、エーテル系又はエステル系のノニオン界面活性剤が該油剤の０〜３０重量％を占めている、１、２、６のいずれかに記載の衣料。 9. On the surface of the elastic fiber, an oil agent of 0.5 to 5.0% by weight based on the fiber weight is attached, and in the oil agent, at least one selected from the group consisting of mineral oil, silicone, and aliphatic ester The seed smoothing agent accounts for 70 to 100% by weight of the oil, and the ether-based or ester-based nonionic surfactant accounts for 0 to 30% by weight of the oil. Clothing .
１０．油剤の３０℃における粘度が、５×１０−６〜４×１０−５ｍ２／ｓである、９に記載の衣料。 10. The clothing of 9 whose viscosity in 30 degreeC of an oil agent is 5 * 10 < -6 > -4 * 10 < -5 > m < 2 > / s.
１１．衣料が、下着またはスポーツウェアーまたは裏地またはストッキングまたは靴下である、１に記載の衣料。11. 2. The garment according to 1, wherein the garment is underwear or sportswear or lining or stockings or socks.
本発明の弾性繊維は、ポリブチレンテレフタレートをハードセグメントとし、ポリオキシエチレングリコールをソフトセグメントとするポリエーテルエステルエラストマーからなる弾性繊維である。 The elastic fiber of the present invention is an elastic fiber made of a polyether ester elastomer having polybutylene terephthalate as a hard segment and polyoxyethylene glycol as a soft segment.
ハードセグメントであるポリブチレンテレフタレートは、ブチレンテレフタレート単位を少なくとも７０モル％以上含有することが好ましい。ブチレンテレフタレートの含有率は、より好ましくは８０モル％以上、さらに好ましくは９０モル％以上である。 The polybutylene terephthalate which is a hard segment preferably contains at least 70 mol% of butylene terephthalate units. The content of butylene terephthalate is more preferably 80 mol% or more, and still more preferably 90 mol% or more.
上記ポリブチレンテレフタレートには、本発明の目的の達成が実質的に損なわれない範囲内で他の成分が共重合されていてもよい。他の共重合成分としては、ジカルボン酸成分では、例えばナフタレンジカルボン酸、イソフタル酸、ジフェニルジカルボン酸、ジフェニルキシエタンジカルボン酸、β−ヒドロキシエトキシ安息香酸、ｐ−オキシ安息香酸、アジピン酸、セバシン酸、１，４−シクロヘキサンジカルボン酸のような芳香族、脂肪族、脂環族のジカルボン酸成分を挙げることができる。さらに、トリメリット酸、ピロメリット酸、のような三官能性以上のポリカルボン酸を共重合成分として用いても良い。また、ジオール成分では、例えばトリメチレングリコール、エチレングリコール、シクロヘキサン−１，４−ジメタノール、ネオペンチルグリコールのような脂肪族、脂環族、芳香族のジオール成分を挙げることができる。さらに、グリセリン、トリメチロールプロパン、ペンタエリスリトールのような三官能性以上のポリオールを共重合成分として用いてもよい。 The polybutylene terephthalate may be copolymerized with other components as long as the achievement of the object of the present invention is not substantially impaired. As the other copolymerization component, for the dicarboxylic acid component, for example, naphthalenedicarboxylic acid, isophthalic acid, diphenyldicarboxylic acid, diphenyloxyethanedicarboxylic acid, β-hydroxyethoxybenzoic acid, p-oxybenzoic acid, adipic acid, sebacic acid, Examples thereof include aromatic, aliphatic and alicyclic dicarboxylic acid components such as 1,4-cyclohexanedicarboxylic acid. Furthermore, trifunctional or higher polycarboxylic acids such as trimellitic acid and pyromellitic acid may be used as a copolymerization component. Examples of the diol component include aliphatic, alicyclic, and aromatic diol components such as trimethylene glycol, ethylene glycol, cyclohexane-1,4-dimethanol, and neopentyl glycol. Furthermore, a trifunctional or higher functional polyol such as glycerin, trimethylolpropane, or pentaerythritol may be used as a copolymerization component.
一方、ソフトセグメントであるポリオキシエチレングリコールは、オキシエチレングリコール単位を少なくとも７０モル％以上含有することが好ましい。オキシエチレングリコールの含有量は、より好ましくは８０モル％以上、さらに好ましくは９０モル％以上である。上記ポリオキシエチレングリコールには、本発明の目的の達成が実質的に損なわれない範囲内で、例えば、プロピレングリコール、テトラメチレングリコール、グリセリンなどが共重合されていてもよい。 On the other hand, polyoxyethylene glycol which is a soft segment preferably contains at least 70 mol% of oxyethylene glycol units. The content of oxyethylene glycol is more preferably 80 mol% or more, and still more preferably 90 mol% or more. For example, propylene glycol, tetramethylene glycol, glycerin and the like may be copolymerized with the polyoxyethylene glycol within a range in which the achievement of the object of the present invention is not substantially impaired.
上記ポリオキシエチレングリコールの数平均分子量としては、４００〜８０００が好ましく、なかでも１０００〜６０００が特に好ましい。 The number average molecular weight of the polyoxyethylene glycol is preferably 400 to 8000, and particularly preferably 1000 to 6000.
本発明においては、ハードセグメント：ソフトセグメントの重量比率は、７０：３０〜３０：７０の範囲にあることが好ましく、より好ましくは６０：４０〜４０：６０の範囲である。ハードセグメントの重量比率が７０％を超えると、弾性繊維の伸度が低くなり、高ストレッチ用途に使用することが難しくなり、吸湿性が低下する傾向にある。また、ハードセグメントの重量比率が３０％未満であると、ポリブチレンテレフタレート結晶部の割合が低くなるため強度が低下する傾向にあり、添加したポリオキシエチレングリコールをすべて共重合させることが困難となり、精練・染色などの高次加工工程や、製品として使用される場合の洗濯堅牢性が劣ったものになりやすい。 In the present invention, the hard segment: soft segment weight ratio is preferably in the range of 70:30 to 30:70, more preferably in the range of 60:40 to 40:60. When the weight ratio of the hard segment exceeds 70%, the elongation of the elastic fiber becomes low, and it becomes difficult to use for high stretch applications, and the hygroscopicity tends to be lowered. Further, if the weight ratio of the hard segment is less than 30%, the ratio of the polybutylene terephthalate crystal part tends to be low, so the strength tends to decrease, and it becomes difficult to copolymerize all of the added polyoxyethylene glycol. Higher processing processes such as scouring and dyeing, and washing fastness when used as products tend to be inferior.
本発明においては、弾性繊維の３５℃９５％ＲＨでの吸湿率が５％以上、吸水伸長率が１０％以上であることが肝要である。これにより、かかる弾性繊維からなる織編物は、汗などを吸水した際には繊維が伸長し織編物の目が開いて衣料内部の湿度を逃がし、乾燥した際には繊維は収縮してもとの長さに戻り、織編物の目が詰まって、衣料内部の温度を逃がさない、いわゆる自己調節機能を有する、快適性に優れた布帛となる。 In the present invention, it is important that the elastic fiber has a moisture absorption rate of 5% or more at 35 ° C. and 95% RH and a water absorption elongation rate of 10% or more. As a result, the woven or knitted fabric made of such elastic fibers stretches when the sweat is absorbed, opens the eyes of the woven or knitted fabric to release the moisture inside the garment, and shrinks when dried. Thus, the fabric of the knitted and knitted fabric is clogged and has a so-called self-adjusting function that does not let the temperature inside the garment escape.
吸湿率が５％未満では、ベタツキ感、ムレ感があり、吸水伸長率が１０％未満では、吸放水による可逆的伸長収縮特性が不十分となり、織編物の目が十分に開いたり閉じたりせず、快適性に優れた布帛が得られない。一方、前述したポリエーテルエステルからなる本発明の弾性繊維においては、上記の、吸湿率あるいは吸水伸長率が大きくなり過ぎると、弾性性能、耐熱性、耐候(光)性、耐薬品性などが悪化する傾向がある。このため、吸湿率は５〜４５％の範囲が好ましく、より好ましくは１０〜４０％の範囲である。また、吸水伸長率は１０〜１００％の範囲が好ましく、より好ましくは１０〜８０％の範囲であり、さらに好ましくは１５〜６０％の範囲である。 When the moisture absorption rate is less than 5%, there is a sticky feeling and stuffiness, and when the water absorption elongation rate is less than 10%, the reversible stretch / shrinkage characteristics due to water absorption / release are insufficient, and the knitted or knitted fabric eyes are sufficiently opened or closed. Therefore, a fabric excellent in comfort cannot be obtained. On the other hand, in the elastic fiber of the present invention composed of the above-described polyether ester, if the moisture absorption rate or the water absorption elongation rate becomes too large, the elastic performance, heat resistance, weather resistance (light) resistance, chemical resistance, etc. deteriorate. Tend to. For this reason, the moisture absorption is preferably in the range of 5 to 45%, more preferably in the range of 10 to 40%. Further, the water absorption elongation is preferably in the range of 10 to 100%, more preferably in the range of 10 to 80%, and still more preferably in the range of 15 to 60%.
本発明においては、弾性繊維の表面に、該繊維重量を基準として０．５〜５．０重量％の油剤が付着しており、該油剤において、鉱物油、シリコーン、及び脂肪族エステルからなる群より選らばれる少なくとも１種の平滑剤が該油剤の７０〜１００重量％を占めていることが好ましい。 In the present invention, 0.5 to 5.0% by weight of an oil agent is attached to the surface of the elastic fiber based on the weight of the fiber, and the oil agent includes a group consisting of mineral oil, silicone, and aliphatic ester. It is preferable that at least one smoothing agent selected from 70% to 100% by weight of the oil agent.
上記の鉱物油、シリコーン、脂肪族エステルといった平滑剤は弾性繊維を膨潤させることが少なく、これに起因する摩擦増大や力学的特性の低下がなく、製糸工程や後加工工程での工程安定性が良好となる。これらの平滑剤の含有量（複数種を用いる場合はこれらの合計の含有量）は、７０〜１００重量％とすることで、製糸時の走行安定性が向上し、糸の異常伸長やスカムの発生を抑制することができる。 The above smoothing agents such as mineral oil, silicone, and aliphatic ester rarely swell elastic fibers, and there is no increase in friction and deterioration of mechanical properties due to this, and the process stability in the yarn making process and post-processing process is low. It becomes good. The content of these smoothing agents (the total content in the case where a plurality of types are used) is 70 to 100% by weight, so that the running stability at the time of yarn production is improved, abnormal yarn elongation and scum Occurrence can be suppressed.
上記の鉱物油としては、３０℃における粘度が５×１０−６〜４×１０−５ｍ２／ｓであるものが好ましく、かかる粘度範囲の鉱物油は、保存中に該鉱物油が揮散して弾性繊維上の油剤組成比率が変化することが少なく、高い平滑性を維持できる。また、シリコーンは、ポリジメチルシシロキサンであることが好ましく、３０℃におけるその粘度は鉱物油の場合と同様の理由により５×１０−６〜４×１０−５ｍ２／ｓであるものが好ましい。さらに、上記の脂肪族エステルとしては、脂肪酸モノアルキルエステル、脂肪族ジカルボン酸ジアルキルエステル、脂肪族多価アルコールのモノもしくは多脂肪酸エステル等の化合物であり、分子量２５０〜５５０の範囲のものが好ましい。かかる分子量の範囲とすることで、高い平滑性を維持することができる。好ましく用いられる脂肪族エステルとしては、例えば脂肪酸モノアルキルエステルとしては、オクチルオクタノエート、オクチルステアレート、イソトリデシルラウレート、イソトリデシルオレート、ラウリルオレートなどがあげられ、脂肪族ジカルボン酸ジアルキルエステルとしては、ジイソオクチルアジペートなどがあげられ、脂肪族多価アルコールのモノもしくは多脂肪酸エステルとしては、トリメチロールプロパントリオクタネートなどがあげられる。なかでも、脂肪酸モノアルキルエステルが好ましい。 As said mineral oil, that whose viscosity in 30 degreeC is 5 * 10 < -6 > -4 * 10 < -5 > m < 2 > / s is preferable, and mineral oil of this viscosity range volatilizes this mineral oil during storage. Therefore, the oil composition ratio on the elastic fiber is hardly changed, and high smoothness can be maintained. In addition, the silicone is preferably polydimethylsiloxane, and its viscosity at 30 ° C. is preferably 5 × 10 −6 to 4 × 10 −5 m 2 / s for the same reason as in the case of mineral oil. . Furthermore, the aliphatic ester is a compound such as a fatty acid monoalkyl ester, an aliphatic dicarboxylic acid dialkyl ester, a mono- or multi-fatty acid ester of an aliphatic polyhydric alcohol, and preferably has a molecular weight in the range of 250 to 550. By setting the molecular weight within this range, high smoothness can be maintained. Examples of preferably used aliphatic esters include fatty acid monoalkyl esters such as octyl octanoate, octyl stearate, isotridecyl laurate, isotridecyl oleate, lauryl oleate, and the like, and aliphatic dicarboxylic acid dialkyl esters. Examples thereof include diisooctyl adipate, and examples of mono- or multi-fatty acid esters of aliphatic polyhydric alcohols include trimethylolpropane trioctanate. Of these, fatty acid monoalkyl esters are preferred.
一方、エーテル系又はエステル系のノニオン界面活性剤は、３０℃における粘度が８×１０−６〜５×１０−５ｍ２／ｓであるものが好ましい。好ましく用いられるエーテル系ノニオン界面活性剤としては、例えばポリアルキレングリコールアルキルエーテル、ポリアルキレングリコールアリールエーテルなどがあげられ、エステル系ノニオン界面活性剤としては多価アルコール部分エステルのアルキレンオキサイド付加物等が例示され、なかでもポリアルキレングリコールアルキルエーテルが好ましい。この際アルキル基の炭素数は８〜２０の範囲が、弾性繊維が膨潤しにくく、高い平滑性も同時に達成できる。ポリアルキレングリコール鎖のアルキレン基の炭素数は炭素数２〜３、特に２が好ましく、その連鎖数（アルコールへのエチレンオキサイドの付加モル数）は３〜２０の範囲が適当である。この連鎖数の範囲とすることで、上記の鉱物油、シリコーン又は脂肪族エステルからなる平滑剤との相溶性が低下しない。 On the other hand, the ether-based or ester-based nonionic surfactant preferably has a viscosity at 30 ° C. of 8 × 10 −6 to 5 × 10 −5 m 2 / s. Preferred examples of the ether-based nonionic surfactant include polyalkylene glycol alkyl ether and polyalkylene glycol aryl ether, and examples of the ester-based nonionic surfactant include alkylene oxide adducts of polyhydric alcohol partial esters. Of these, polyalkylene glycol alkyl ether is preferred. In this case, when the carbon number of the alkyl group is in the range of 8 to 20, the elastic fiber is less likely to swell and high smoothness can be achieved at the same time. The number of carbon atoms of the alkylene group of the polyalkylene glycol chain is preferably 2 to 3, more preferably 2, and the chain number (number of moles of ethylene oxide added to the alcohol) is suitably in the range of 3 to 20. By setting it as the range of this chain number, compatibility with the smoothing agent which consists of said mineral oil, silicone, or aliphatic ester does not fall.
なお、前述した鉱物油、シリコーンなどが、その３０℃における粘度が５×１０−６〜２×１０−５ｍ２／ｓの場合は、上記のエーテル系又はエステル系のノニオン界面活性剤は必ずしも油剤に含まれていなくてもよいが、上記粘度が２×１０−５ｍ２／ｓを越えるような場合は、該ノニオン界面活性剤が３０重量％以下含まれていることが取扱い性の点で好ましい。 When the above-described mineral oil, silicone, etc. have a viscosity at 30 ° C. of 5 × 10 −6 to 2 × 10 −5 m 2 / s, the above ether-based or ester-based nonionic surfactant is not necessarily used. Although it may not be contained in the oil agent, in the case where the viscosity exceeds 2 × 10 −5 m 2 / s, it is easy to handle that the nonionic surfactant is contained in an amount of 30% by weight or less. Is preferable.
本発明で用いられる油剤は、上記の成分から構成されるものであるが、必要に応じて、本発明の目的を損なわない範囲内で他の配合剤を少量添加してもよい。例えば他のノニオン界面活性剤、アニオン性又はカチオン性のイオン界面活性剤、酸化防止剤、紫外線吸収剤などの安定性向上剤などの平滑助剤を少量添加してもよい。 Although the oil agent used by this invention is comprised from said component, you may add a small amount of another compounding agent within the range which does not impair the objective of this invention as needed. For example, a small amount of smoothing aids such as other nonionic surfactants, anionic or cationic ionic surfactants, antioxidants, stability improvers such as ultraviolet absorbers may be added.
なお、本発明で用いられる上述の油剤は、３０℃での粘度が５×１０−６〜４×１０−５ｍ２／ｓであるものが好ましい。かかる粘度の範囲とすることで弾性繊維の保存中に油剤成分が揮散にくく、高い平滑性を維持することができる。なお、油剤の３０℃における粘度が２×１０−５〜４×１０−５ｍ２／ｓと高い場合には、これをニート油剤として紡糸時に付与する際には例えば加温して２×１０−５ｍ２／ｓ以下にするのが好ましい。但し、油剤をあまり高温に加温すると得られる繊維物性に影響を及ぼし安野で、高々６０℃に留めることが好ましい。 In addition, the above-mentioned oil agent used in the present invention preferably has a viscosity at 30 ° C. of 5 × 10 −6 to 4 × 10 −5 m 2 / s. By setting it as the range of this viscosity, an oil agent component cannot volatilize easily during preservation | save of an elastic fiber, and high smoothness can be maintained. In addition, when the viscosity at 30 ° C. of the oil is as high as 2 × 10 −5 to 4 × 10 −5 m 2 / s, when it is applied as a neat oil during spinning, for example, it is heated to 2 × 10 It is preferable to set it to −5 m 2 / s or less. However, it is preferable to keep the temperature of the oil agent at 60 ° C. at most at Anno because it affects the fiber properties obtained when the oil agent is heated to a very high temperature.
次に、上記油剤の弾性繊維への付着量は、該繊維重量を基準として好ましくは０．５〜５．０重量％、より好ましくは１．０〜４．０重量％であり、これにより製糸時に糸切れやスカム発生などのトラブルが起こりにくく、工程安定性が向上する。 Next, the amount of the oil agent attached to the elastic fiber is preferably 0.5 to 5.0% by weight, more preferably 1.0 to 4.0% by weight, based on the weight of the fiber. Sometimes troubles such as yarn breakage and scum are less likely to occur, and process stability is improved.
前述した高い吸湿率及び吸水伸長率は、上記ポリエーテルエステルエラストマーに、下記一般式（１）で表される有機スルホン酸金属塩を共重合し、かつ弾性繊維の固有粘度を０．９以上とすることで、より容易に達成することができる。 The high moisture absorption rate and water absorption elongation rate described above are obtained by copolymerizing the above-mentioned polyether ester elastomer with an organic sulfonic acid metal salt represented by the following general formula (1) and setting the intrinsic viscosity of the elastic fiber to 0.9 or more. This can be achieved more easily.
式中、Ｒ１は芳香族炭化水素基または脂肪族炭化水素基であり、好ましくは炭素数６〜１５の芳香族炭化水素基または炭素数１０以下の脂肪族炭化水素基である。特に好ましいＲ１は、炭素数６〜１２の芳香族炭化水素基、とりわけベンゼン環である。Ｍ１はアルカリ金属またはアルカリ土類金属であり、ｊは１または２である。なかでもＭ１がアルカリ金属（例えばリチウム、ナトリウムまたはカリウム）であり、かつｊが１であるものが好ましい。Ｘ１はエステル形成性官能基を示し、Ｘ２はＸ１と同一もしくは異なるエステル形成性官能基を示すかあるいは水素原子を示すが、エステル形成性官能基であるのが好ましい。エステル形成性官能基としてはポリエーテルエステルの主鎖または末端に反応して結合する基であればよく具体的には下記の基を挙げることができる。 In the formula, R1 is 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 10 or less carbon atoms. Particularly preferred R 1 is an aromatic hydrocarbon group having 6 to 12 carbon atoms, particularly a benzene ring. M1 is an alkali metal or alkaline earth metal, and j is 1 or 2. Among them, those in which M1 is an alkali metal (for example, lithium, sodium or potassium) and j is 1 are preferable. X1 represents an ester-forming functional group, and X2 represents the same or different ester-forming functional group as X1, or represents a hydrogen atom, but is preferably an ester-forming functional group. The ester-forming functional group may be any group that reacts with and bonds to the main chain or terminal of the polyether ester, and specifically includes the following groups.
上記一般式（１）で表わされる有機スルホン酸金属塩の好ましい具体例としては、３，５−ジカルボメトキシベンゼンスルホン酸ナトリウム、３,５−ジカルボメトキシベンゼンスルホン酸カリウム、３，５−ジカルボメトキシベンゼンスルホン酸リチウム、３，５−ジカルボキシベンゼンスルホン酸ナトリウム、３，５−ジカルボキシベンゼンスルホン酸カリウム、３，５−ジカルボキシベンゼンスルホン酸リチウム、３，５−ジ（β−ヒドロキシエトキシカルボニル）ベンゼンスルホン酸ナトリウム、３，５−ジ（β−ヒドロキシエトキシカルボニル）ベンゼンスルホン酸カリウム、３，５−ジ（β−ヒドロキシエトキシカルボニル）ベンゼンスルホン酸リチウム、２，６−ジカルボメトキシナフタレン−４−スルホン酸ナトウリム、２，６−ジカルボメトキシナフタレン−４−スルホン酸カリウム、２，６−ジカルボメトキシナフタレン−４−スルホン酸リチウム、２，６−ジカルボキシナフタレン−４−スルホン酸ナトリウム、２，６−ジカルボメトキシスフタレン−１−スルホン酸ナトリウム、２，６−ジカルボメトキシナフタレン−３−スルホン酸ナトリウム、２，６−ジカルボメトキシナフタレン−４，８−ジスルホン酸ナトリウム、２，６−ジカルボキシナフタレン−４，８−ジスルホン酸ナトリウム、２，５−ビス（ヒドロエトキシ）ベンゼンスルホン酸ナトリウム、α−ナトリウムスルホコハク酸などをあげることができる。上記有機スルホン酸金属塩は１種のみを単独で用いても、２種以上併用してもよい。 Preferable specific examples of the organic sulfonic acid metal salt represented by the general formula (1) include sodium 3,5-dicarbomethoxybenzenesulfonate, potassium 3,5-dicarbomethoxybenzenesulfonate, 3,5-dicarboxylate. Lithium carbomethoxybenzenesulfonate, sodium 3,5-dicarboxybenzenesulfonate, potassium 3,5-dicarboxybenzenesulfonate, lithium 3,5-dicarboxybenzenesulfonate, 3,5-di (β-hydroxyethoxy) Carbonyl) sodium benzenesulfonate, potassium 3,5-di (β-hydroxyethoxycarbonyl) benzenesulfonate, lithium 3,5-di (β-hydroxyethoxycarbonyl) benzenesulfonate, 2,6-dicarbomethoxynaphthalene 4-sulphonic acid sodium rim, 2,6 -Potassium dicarbomethoxynaphthalene-4-sulfonate, lithium 2,6-dicarbomethoxynaphthalene-4-sulfonate, sodium 2,6-dicarboxynaphthalene-4-sulfonate, 2,6-dicarbomethoxysphthalene -1-sodium sulfonate, 2,6-dicarbomethoxynaphthalene-3-sodium sulfonate, 2,6-dicarbomethoxynaphthalene-4,8-sodium disulfonate, 2,6-dicarboxynaphthalene-4,8 Examples thereof include sodium disulfonate, sodium 2,5-bis (hydroethoxy) benzenesulfonate, α-sodium sulfosuccinic acid, and the like. The said organic sulfonic acid metal salt may be used individually by 1 type, or may be used together 2 or more types.
本発明においては、下記一般式（２）で表される有機スルホン酸金属塩を共重合させることが、ポリエーテルエステルエラストマーの固有粘度を容易に０．９以上とすることができる点、さらに得られる弾性繊維の吸湿率および吸水伸長率を格段に高くできる点で好ましい。我々の研究によれば、かかる有機スルホン酸金属塩を共重合させることにより、吸水伸長率２０％以上といった極めて高い水準を達成でき、より快適性に優れた布帛が容易に得られることがわかった。 In the present invention, copolymerization of an organic sulfonic acid metal salt represented by the following general formula (2) can easily increase the intrinsic viscosity of the polyetherester elastomer to 0.9 or more. It is preferable in that the moisture absorption rate and water absorption elongation rate of the elastic fiber can be remarkably increased. According to our research, it has been found that by copolymerizing such organic sulfonic acid metal salts, it is possible to achieve a very high level of 20% or more of water absorption elongation and easily obtain a fabric with superior comfort. .
上記有機スルホン酸金属塩の共重合量は、あまり多すぎると弾性繊維の融点が低下して耐熱性、耐候(光)性、耐薬品性などが低下する傾向にあるため、ポリエーテルエステルエラストマーを構成する全酸成分を基準として０．１〜２０モル％の範囲とするのが好ましい。逆に、上記共重合量が少なすぎても、吸湿率および吸水伸長率が低下する傾向にあり、０．５〜１５モル％の範囲とするのがより好ましい。 If the copolymerization amount of the organic sulfonic acid metal salt is too large, the melting point of the elastic fiber is lowered, and the heat resistance, weather resistance (light), chemical resistance, etc. tend to be lowered. It is preferable to set it as the range of 0.1-20 mol% on the basis of the total acid component to comprise. On the other hand, even if the amount of copolymerization is too small, the moisture absorption rate and the water absorption elongation rate tend to decrease, and it is more preferably in the range of 0.5 to 15 mol%.
本発明に用いるポリエーテルエステルエラストマーは、たとえば、テレフタル酸ジメチル、テトラメチレングリコールおよびポリオキシエチレングリコールとを含む原料を、エステル交換触媒の存在下でエステル交換反応させ、ビス（ω−ヒドロキシブチル）テレフタレート及び／またはオリゴマーを形成させ、その後、重縮合触媒及び安定剤の存在下で高温減圧下にて溶融重縮合を行うことにより得ることができる。 The polyether ester elastomer used in the present invention is obtained by subjecting a raw material containing, for example, dimethyl terephthalate, tetramethylene glycol, and polyoxyethylene glycol to a transesterification reaction in the presence of a transesterification catalyst to produce bis (ω-hydroxybutyl) terephthalate. And / or forming an oligomer, and then performing melt polycondensation under high temperature and reduced pressure in the presence of a polycondensation catalyst and a stabilizer.
上記のエステル交換触媒としては、ナトリウムなどのアルカリ金属塩、マグネシウム、カルシウムなどのアルカリ土類金属塩、チタン、亜鉛、マンガン等の金属化合物を使用するのが好ましい。 As the transesterification catalyst, an alkali metal salt such as sodium, an alkaline earth metal salt such as magnesium or calcium, or a metal compound such as titanium, zinc or manganese is preferably used.
重縮合触媒としては、ゲルマニウム化合物、アンチモン化合物、チタン化合物、コバルト化合物、錫化合物を使用するのが好ましい。触媒の使用量は、エステル交換反応、重縮合反応を進行させるために必要な量であるならば特に限定されるものではなく、また、複数の触媒を併用することも可能である。 As the polycondensation catalyst, it is preferable to use a germanium compound, an antimony compound, a titanium compound, a cobalt compound, or a tin compound. The amount of the catalyst used is not particularly limited as long as it is a necessary amount for proceeding the transesterification reaction and polycondensation reaction, and a plurality of catalysts can be used in combination.
また、上記ポリエーテルエステルには、後述するヒンダードフェノール系化合物やヒンダードアミン系化合物が添加されていることが、溶融紡糸時のポリマーの固有粘度の低下を抑制するだけでなく、得られた該弾性繊維の熱劣化、酸化劣化、光劣化などが抑制する効果をも有しており、より好ましい。 Further, the addition of a hindered phenol compound or a hindered amine compound, which will be described later, to the polyether ester not only suppresses a decrease in the intrinsic viscosity of the polymer during melt spinning, but also provides the obtained elasticity. It also has an effect of suppressing heat deterioration, oxidation deterioration, light deterioration, etc. of the fiber, and is more preferable.
なかでも、下記一般式（３）で示される分子中に二重結合を有するヒンダードフェノール系化合物を使用することは、本発明のポリエーテルエステルエラストマーの重縮合反応を促進する効果をも持つため、高固有粘度をもつ弾性繊維が得られ易く、高い吸湿性と吸水伸長性を有するポリエーテルエステル弾性繊維を容易に製造できる点で、より好ましい。 Especially, since it has the effect which accelerates | stimulates the polycondensation reaction of the polyetherester elastomer of this invention to use the hindered phenol type compound which has a double bond in the molecule | numerator shown by following General formula (3). It is more preferable in that an elastic fiber having a high intrinsic viscosity is easily obtained, and a polyether ester elastic fiber having high hygroscopicity and water absorption elongation can be easily produced.
式（３）中、置換基Ｒ３およびＲ４は、各々独立に、炭素数１〜６の１価の有機基を示し、ここで置換基Ｒ３およびＲ４のいずれかあるいは両方が複数個存在するときは、複数個存在する置換基は同一であっても異なっていてもよく、ｍおよびｎは各々独立に０〜４の整数であり、そしてＲ５は水素原子または炭素数１〜５の有機基を示す。 In the formula (3), the substituents R3 and R4 each independently represent a monovalent organic group having 1 to 6 carbon atoms, and when either or both of the substituents R3 and R4 are present, A plurality of substituents may be the same or different, m and n are each independently an integer of 0 to 4, and R5 represents a hydrogen atom or an organic group having 1 to 5 carbon atoms. .
かかる分子中に二重結合を有するヒンダードフェノール系化合物の具体例として、下記（４）〜（７）の化合物を挙げることができる。なかでも下記式（４）で示されるものが、前述した高い吸湿性と吸水伸長性を有する弾性繊維が得られ易く、特に好ましい。 Specific examples of the hindered phenol compound having a double bond in the molecule include the following compounds (4) to (7). Among them, the one represented by the following formula (4) is particularly preferable because it is easy to obtain the above-described elastic fiber having high hygroscopicity and water absorption elongation.
エステル交換触媒の供給は、原料調製時の他、エステル交換反応の初期の段階において行うことができる。また、安定剤の供給は、重縮合反応初期までに行うことができるが、エステル交換反応終了時に添加することが好ましい。さらに、重縮合触媒は重縮合反応工程の初期までに供給することができる。 The transesterification catalyst can be supplied at the initial stage of the transesterification reaction in addition to the preparation of the raw material. The stabilizer can be supplied before the beginning of the polycondensation reaction, but it is preferably added at the end of the transesterification reaction. Furthermore, the polycondensation catalyst can be supplied by the early stage of the polycondensation reaction step.
なお、弾性繊維の固有粘度を０．９以上にする方法としては、上述した方法以外にも、ポリエーテルエステルエラストマーを固相重合する方法やポリエステルエーテルエラストマーの合成段階や溶融紡糸段階で鎖延長剤を使用する方法なども採用することができる。この際に使用する鎖延長剤の好ましい具体例としては、２，２’−ビス（２−オキサゾリン）などのオキサゾリン化合物やＮ，Ｎ’−テレフタロイルビスカプロラクタムなどを挙げることができる。 In addition to the above-mentioned method, the method of making the intrinsic viscosity of the elastic fiber 0.9 or more is a method of solid-phase polymerization of a polyether ester elastomer, a chain extender in the synthesis stage of a polyester ether elastomer or a melt spinning stage. A method of using can also be adopted. Preferable specific examples of the chain extender used at this time include oxazoline compounds such as 2,2'-bis (2-oxazoline), N, N'-terephthaloylbiscaprolactam and the like.
前述したように、弾性繊維が以上に述べたポリエーテルエステルエラストマーからなることに加え、弾性繊維の固有粘度が０．９以上であることが好ましい。上記の固有粘度が０．９以上では、極めて高い吸湿率および吸水伸長率を実現することができ、快適性に優れた布帛を容易に得ることができる。一方で、固有粘度があまり大きくなり過ぎると製糸性が低下するだけでなく、製造コストが高くなる。このため、固有粘度は０．９〜１．２の範囲にあることがより好ましい。 As described above, it is preferable that the elastic fiber has an intrinsic viscosity of 0.9 or more in addition to the above-described polyether ester elastomer. When the intrinsic viscosity is 0.9 or more, a very high moisture absorption rate and water absorption elongation rate can be realized, and a fabric excellent in comfort can be easily obtained. On the other hand, when the intrinsic viscosity is too large, not only the yarn-making property is lowered but also the production cost is increased. For this reason, the intrinsic viscosity is more preferably in the range of 0.9 to 1.2.
上記弾性繊維においては、破断伸度を４００％以上とすることが、吸湿性を５％以上、吸水伸長率を１０％以上とすることができる点、また、製織編の際に工程の僅かなブレによる断糸を少なくできる点で好ましい。上記破断伸度としては、４００〜９００％の範囲がより好ましく、さらに好ましくは４００〜８００％の範囲である。 In the elastic fiber, the elongation at break is set to 400% or more, the hygroscopicity can be set to 5% or more, and the water absorption elongation can be set to 10% or more. This is preferable in that thread breakage due to blurring can be reduced. As said breaking elongation, the range of 400-900% is more preferable, More preferably, it is the range of 400-800%.
また、弾性繊維の沸水収縮率を１０％以上とすることが、吸湿性を５％以上、吸水伸長率を１０％以上とする上でより好ましい。 Moreover, it is more preferable that the elastic fiber has a boiling water shrinkage of 10% or more in order to make the hygroscopicity 5% or more and the water absorption elongation 10% or more.
本発明の弾性繊維は、例えば、ペレット状としたポリエーテルエステルを、紡糸口金から溶融して押し出し、口金直下から少なくとも１０ｃｍ、好ましくは少なくとも１５ｃｍの間は保温し、口金下直下から５ｍ以内、好ましくは４ｍ以内の位置で油剤を付与し、引取速度３００〜１２００ｍ／分、好ましくは４００〜９８０ｍ／分で引取り、巻取ドラフト率をさらに該引取速度の１．３〜１．６、好ましくは１．４〜１．５で巻き取ることにより製造することができる。ただし、巻取ドラフトが１．３未満では、ゴデットローラ間およびゴデットローラと捲取機の間において、繊維にかかる張力が不足し、繊維がゴデットローラに捲き付いて断糸してしまうため、好ましくない。上記のように、口金下を保温し、紡速をできるだけ低速に抑え、油剤付与装置までの距離が長くならないようにして配向が進まないようにし、さらに引取った後の弾性繊維ができるだけ繊維が引き伸ばされないように、繊維を巻取ることができる範囲内で巻取ドラフトをできるだけ小さくして巻取ることが、吸湿率を５％以上、吸水伸長率を１０％以上とする上では好ましい。かかる観点から、弾性繊維は、これを巻取った後、あるいは、引取り後連続して、延伸、あるいはさらに熱処理することは好ましくない。 The elastic fiber of the present invention is, for example, a pelletized polyether ester melted and extruded from a spinneret, and kept at least 10 cm, preferably at least 15 cm from directly under the die, within 5 m from immediately below the die, preferably Is applied at a position within 4 m, and is taken up at a take-up speed of 300 to 1200 m / min, preferably 400 to 980 m / min, and the take-up draft rate is further set to 1.3 to 1.6 of the take-up speed, preferably It can manufacture by winding up by 1.4-1.5. However, if the take-up draft is less than 1.3, the tension applied to the fibers is insufficient between the godet rollers and between the godet rollers and the take-up machine, and the fibers come into contact with the godet rollers and break the yarn. As mentioned above, keep the bottom of the base warm, keep the spinning speed as low as possible, keep the distance to the oil application device not long, so that the orientation does not advance, and the elastic fiber after taking up is as much fiber as possible In order to prevent the fibers from being stretched, it is preferable to reduce the winding draft as much as possible within the range in which the fibers can be wound in order to achieve a moisture absorption rate of 5% or more and a water absorption elongation rate of 10% or more. From this point of view, it is not preferable to stretch or further heat-treat the elastic fiber after winding it or continuously after pulling it.
一方、有機スルホン酸金属塩を実質的に共重合していないポリエーテルエステルからなる弾性繊維であっても、３５℃９５％ＲＨの吸湿率が５％以上、吸水伸長率が１０％以上の弾性繊維とすることができる。 On the other hand, even an elastic fiber made of a polyether ester that is not substantially copolymerized with an organic sulfonic acid metal salt has an elasticity of 35% at 95% RH of 5% or more and a water absorption elongation of 10% or more. It can be a fiber.
すなわち、弾性繊維が示差走査型熱量計により得られるＤＳＣ曲線で２つの結晶融解ピークを有し、低温側の結晶融解ピーク高さＨｍ１と高温側の結晶融解ピーク高さＨｍ２との比Ｈｍ１／Ｈｍ２が０．６〜１．２の範囲であり、かつ破断伸度が４００％以上であるものは、上記のような高い吸湿率および吸水伸長率を容易に達成できる。 That is, the elastic fiber has two crystal melting peaks in the DSC curve obtained by the differential scanning calorimeter, and the ratio Hm1 / Hm2 between the crystal melting peak height Hm1 on the low temperature side and the crystal melting peak height Hm2 on the high temperature side. In the range of 0.6 to 1.2 and the elongation at break of 400% or more can easily achieve the high moisture absorption rate and water absorption elongation rate as described above.
ポリエーテルエステルの、ハードセグメント：ソフトセグメントの比率が、重量を基準として３０：７０〜７０：３０であることが好ましいことは前にも述べたが、ハードセグメントの比率を７０重量％以下とすることは、Ｈｍ１／Ｈｍ２の比率を１．２以下とする上で好ましい。 As described above, it is preferable that the ratio of the hard segment: soft segment of the polyether ester is 30:70 to 70:30 based on the weight. However, the ratio of the hard segment is set to 70% by weight or less. This is preferable when the ratio of Hm1 / Hm2 is 1.2 or less.
上記のように、Ｈｍ１／Ｈｍ２が０．６〜１．２の範囲にあるものが、高い吸湿率や吸水伸長率を示す理由としては以下のことが考えられる。２つの結晶融解ピークは、サイズが大きく異なる２つのタイプの結晶が存在することによるものと考えられ、低温側のピークがサイズの小さな結晶の融解温度ピーク、高温側のピークがサイズの大きな結晶の融解温度ピークであると推される。このことは、繊維の横断面を原子間力顕微鏡により硬軟を走査し、硬部を結晶性のハードセグメント、軟部をソフトセグメントに帰属させて考えることでほぼ確認されている。また、ポリエーテルエステルは、ソフトセグメントを構成するポリオキシエチレングリコールが水分子を収着し抱水することで吸湿性が発現しているものと考えられる。以上のことから、Ｈｍ１／Ｈｍ２が１．２以下では、サイズの小さな結晶の数が少なく、ハードセグメントを拘束する結晶架橋点数も少ないことから、ソフトセグメントの膨潤が妨げられず、十分に抱水でき、吸湿率および吸水伸長が著しく向上するためと考えられる。一方、Ｈｍ１／Ｈｍ２が０．６以上では、結晶架橋点数の低下しすぎず、繊維の伸長弾性が高く維持され、繊維物性として実用的なレベルにある。Ｈｍ１／Ｈｍ２のより好ましい範囲は０．８〜１．２である。 As described above, the reason why Hm1 / Hm2 is in the range of 0.6 to 1.2 shows a high moisture absorption rate and water absorption elongation rate as follows. The two crystal melting peaks are thought to be due to the presence of two types of crystals that are significantly different in size. The low temperature peak is the melting temperature peak of the small crystal and the high temperature peak is the large size of the crystal. Presumed to be the melting temperature peak. This is almost confirmed by scanning the cross-section of the fiber with an atomic force microscope for hard and soft, and considering the hard part as a crystalline hard segment and the soft part as a soft segment. In addition, it is considered that the polyether ester exhibits hygroscopicity when the polyoxyethylene glycol constituting the soft segment sorbs and hydrates water molecules. From the above, when Hm1 / Hm2 is 1.2 or less, the number of small-sized crystals is small and the number of crystal crosslinking points that constrain the hard segment is small. This is thought to be because the moisture absorption rate and the water absorption elongation are remarkably improved. On the other hand, when Hm1 / Hm2 is 0.6 or more, the number of crystal crosslinking points does not decrease too much, the elongation elasticity of the fiber is maintained high, and the fiber physical properties are at a practical level. A more preferable range of Hm1 / Hm2 is 0.8 to 1.2.
また、２つの結晶融解ピークの温度Ｔｍ１及びＴｍ２が２００℃以上であることが好ましく、十分な耐熱性を維持できる。一方、結晶融解ピーク温度Ｔｍ１及びＴｍ２が２２５℃以下であることが好ましく、繊維の弾性を高くすることができる。これは、Ｔｍ１及びＴｍ２がかかる関係にあるものは、結晶のサイズが大きくなり過ぎず、結晶架橋点数が低下し過ぎないためと考えられる。 Moreover, it is preferable that temperature Tm1 and Tm2 of two crystal melting peaks are 200 degreeC or more, and sufficient heat resistance can be maintained. On the other hand, the crystal melting peak temperatures Tm1 and Tm2 are preferably 225 ° C. or lower, and the elasticity of the fiber can be increased. This is probably because Tm1 and Tm2 are in such a relationship that the crystal size does not become too large and the number of crystal crosslinking points does not decrease too much.
さらに、前述したように弾性繊維の破断伸度は４００％以上とすることが好ましく、より好ましくは５００〜１０００％の範囲、さらに好ましくは６００〜９００％の範囲である。破断伸度が４００％以上において、より高い吸湿率や吸水伸張率を達成できる。また、製編・製織の際、破断伸度が十分に大きいため、工程の条件の僅かなブレによっても弾性繊維が断糸しにくくなる。 Furthermore, as described above, the breaking elongation of the elastic fiber is preferably 400% or more, more preferably in the range of 500 to 1000%, and still more preferably in the range of 600 to 900%. When the breaking elongation is 400% or more, higher moisture absorption and water absorption elongation can be achieved. Further, since the breaking elongation is sufficiently large during knitting / weaving, the elastic fiber is less likely to be broken even by slight fluctuations in process conditions.
上記の２つの結晶融解ピーク温度をもつ弾性繊維は、例えば、ペレット状としたポリエーテルエステルを、紡糸口金から溶融して押し出し、口金下直下から少なくとも１０ｃｍ、好ましくは少なくとも１５ｃｍの間は保温し、口金下直下から５ｍ以内、好ましくは４ｍ以内の位置で油剤を付与し、引取速度３００〜１２００ｍ／分、好ましくは４００〜９８０ｍ／分で引取り、巻取ドラフト率をさらに該引取速度の１．０〜１．２、好ましくは１．０〜１．１で巻き取ることにより製造することができる。つまり、上記のように、口金下を保温し、紡速をできるだけ低速に抑え、油剤付与装置までの距離が長くならないようにして配向が進まないようにし、さらに引取った後の弾性繊維ができるだけ繊維が引き伸ばされないように巻取ドラフトをできるだけ小さくして巻取ることが、小さいサイズの結晶を増やさず、前述した２つの結晶溶解ピーク高さを０．６〜１．２の範囲とする上で好ましい。かかる観点から、ポリエーテルエステル弾性繊維は、これを巻取った後、あるいは、引取り後連続して、延伸、あるいはさらに熱処理することは好ましくない。 The elastic fiber having the above two crystal melting peak temperatures is obtained by, for example, extruding the pelletized polyether ester by melting it from the spinneret and keeping it warm for at least 10 cm, preferably at least 15 cm from directly below the base. The oil agent is applied at a position within 5 m, preferably within 4 m from directly under the base, and the take-up speed is 300 to 1200 m / min, preferably 400 to 980 m / min. It can manufacture by winding by 0-1.2, Preferably it is 1.0-1.1. In other words, as described above, the temperature below the base is kept warm, the spinning speed is kept as low as possible, the distance to the oil application device is not increased so that the orientation does not progress, and the elastic fiber after being pulled is as much as possible. Taking up the winding draft as small as possible so that the fibers are not stretched does not increase the size of the small crystals, and the above two crystal dissolution peak heights are in the range of 0.6 to 1.2. Is preferable. From this point of view, it is not preferable to stretch or further heat-treat the polyether ester elastic fiber after winding it or continuously after pulling it.
以下、実施例により本発明を具体的に説明する。なお、実施例中の各物性は下記の方法より測定した。 Hereinafter, the present invention will be described specifically by way of examples. In addition, each physical property in an Example was measured with the following method.
（１）吸湿率
試料を所定の条件に調節した恒温恒湿室中に２４時間調湿し、絶乾試料の重量と調湿試料の重量から次式により吸湿率を求めた。
吸湿率（％）＝（調湿試料の重量−絶乾試料の重量）×１００／絶乾試料の重量
(1) Moisture absorption rate The sample was conditioned for 24 hours in a constant temperature and humidity chamber adjusted to predetermined conditions, and the moisture absorption rate was determined from the weight of the absolutely dry sample and the weight of the humidity control sample by the following equation.
Moisture absorption rate (%) = (weight of humidity control sample−weight of absolute dry sample) × 100 / weight of absolute dry sample
（２）吸水伸長率・吸湿伸長率
繊維をかせ取りし、無緊張下にて３０分間沸水処理後、２０℃６５％ＲＨで風乾・調湿した後に非接触の１６０℃環境下で無緊張下にて２分間乾熱処理した糸を２０℃６５％ＲＨの環境下に２４時間放置し、これに０．８８×１０−３ｃＮ／ｄｔｅｘの荷重を掛けて測定した糸の長さを「乾燥時の糸の長さ」とし、その後この糸を２０℃に調節された軟化水中に１分間浸漬後、水中から引き上げ、繊維表面に残存している水分を２０℃６５％ＲＨで風乾させた濾紙で挟み、水平な台の上に置いて１．５ｇ／ｃｍ２の重しを乗せ２秒間放置して繊維表面の余分な水分を拭き取った後、１０秒後に０．８８×１０−３ｃＮ／ｄｔｅｘの荷重を掛けて測定した長さを「吸水時の糸の長さ」とし、下記の式により吸水伸長率を計算した。測定は全て２０℃６５％ＲＨの環境下で行った。
吸水伸長率＝（吸水時の糸の長さ−乾燥時の糸の長さ）÷乾燥時の糸の長さ×１００％
また上記と同様にして「乾燥時の糸の長さ」を測定し、その後この測定をした糸を３５℃９５％ＲＨに調節された恒温恒湿室内で２４時間調湿後、恒温恒湿室内で０．８８×１０−３ｃＮ／ｄｔｅｘの荷重を掛けて測定した長さを「吸湿時の糸の長さ」とし、下記の式により吸湿伸長率を計算した。
吸湿伸長率＝（吸湿時の糸の長さ−乾燥時の糸の長さ）÷乾燥時の糸の長さ×１００％
(2) Water absorption elongation rate / Hygroscopic elongation rate Fibers are collected, treated with boiling water for 30 minutes under no tension, air-dried and conditioned at 20 ° C. and 65% RH, and then under no tension in a non-contact 160 ° C. environment The yarn subjected to dry heat treatment for 2 minutes at 20 ° C. in an environment of 65% RH for 24 hours and subjected to a load of 0.88 × 10 −3 cN / dtex was measured. After that, the yarn was dipped in softened water adjusted to 20 ° C. for 1 minute, then pulled up from the water, and the moisture remaining on the fiber surface was air-dried at 20 ° C. and 65% RH. After sandwiching, placing on a horizontal table and placing a weight of 1.5 g / cm 2 and leaving for 2 seconds to wipe off excess moisture on the fiber surface, 10 seconds later, 0.88 × 10 −3 cN / dtex The length measured by applying the load is the "thread length at the time of water absorption" and The elongation rate was calculated. All measurements were performed in an environment of 20 ° C. and 65% RH.
Water absorption elongation = (yarn length at water absorption−yarn length at drying) ÷ yarn length at drying × 100%
In the same manner as described above, the “yarn length during drying” was measured, and then the yarn thus measured was conditioned for 24 hours in a constant temperature and humidity chamber adjusted to 35 ° C. and 95% RH, and then the constant temperature and humidity chamber. Then, the length measured by applying a load of 0.88 × 10 −3 cN / dtex was defined as “the length of the yarn at the time of moisture absorption”, and the moisture absorption elongation rate was calculated by the following formula.
Hygroscopic elongation = (yarn length when absorbing moisture−yarn length when drying) ÷ yarn length when drying × 100%
（３）破断強度・破断伸度
２０℃×６５％ＲＨに調湿された恒温恒湿室内にて、東洋ボールドウィン社製テンシロンＲＴＭ−１００引張試験機を用い、引張テストをすることにより測定した。
(3) Breaking strength / breaking elongation It measured by performing a tensile test using a Tensilon RTM-100 tensile tester manufactured by Toyo Baldwin in a constant temperature and humidity chamber adjusted to 20 ° C. × 65% RH.
（４）ベタツキ感、ムレ感
弾性繊維を、筒編み機を用いて１３２ｇ／ｍ２のニットとし、これを任意に選んだ５人のひじとひざにつけ、１日過ごしてもらい、ベタツキ感、ムレ感を評価した。結果をそれぞれ、ベタツキ感、ムレ感が少ない（少）、大きい（大）で示した。
(4) Sticky feeling, stuffiness The elastic fiber is knitted at 132 g / m 2 using a cylinder knitting machine, and this is put on the elbows and knees of 5 people who choose it arbitrarily. Evaluated. The results are shown as sticky feeling, stuffiness feeling less (small) and larger (large), respectively.
（５）結晶融解ピーク温度Ｔｍ１、Ｔｍ２
示差走査型熱量計（ＴＡ Ｉｎｓｔｒｕｍｅｎｔ社２９２０型ＤＳＣ）を用い、窒素気流下２０℃／分の昇温速度で走査して測定した。そして、２つの結晶融解ピークのうち、低温側のピーク温度をＴｍ１、高温側のピーク温度をＴｍ２とした。
(5) Crystal melting peak temperatures Tm1, Tm2
Using a differential scanning calorimeter (TA Instrument 2920 type DSC), the measurement was performed by scanning at a rate of temperature increase of 20 ° C./min under a nitrogen stream. Of the two crystal melting peaks, the peak temperature on the low temperature side was Tm1, and the peak temperature on the high temperature side was Tm2.
（６）結晶融解ピーク高さの比Ｈｍ１／Ｈｍ２
上記の２つの結晶融解ピークのうち、低温側（ピーク温度Ｔｍ１側）及び高温側（ピーク温度Ｔｍ２側）の、ベースラインからの結晶融解ピークトップまでの高さを測定し、それぞれＨｍ１、Ｈｍ２とし、その比Ｈｍ１／Ｈｍ２を求めた。
(6) Ratio of crystal melting peak height Hm1 / Hm2
Among the above two crystal melting peaks, the height from the baseline to the crystal melting peak top on the low temperature side (peak temperature Tm1 side) and the high temperature side (peak temperature Tm2 side) is measured as Hm1 and Hm2, respectively. The ratio Hm1 / Hm2 was determined.
［実施例１］
ジメチルテレフタレート１００重量部、３，５−ジ（β−ヒドロキシエトキシカルボニル）ベンゼンスルホン酸ナトリウムの４０重量％エチレングリコール溶液２３重量部（全酸成分に対して５．０モル％）、ポリオキシエチレングリコール（数平均分子量４０００）１１３．４重量部、１，４−ブタンジオール７３．５重量部（全酸成分の１．４モル倍）および触媒としてテトラブチルチタネート０．４重量部を反応槽に仕込み、内温２００℃でエステル交換反応を行った。理論量の約８０％のメタノールが留出した時点で前述したヒンダードフェノール系化合物（４）０．４重量部を添加した後、昇温、減圧による重縮合反応を開始した。重縮合反応は約３０分かけて３０ｍｍＨｇとし、さらに３０分かけて３ｍｍＨｇとし、以後１ｍｍＨｇの真空下で内温２５０℃にて２００分間反応を行い、その時点で下記ヒンダードフェノール系化合物（８）１重量部と、下記ヒンダードアミン系化合物（９）２重量部を添加し、その後さらに２０分間１ｍｍＨｇ以下の真空下、２５０℃で２０分間反応した。生成したポリエーテルエステルエラストマーの固有粘度は１．１０であり、ポリブチレンテレフタレート（ハードセグメント）／ポリオキシエチレングリコール（ソフトセグメント）の重量比率は５０／５０であった。
[Example 1]
100 parts by weight of dimethyl terephthalate, 23 parts by weight of 40% ethylene glycol solution of sodium 3,5-di (β-hydroxyethoxycarbonyl) benzenesulfonate (5.0 mol% based on the total acid components), polyoxyethylene glycol (Number average molecular weight 4000) 113.4 parts by weight, 1,4-butanediol 73.5 parts by weight (1.4 mol times the total acid component), and 0.4 parts by weight of tetrabutyl titanate as a catalyst were charged into the reaction vessel. The transesterification was carried out at an internal temperature of 200 ° C. When about 80% of the theoretical amount of methanol was distilled, 0.4 part by weight of the hindered phenol compound (4) was added, and then a polycondensation reaction was started by raising the temperature and reducing the pressure. The polycondensation reaction was carried out to 30 mmHg over about 30 minutes, and further over 3 minutes to 3 mmHg. Thereafter, the reaction was carried out for 200 minutes at an internal temperature of 250 ° C. under a vacuum of 1 mmHg. At that time, the following hindered phenol compound (8) 1 part by weight and 2 parts by weight of the following hindered amine compound (9) were added, followed by further reaction at 250 ° C. for 20 minutes under a vacuum of 1 mmHg or less for 20 minutes. The intrinsic viscosity of the produced polyether ester elastomer was 1.10, and the weight ratio of polybutylene terephthalate (hard segment) / polyoxyethylene glycol (soft segment) was 50/50.
得られたポリエーテルエステルエラストマーを２３０℃で溶融し、紡糸口金より吐出量３．０５ｇ／分で押出した。この際、口金直下から９ｃｍを保温した。この溶融ポリマーに口金下３ｍの位置で、３０℃における粘度が１×１０−５ｍ２／ｓのポリジメチルシロキサン１００％からなる油剤を繊維重量を基準として３．０重量％付与し、ゴデットローラで５１０ｍ／分で引取り、さらに７５０ｍ（巻取ドラフト１．４７）で巻き取って４４デシテックス／１フィラメントのポリエーテルエステル弾性繊維を得た。結果を表１に示す。 The obtained polyetherester elastomer was melted at 230 ° C. and extruded from the spinneret at a discharge rate of 3.05 g / min. At this time, 9 cm was kept from directly under the base. An oil agent composed of 100% polydimethylsiloxane having a viscosity of 1 × 10 −5 m 2 / s at 30 ° C. at a position 3 m below the die is applied to the molten polymer by 3.0% by weight based on the fiber weight. The film was taken up at 510 m / min and further taken up at 750 m (winding draft 1.47) to obtain a polyether ester elastic fiber having 44 dtex / filament. The results are shown in Table 1.
次に上記弾性繊維を、筒編み機を用いて１３２ｇ／ｍ２のニットとした。このニットを２０℃６５％ＲＨの環境下に２４時間放置した後と、さらにこれを２０℃軟化水中に１分間浸漬し水から取り出しニット表面に付着している水分を濾紙で挟んで取り除いた後とで、それぞれのニットの目開きを観察した。その結果、軟化水中に浸漬した後では、ニットの目開きが大きくなっているのが確認できた。 Next, the elastic fiber was knitted to 132 g / m 2 using a cylindrical knitting machine. After leaving this knit in an environment of 20 ° C. and 65% RH for 24 hours, and further immersing it in 20 ° C. softened water for 1 minute, removing it from the water, and removing the water adhering to the knit surface with filter paper Then, the opening of each knit was observed. As a result, it was confirmed that the knit opening was increased after being immersed in softened water.
［実施例２］
ポリオキシエチレングリコール（数平均分子量４０００）に代えて、ポリオキシエチレングリコール（数平均分子量２０００）を使用する以外は実施例１と同様に行い、固有粘度が１．１６の弾性繊維を得た。結果を表１に示す。
[Example 2]
An elastic fiber having an intrinsic viscosity of 1.16 was obtained in the same manner as in Example 1 except that polyoxyethylene glycol (number average molecular weight 2000) was used instead of polyoxyethylene glycol (number average molecular weight 4000). The results are shown in Table 1.
［実施例３］
ポリオキシエチレングリコール（数平均分子量４０００）の共重合量割合をハードセグメント／ソフトセグメントの重量比率が６０／４０重量％となるように変えた以外は実施例１と同様に行い、固有粘度が１．１２のポリエーテルエステル弾性フィラメントを得た。結果を表１に示す。
[Example 3]
The intrinsic viscosity was 1 except that the copolymerization ratio of polyoxyethylene glycol (number average molecular weight 4000) was changed so that the weight ratio of hard segment / soft segment was 60/40% by weight. .12 polyetherester elastic filaments were obtained. The results are shown in Table 1.
［実施例４］
５−Ｎａスルホイソフタル酸ジヒドロキシエチルエステル（３，５−ジ（β−ヒドロキシエトキシカルボニル）ベンゼンスルホン酸ナトリウムに同じ）の共重合量を、ポリエーテルエステルエラストマーを構成する全酸成分に対して２．０モル％とした以外は実施例１と同様に行い、固有粘度が１．１８のポリエーテルエステル弾性フィラメントを得た。結果を表１に示す。
[Example 4]
The copolymerization amount of 5-Na sulfoisophthalic acid dihydroxyethyl ester (same as sodium 3,5-di (β-hydroxyethoxycarbonyl) benzenesulfonate) was adjusted to 2. A polyetherester elastic filament having an intrinsic viscosity of 1.18 was obtained in the same manner as in Example 1 except that the amount was 0 mol%. The results are shown in Table 1.
［比較例１］
５−Ｎａスルホイソフタル酸ジヒドロキシエチルエステル（３，５−ジ（β−ヒドロキシエトキシカルボニル）ベンゼンスルホン酸ナトリウムに同じ）に代えて、５−Ｎａスルホイソフタル酸ジメチルを使用した以外は実施例１と同様に合成反応を行って固有粘度が１．１０のポリエーテルエステルエラストマーを得た。このポリエーテルエステルエラストマーを用いて、以下実施例１と同様に溶融紡糸を行った。結果を表１に示す。
[Comparative Example 1]
Similar to Example 1 except that dimethyl 5-Na sulfoisophthalate was used instead of 5-hydroxysulfoisophthalic acid dihydroxyethyl ester (same as sodium 3,5-di (β-hydroxyethoxycarbonyl) benzenesulfonate) A polyether ester elastomer having an intrinsic viscosity of 1.10 was obtained by performing a synthesis reaction. Using this polyetherester elastomer, melt spinning was performed in the same manner as in Example 1. The results are shown in Table 1.
［実施例５及び比較例２］
紡糸速度、巻取速度を表１に示すように変更した以外は、実施例１と同様にして弾性繊維を得た。結果を表１に示す。
[Example 5 and Comparative Example 2]
Elastic fibers were obtained in the same manner as in Example 1 except that the spinning speed and the winding speed were changed as shown in Table 1. The results are shown in Table 1.
［比較例３］
実施例１と同一の方法で得た弾性繊維を、２つの非加熱ローラ間で、延伸倍率２．０倍で延伸を施し、巻取り弾性繊維を得た。結果を表１に示す。
[Comparative Example 3]
The elastic fiber obtained by the same method as in Example 1 was stretched at a stretch ratio of 2.0 times between two non-heated rollers to obtain a wound elastic fiber. The results are shown in Table 1.
［実施例６］
実施例１で得られた弾性繊維を、経密度５２本／２．５４ｃｍ、緯密度６０本／２．５４ｃｍの丸編み（スムース）とし、これを脇の下と胸部に用いた、男性用下着及びスポーツウェアー（何れも上半身）を作成した。これらの下着及びスポーツウェアーをそれぞれ５人に着用してもらい２時間運動してもらったが、何れも、上記弾性繊維を用いていないものに比べ、ベタツキ感、むれ感が少なく、快適性に優れていた。
[Example 6]
Men's underwear and sports using the elastic fiber obtained in Example 1 as a circular knitting (smooth) with a warp density of 52 / 2.54 cm and a weft density of 60 / 2.54 cm, which was used for the armpit and chest. Created wear (both upper body). These underwear and sportswear were each worn by 5 people and exercised for 2 hours, but both of them were less sticky and non-sticky than those not using the above elastic fibers, and were excellent in comfort. It was.
［実施例７］
ハードセグメントとしてポリブチレンテレフタレートを４９．８重量部、ソフトセグメントとして分子量４０００のポリオキシエチレングリコール５０．２重量部からなるポリエーテルエステルを、２３０℃で溶融し、紡糸口金より吐出量３．０５ｇ／分で溶融押出した。この際、口金直下から９ｃｍを保温した。この溶融ポリマーに口金下３ｍの位置で、３０℃における粘度が１×１０−５ｍ２／ｓのポリジメチルシロキサン１００％からなる油剤を繊維重量を基準として３．０重量％付与し、ゴデットローラで７０５ｍ／分で引取り、さらに７５０ｍ／分（巻取ドラフト１．０６）で捲取って、４０デニール／１フィラメントの弾性繊維を得た。結果を表２に示す。
[Example 7]
Polyether ester comprising 49.8 parts by weight of polybutylene terephthalate as a hard segment and 50.2 parts by weight of polyoxyethylene glycol having a molecular weight of 4000 as a soft segment is melted at 230 ° C. and discharged from a spinneret at a discharge rate of 3.05 g / Melt extruded in minutes. At this time, 9 cm was kept from directly under the base. An oil agent composed of 100% polydimethylsiloxane having a viscosity of 1 × 10 −5 m 2 / s at 30 ° C. at a position 3 m below the die is applied to the molten polymer by 3.0% by weight based on the fiber weight. The sample was taken up at 705 m / min and further taken up at 750 m / min (winding draft 1.06) to obtain an elastic fiber of 40 denier / filament. The results are shown in Table 2.
弾性繊維を１３２ｇ／ｍ２のニットとし、これを２０℃６５ＲＨ％の環境に２４時間放置した後と、さらにこれを３５℃９５ＲＨ％の恒温恒湿室中に２４時間放置した後でニットの目開きをそれぞれ観察したが、３５℃９５ＲＨ％では空隙が大きくなっているのが確認できた。 The elastic fiber was made into a knit of 132 g / m 2 , which was left in an environment of 20 ° C. and 65 RH% for 24 hours, and further left in a constant temperature and humidity chamber of 35 ° C. and 95 RH% for 24 hours. Each opening was observed, and it was confirmed that the voids were large at 35 ° C. and 95 RH%.
さらに、上記とは別に準備した１３２ｇ／ｍ２のニットを、２０℃６５ＲＨ％の環境下に２４時間放置した後と、２０℃に調節された軟化水中に１分間浸漬し水中から引き上げ、ニット表面に残存している水分を濾紙で挟んでとった後で、ニットの目開きをそれぞれ観察したが、軟化水中に浸漬した後は空隙が大きくなっているのが確認できた。 Furthermore, after the 132 g / m 2 knit prepared separately was left in an environment of 20 ° C. and 65 RH% for 24 hours, it was immersed in softened water adjusted to 20 ° C. for 1 minute and pulled out of the water, After the moisture remaining in the filter was sandwiched between filter papers, the openings of the knit were observed, but it was confirmed that the voids became large after being immersed in the softened water.
［実施例８〜１１、比較例４］
ポリオキシエチレングリコールの比率、紡糸速度、巻取速度を表２に示すように変更した以外は、実施例７と同様にして弾性繊維を得た。結果を表２に示す。
[Examples 8 to 11, Comparative Example 4]
Elastic fibers were obtained in the same manner as in Example 7 except that the ratio of polyoxyethylene glycol, spinning speed, and winding speed were changed as shown in Table 2. The results are shown in Table 2.
さらに実施例７と同様にして、吸湿前後、吸水前後のニットの目開きをそれぞれ観察したが、実施例８〜１１は実施例７と同様に空隙が大きくなっているのが確認されたが、比較例４は空隙がほとんど変化しなかった。 Further, as in Example 7, the knit openings of the knit before and after moisture absorption and before and after water absorption were observed, respectively, but it was confirmed that Examples 8 to 11 had larger gaps as in Example 7, In Comparative Example 4, the voids hardly changed.
［実施例１２］
実施例７で得られた弾性繊維を用いて、実施例６と同様にして男性用下着及びスポーツウェアーを作成し着用評価したが、何れも、上記弾性繊維を用いていないものに比べ、ベタツキ感、むれ感が少なく、快適性に優れていた。
[Example 12]
Men's underwear and sportswear were created and evaluated using the elastic fiber obtained in Example 7 in the same manner as in Example 6, but both were sticky compared to those not using the elastic fiber. There was little feeling of stuffiness and excellent comfort.
本発明の弾性繊維は、ポリエーテルエステルからなるためリサイクル性に優れている。また、本発明の弾性繊維は、吸放湿性が良好であり、吸放水により可逆的に伸縮するため、吸放水により布帛の目開きが変化する自己調節機能を発現し、快適性に優れた布帛を得ることができる。このため、上記弾性繊維を衣料とし、特にスポーツ衣料、インナー、裏地、ストッキング、靴下など用途で優れた性能を発揮する。 Since the elastic fiber of the present invention is made of a polyether ester, it is excellent in recyclability. In addition, the elastic fiber of the present invention has a good moisture absorption and release property, and reversibly expands and contracts by absorbing and releasing water. Therefore, the elastic fiber expresses a self-adjusting function that changes the opening of the fabric by absorbing and releasing water, and has excellent comfort. Can be obtained. For this reason, the above-mentioned elastic fiber is used as clothing, and it exhibits excellent performance in applications such as sports clothing, innerwear, lining, stockings, and socks.
Claims (11)
２００℃≦Ｔｍ１＜Ｔｍ２≦２２５℃The clothing according to claim 6, wherein the crystal melting peak temperature Tm1 on the low temperature side and the crystal melting peak temperature Tm2 on the high temperature side of the two crystal melting peaks satisfy the following formula.
200 ° C ≦ Tm1 <Tm2 ≦ 225 ° C
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011048888A1 (en) | 2009-10-20 | 2011-04-28 | 帝人ファイバー株式会社 | Polyester fibers, process for production of the polyester fibers, cloth, fiber product, and polyester molded article |
Families Citing this family (32)
| 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 |
| US9700077B2 (en) | 2004-03-19 | 2017-07-11 | Nike, Inc. | Article of apparel with variable air permeability |
| US7437774B2 (en) | 2004-03-19 | 2008-10-21 | Nike, Inc. | Article of apparel incorporating a zoned modifiable textile structure |
| JP2007023417A (en) * | 2005-07-15 | 2007-02-01 | Teijin Fibers Ltd | Moisture-absorbing bulky elastic yarn and method for producing the same |
| US8187984B2 (en) | 2006-06-09 | 2012-05-29 | Malden Mills Industries, Inc. | Temperature responsive smart textile |
| JP4983138B2 (en) * | 2006-08-03 | 2012-07-25 | パナソニック株式会社 | Polymer heating element |
| US8389100B2 (en) | 2006-08-29 | 2013-03-05 | Mmi-Ipco, Llc | Temperature responsive smart textile |
| JP2008057099A (en) | 2006-08-29 | 2008-03-13 | Mmi-Ipco Llc | Temperature responsive smart textile |
| JP2008069124A (en) * | 2006-09-15 | 2008-03-27 | Teijin Fibers Ltd | Cosmetic |
| JP4947796B2 (en) * | 2007-06-08 | 2012-06-06 | 竹本油脂株式会社 | Synthetic fiber straight-twisting agent, synthetic fiber false twisted yarn processing method using the same, and synthetic fiber false twisted yarn |
| JP2009235242A (en) * | 2008-03-27 | 2009-10-15 | Teijin Fibers Ltd | Copolyester and polyester fiber |
| JP2009235243A (en) * | 2008-03-27 | 2009-10-15 | Teijin Fibers Ltd | Copolyester and polyester fiber |
| US10039610B2 (en) | 2008-08-08 | 2018-08-07 | Medline Industries, Inc. | Zip strip draping system and methods of manufacturing same |
| JP5748475B2 (en) * | 2010-12-24 | 2015-07-15 | 株式会社ムツミテキスタイル | Circular knitted fabric made of polyurethane elastic fiber, method for producing the same, and elastic clothing and elastic clothing material using the circular knitted fabric |
| TW201233858A (en) * | 2010-12-20 | 2012-08-16 | Toray Opelontex Co Ltd | Knitting having elastic fibers, the method for preparation thereof, and stretchable clothes and stretchable cloth materials using the same |
| USD779156S1 (en) | 2011-10-18 | 2017-02-21 | Medline Industries, Inc. | Medical gown |
| USD791434S1 (en) | 2011-10-18 | 2017-07-11 | Medline Industries, Inc. | Medical gown |
| USD821704S1 (en) | 2011-10-18 | 2018-07-03 | Medline Industries, Inc. | Medical gown |
| US10455872B2 (en) | 2011-10-18 | 2019-10-29 | Medline Industries, Inc. | Disposable medical gown |
| USD863727S1 (en) | 2011-10-18 | 2019-10-22 | Medline Industries, Inc. | Medical gown |
| USD785284S1 (en) | 2011-10-18 | 2017-05-02 | Medline Industries, Inc. | Medical gown |
| CA144409S (en) | 2011-10-18 | 2013-06-18 | Medline Ind Inc | Medical gown |
| US10441010B2 (en) | 2011-10-18 | 2019-10-15 | Medline Industries, Inc. | Disposable medical gown |
| USD836297S1 (en) | 2011-10-18 | 2018-12-25 | Medline Industries, Inc. | Medical gown |
| USD774729S1 (en) | 2011-10-18 | 2016-12-27 | Medline Industries, Inc. | Medical gown |
| KR101494319B1 (en) | 2013-07-30 | 2015-02-23 | 주식회사 휴비스 | Hot Melt Adhesive Fiber Having Lower Compression Set |
| US11116263B2 (en) | 2013-11-21 | 2021-09-14 | Medline Industries, Inc. | Gown for self-donning while maintaining sterility and methods therefor |
| KR102291563B1 (en) * | 2014-12-30 | 2021-08-19 | 코오롱플라스틱 주식회사 | Composition for 3D Printing and Filament for 3D Printer |
| KR102400353B1 (en) * | 2015-04-13 | 2022-05-24 | 주식회사 휴비스 | Self-ventilated elastomer fiber by moisture sensitive mechanism |
| KR101822643B1 (en) | 2015-12-28 | 2018-01-30 | 주식회사 휴비스 | Stretching The Core With A Polyester-Based Elastic Non-woven Fabric |
| EP3763872B1 (en) * | 2018-03-07 | 2024-01-10 | Kuraray Co., Ltd. | Melt-anisotropic aromatic polyester multifilament |
| KR101970598B1 (en) * | 2018-06-15 | 2019-05-17 | (주) 정산인터내셔널 | Textile with enhanced transparency using yarn of polyester-ether block copolymer and manufacturing method thereof |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR870001132B1 (en) * | 1983-04-14 | 1987-06-09 | 도오요오 보오세끼 가부시끼가이샤 | Antistatic fiber containing polyoxyalkylene glycol |
| JPH073029B2 (en) * | 1986-03-28 | 1995-01-18 | 東レ株式会社 | Method for manufacturing absorbent web |
| US4906729A (en) * | 1988-08-05 | 1990-03-06 | E. I. Du Pont De Nemours And Company | Thermoplastic copolyetherester elastomers |
| JPH08209459A (en) * | 1995-02-07 | 1996-08-13 | Nippon Ester Co Ltd | Production of polyetherester elastic yarn |
| JP3577362B2 (en) * | 1995-06-12 | 2004-10-13 | 帝人ファイバー株式会社 | Thermal adhesive fiber and paper for papermaking |
| JP3592842B2 (en) * | 1996-07-08 | 2004-11-24 | 帝人ファイバー株式会社 | Polyester elastic fiber and stretchable wet nonwoven fabric comprising the same |
| JPH11279883A (en) | 1998-03-24 | 1999-10-12 | Mitsubishi Rayon Co Ltd | Polyester conjugate yarn |
| JP2000073232A (en) * | 1998-08-26 | 2000-03-07 | Nippon Ester Co Ltd | Moisture-absorbing polyester fiber |
| TW562889B (en) * | 2000-07-31 | 2003-11-21 | Sanyo Chemical Ind Ltd | Lubricants for elastic fiber |
| JP4064149B2 (en) * | 2002-05-17 | 2008-03-19 | 帝人ファイバー株式会社 | Elastomer composition and fiber comprising the same |
-
2004
- 2004-06-18 EP EP04746409A patent/EP1643019B1/en not_active Expired - Lifetime
- 2004-06-18 JP JP2005507293A patent/JP4202361B2/en not_active Expired - Lifetime
- 2004-06-18 WO PCT/JP2004/008940 patent/WO2004113599A1/en active Application Filing
- 2004-06-18 KR KR1020057024465A patent/KR101183498B1/en active IP Right Grant
- 2004-06-18 TW TW093117766A patent/TWI285688B/en not_active IP Right Cessation
- 2004-06-18 TW TW095148263A patent/TW200722563A/en unknown
- 2004-06-18 US US10/561,155 patent/US20060177655A1/en not_active Abandoned
- 2004-06-18 CA CA2529842A patent/CA2529842C/en not_active Expired - Fee Related
- 2004-06-18 DE DE602004029254T patent/DE602004029254D1/en not_active Expired - Lifetime
-
2008
- 2008-05-19 HK HK08105508.6A patent/HK1116520A1/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011048888A1 (en) | 2009-10-20 | 2011-04-28 | 帝人ファイバー株式会社 | Polyester fibers, process for production of the polyester fibers, cloth, fiber product, and polyester molded article |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| HK1116520A1 (en) | 2008-12-24 |
| EP1643019B1 (en) | 2010-09-22 |
| CA2529842A1 (en) | 2004-12-29 |
| TW200502451A (en) | 2005-01-16 |
| KR20060021910A (en) | 2006-03-08 |
| CA2529842C (en) | 2011-07-12 |
| EP1643019A4 (en) | 2007-09-05 |
| JPWO2004113599A1 (en) | 2006-07-20 |
| DE602004029254D1 (en) | 2010-11-04 |
| US20060177655A1 (en) | 2006-08-10 |
| EP1643019A1 (en) | 2006-04-05 |
| TWI285688B (en) | 2007-08-21 |
| KR101183498B1 (en) | 2012-09-20 |
| WO2004113599A1 (en) | 2004-12-29 |
| TW200722563A (en) | 2007-06-16 |
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