JP2008222963A - Copolymerized polyester, copolymerized polyester fiber and fiber product - Google Patents
Copolymerized polyester, copolymerized polyester fiber and fiber product Download PDFInfo
- Publication number
- JP2008222963A JP2008222963A JP2007066929A JP2007066929A JP2008222963A JP 2008222963 A JP2008222963 A JP 2008222963A JP 2007066929 A JP2007066929 A JP 2007066929A JP 2007066929 A JP2007066929 A JP 2007066929A JP 2008222963 A JP2008222963 A JP 2008222963A
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- JP
- Japan
- Prior art keywords
- polyester
- fiber
- copolymerized
- copolyester
- copolymerized polyester
- 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.)
- Pending
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- 229920000728 polyester Polymers 0.000 title claims abstract description 72
- 239000000835 fiber Substances 0.000 title claims abstract description 67
- 230000003373 anti-fouling effect Effects 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 21
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 8
- 229920000570 polyether Polymers 0.000 claims abstract description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 56
- 229920001634 Copolyester Polymers 0.000 claims description 32
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 23
- 238000007334 copolymerization reaction Methods 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 9
- 230000001588 bifunctional effect Effects 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- 229920001283 Polyalkylene terephthalate Polymers 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 abstract description 5
- 159000000009 barium salts Chemical class 0.000 abstract 1
- 239000000470 constituent Substances 0.000 abstract 1
- 150000002696 manganese Chemical class 0.000 abstract 1
- 150000002815 nickel Chemical class 0.000 abstract 1
- 238000005406 washing Methods 0.000 description 29
- -1 vinyl compound Chemical class 0.000 description 26
- 238000000034 method Methods 0.000 description 17
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 16
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 239000000523 sample Substances 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 239000002202 Polyethylene glycol Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 229920001223 polyethylene glycol Polymers 0.000 description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- DROUXQVANDGZEF-UHFFFAOYSA-L COC(=O)C1=CC(=CC(=C1)S(=O)(=O)[O-])C(=O)OC.COC(=O)C1=CC(=CC(=C1)S(=O)(=O)[O-])C(=O)OC.[Ni+2] Chemical compound COC(=O)C1=CC(=CC(=C1)S(=O)(=O)[O-])C(=O)OC.COC(=O)C1=CC(=CC(=C1)S(=O)(=O)[O-])C(=O)OC.[Ni+2] DROUXQVANDGZEF-UHFFFAOYSA-L 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000011109 contamination Methods 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- 238000009987 spinning Methods 0.000 description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000004753 textile Substances 0.000 description 4
- 239000002759 woven fabric Substances 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 230000036561 sun exposure Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- PIIRYSWVJSPXMW-UHFFFAOYSA-N 1-octyl-4-(4-octylphenoxy)benzene Chemical compound C1=CC(CCCCCCCC)=CC=C1OC1=CC=C(CCCCCCCC)C=C1 PIIRYSWVJSPXMW-UHFFFAOYSA-N 0.000 description 2
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 2
- NVPKZXUQDHHAMH-UHFFFAOYSA-L COC(=O)C1=CC(=CC(=C1)S(=O)(=O)[O-])C(=O)OC.COC(=O)C1=CC(=CC(=C1)S(=O)(=O)[O-])C(=O)OC.[Mn+2] Chemical compound COC(=O)C1=CC(=CC(=C1)S(=O)(=O)[O-])C(=O)OC.COC(=O)C1=CC(=CC(=C1)S(=O)(=O)[O-])C(=O)OC.[Mn+2] NVPKZXUQDHHAMH-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-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
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229940077388 benzenesulfonate Drugs 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012510 hollow fiber Substances 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 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
- 238000002074 melt spinning Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 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
- 238000007670 refining Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 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
- OWQPOVKKUWUEKE-UHFFFAOYSA-N 1,2,3-benzotriazine Chemical compound N1=NN=CC2=CC=CC=C21 OWQPOVKKUWUEKE-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-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
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- FSAMVJAGJWGWTQ-UHFFFAOYSA-N 2-hexadecoxyethanol Chemical compound CCCCCCCCCCCCCCCCOCCO FSAMVJAGJWGWTQ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- ZQWYRGRHXNAOLE-UHFFFAOYSA-N 4,8-disulfonaphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=C(S(O)(=O)=O)C2=CC(C(=O)O)=CC(S(O)(=O)=O)=C21 ZQWYRGRHXNAOLE-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- LAAIOVATSILCFR-UHFFFAOYSA-N C(=O)(O)C1=CC2=CC=C(C=C2C(=C1)S(=O)(=O)O)C(=O)O.[Ni] Chemical compound C(=O)(O)C1=CC2=CC=C(C=C2C(=C1)S(=O)(=O)O)C(=O)O.[Ni] LAAIOVATSILCFR-UHFFFAOYSA-N 0.000 description 1
- UBKDYBGHJZNNQO-UHFFFAOYSA-L C(=O)(O)C=1C=C(C=C(C1)C(=O)O)S(=O)(=O)[O-].[Ba+2].C(=O)(O)C=1C=C(C=C(C1)C(=O)O)S(=O)(=O)[O-] Chemical compound C(=O)(O)C=1C=C(C=C(C1)C(=O)O)S(=O)(=O)[O-].[Ba+2].C(=O)(O)C=1C=C(C=C(C1)C(=O)O)S(=O)(=O)[O-] UBKDYBGHJZNNQO-UHFFFAOYSA-L 0.000 description 1
- YEGGUTCEFOSOHY-UHFFFAOYSA-L C(=O)(O)C=1C=C(C=C(C1)C(=O)O)S(=O)(=O)[O-].[Mn+2].C(=O)(O)C=1C=C(C=C(C1)C(=O)O)S(=O)(=O)[O-] Chemical compound C(=O)(O)C=1C=C(C=C(C1)C(=O)O)S(=O)(=O)[O-].[Mn+2].C(=O)(O)C=1C=C(C=C(C1)C(=O)O)S(=O)(=O)[O-] YEGGUTCEFOSOHY-UHFFFAOYSA-L 0.000 description 1
- IGHYZPPDWWCBTN-UHFFFAOYSA-L C(=O)(O)C=1C=C(C=C(C1)C(=O)O)S(=O)(=O)[O-].[Ni+2].C(=O)(O)C=1C=C(C=C(C1)C(=O)O)S(=O)(=O)[O-] Chemical compound C(=O)(O)C=1C=C(C=C(C1)C(=O)O)S(=O)(=O)[O-].[Ni+2].C(=O)(O)C=1C=C(C=C(C1)C(=O)O)S(=O)(=O)[O-] IGHYZPPDWWCBTN-UHFFFAOYSA-L 0.000 description 1
- YQBAPZJORGZVHR-UHFFFAOYSA-L C(=O)(OC)C1=CC2=C(C=C(C=C2C(=C1)S(=O)(=O)[O-])C(=O)OC)S(=O)(=O)[O-].[Ni+2] Chemical compound C(=O)(OC)C1=CC2=C(C=C(C=C2C(=C1)S(=O)(=O)[O-])C(=O)OC)S(=O)(=O)[O-].[Ni+2] YQBAPZJORGZVHR-UHFFFAOYSA-L 0.000 description 1
- LDPZQFZDQVLZFX-UHFFFAOYSA-L C(=O)(OC)C1=CC2=CC=C(C=C2C=C1S(=O)(=O)[O-])C(=O)OC.[Ni+2].C(=O)(OC)C1=CC2=CC=C(C=C2C=C1S(=O)(=O)[O-])C(=O)OC Chemical compound C(=O)(OC)C1=CC2=CC=C(C=C2C=C1S(=O)(=O)[O-])C(=O)OC.[Ni+2].C(=O)(OC)C1=CC2=CC=C(C=C2C=C1S(=O)(=O)[O-])C(=O)OC LDPZQFZDQVLZFX-UHFFFAOYSA-L 0.000 description 1
- RPNWZFHUFHQMEZ-UHFFFAOYSA-L C(C1=CC=C(C(=O)O)C=C1)(=O)O.O.C(C)(=O)[O-].[Ca+2].C(C)(=O)[O-] Chemical compound C(C1=CC=C(C(=O)O)C=C1)(=O)O.O.C(C)(=O)[O-].[Ca+2].C(C)(=O)[O-] RPNWZFHUFHQMEZ-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-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
- MGGXWQRMLXVTNM-UHFFFAOYSA-N [Ba].COC(C1=CC(C(=O)OC)=CC=C1)=O Chemical compound [Ba].COC(C1=CC(C(=O)OC)=CC=C1)=O MGGXWQRMLXVTNM-UHFFFAOYSA-N 0.000 description 1
- FJXZIUAJCMVENX-UHFFFAOYSA-N [Ni].C(=O)(OC)C1=CC2=CC=C(C=C2C(=C1)S(=O)(=O)O)C(=O)OC Chemical compound [Ni].C(=O)(OC)C1=CC2=CC=C(C=C2C(=C1)S(=O)(=O)O)C(=O)OC FJXZIUAJCMVENX-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000000386 athletic effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- BNZMXLKFDJRNBY-UHFFFAOYSA-L barium(2+);3,5-bis(methoxycarbonyl)benzenesulfonate Chemical compound [Ba+2].COC(=O)C1=CC(C(=O)OC)=CC(S([O-])(=O)=O)=C1.COC(=O)C1=CC(C(=O)OC)=CC(S([O-])(=O)=O)=C1 BNZMXLKFDJRNBY-UHFFFAOYSA-L 0.000 description 1
- IBVWKDVFDAWRFU-UHFFFAOYSA-L benzenesulfonate;nickel(2+) Chemical compound [Ni+2].[O-]S(=O)(=O)C1=CC=CC=C1.[O-]S(=O)(=O)C1=CC=CC=C1 IBVWKDVFDAWRFU-UHFFFAOYSA-L 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 239000003738 black carbon Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000006227 byproduct 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
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
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- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
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- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
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- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 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
- 230000008569 process Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229940087562 sodium acetate trihydrate 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
- 239000007787 solid Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Artificial Filaments (AREA)
Abstract
Description
本発明は共重合ポリエステルならびに該共重合ポリエステルからなる繊維及び繊維製品に関するものである。さらに詳細には、防汚性、なかでも洗濯時における再汚染防止性において特に優れ、しかも日光暴露に伴う防汚性の低下が少ない成形物(繊維等)を与える新規な共重合ポリエステルと、該共重合ポリエステルからなる防汚性の改善された繊維及び繊維製品に関するものである。 The present invention relates to a copolyester and fibers and fiber products comprising the copolyester. More specifically, a novel copolyester that gives a molded product (fiber, etc.) that is particularly excellent in antifouling property, in particular, recontamination prevention during washing, and that has little decrease in antifouling property due to sun exposure, The present invention relates to a fiber and a fiber product having improved antifouling property comprising a copolyester.
ポリエステル繊維は寸法安定性がよく、強く、また皺になり難い等多くの優れた特性を有しているため、従来から多くの分野において利用されている。しかしながら、ポリエステルは疎水性であるため、木綿等の親水性繊維に比較して油性汚れが付着し易く、除去し難く、また洗濯中に汚れが再付着し易い等の問題(再汚染性)がある。
この再汚染性は、ポリエステル繊維が実用化されて以来、常に提起されてきた問題であり、この問題を解消するために多くの方法が提案されている。
Polyester fibers have been used in many fields in the past because they have many excellent properties such as good dimensional stability, strength, and resistance to wrinkles. However, since polyester is hydrophobic, oily stains are more likely to adhere and difficult to remove than hydrophilic fibers such as cotton, and the stains are likely to re-adhere during washing (re-contamination). is there.
This re-contamination property has always been a problem since the practical use of polyester fibers, and many methods have been proposed to solve this problem.
例えば、ポリエチレングリコールとポリエステル樹脂の共重合物からなる溶液もしくは分散液中でポリエステル成形物を浸漬処理する方法(下記特許文献1参照)、ポリエチレングリコールのジメタクリレート等の親水性ビニル化合物をパッド若しくはスプレー後蒸熱処理する方法(下記特許文献2)、あるいは、酸素を含む気体の低温プラズマ処理による方法(下記非特許文献1参照)等が知られている。 For example, a method of immersing a polyester molded product in a solution or dispersion comprising a copolymer of polyethylene glycol and a polyester resin (see Patent Document 1 below), a hydrophilic vinyl compound such as polyethylene glycol dimethacrylate, or a pad or spray. A method of post-steaming heat treatment (Patent Document 2 below), a method by low-temperature plasma treatment of a gas containing oxygen (see Non-Patent Document 1 below), and the like are known.
しかしながら、これらの方法はいずれもポリエステル繊維製品の仕上加工(繊維表面加工)として提案されたものであって、操作が煩雑であるとか、特殊な設備が要るとか、加工の再現性に乏しい等、加工面での問題があり、さらに肌着、白衣等の洗濯頻度の多い衣類等は洗濯回数を重ねるに従って初期の効果が徐々になくなるという問題がある。その上、上記の従来方法のうち親水化加工剤としてポリエチレングリコール化合物を使用する方法では、繊維表面に付着したポリエチレングリコール化合物が日光に含まれる紫外線によって容易に分解脱落して防汚性が低下する傾向があり、屋外で使用するスポーツウェア分野や盛夏用ウェア分野等のように日光に暴露されるような衣料用途での使用が著しく制限されている。 However, these methods are all proposed as finish processing (fiber surface processing) of polyester fiber products, and the operation is complicated, special equipment is required, processing reproducibility is poor, etc. There are problems in terms of processing, and clothing such as underwear and lab coats that are frequently washed has a problem that the initial effect gradually disappears as the number of washing is repeated. In addition, among the above conventional methods, in the method using a polyethylene glycol compound as a hydrophilizing agent, the polyethylene glycol compound adhering to the fiber surface is easily decomposed and dropped by ultraviolet rays contained in sunlight, and the antifouling property is lowered. There is a tendency, and the use in apparel that is exposed to sunlight, such as the field of sportswear used outdoors and the field of midsummer clothing, is remarkably restricted.
一方、ポリマー改質による防汚性ポリエステル繊維として、片末端封鎖ポリエチレングリコールをポリエステル主鎖の末端に共重合した防汚性ポリエステル繊維が提案されている(下記特許文献3〜6参照)。この方法によれば、末端に共重合されたポリエチレングリコールの作用によって、繊維形成過程で特異的な繊維微細構造の形成がなされ、そのため従来にない優れた防汚性の初期性能が得られる。さらに、該ポリエチレングリコール鎖はポリエステル主鎖と強大な共有結合力によって分子結合されているため、その洗濯耐久性が著しく改良される。しかしながら、このような防汚性ポリエステル繊維も親水化成分としてポリエチレングリコール化合物を用いるため、上記した繊維表面加工法に比べれば格段の優位性があるものの、日光に長時間暴露されるような用途においては防汚性の低下が問題となる場合もあり、さらなる改善が望まれていた。 On the other hand, as an antifouling polyester fiber by polymer modification, an antifouling polyester fiber obtained by copolymerizing one end-capped polyethylene glycol at the end of a polyester main chain has been proposed (see Patent Documents 3 to 6 below). According to this method, a specific fiber microstructure is formed in the fiber formation process by the action of polyethylene glycol copolymerized at the terminal, and therefore, an excellent antifouling initial performance which is not conventionally obtained can be obtained. Furthermore, since the polyethylene glycol chain is molecularly bonded to the polyester main chain by a strong covalent bond, its washing durability is remarkably improved. However, since such an antifouling polyester fiber also uses a polyethylene glycol compound as a hydrophilic component, it has a significant advantage over the fiber surface processing method described above, but in applications where it is exposed to sunlight for a long time. In some cases, deterioration of the antifouling property becomes a problem, and further improvement has been desired.
本発明は、上記背景技術に鑑みされたもので、その目的は、従来のものに比べて防汚性及びその洗濯耐久性が大幅に改良され、特に洗濯による再汚染防止性、黒ずみ防止性が格段に改良され、しかも日光暴露に伴う防汚性及びその洗濯耐久性の低下が少ない、新規な共重合ポリエステル、その繊維及び繊維製品を提供することにある。 The present invention has been made in view of the above-described background art, and its object is to significantly improve the antifouling property and its washing durability as compared with the conventional ones. It is an object of the present invention to provide a novel copolyester, its fiber and fiber product, which are remarkably improved and have little antifouling property and decrease in washing durability due to sun exposure.
本発明者らは、上記目的を達成すべく、上述した片末端封鎖ポリエチレングリコールをポリエステル主鎖の末端に共重合した防汚性ポリエステルに着目して種々検討を行った。その結果、該防汚性ポリエステルを構成する片末端封鎖ポリエチレングリコールを共重合したポリエステルに、さらに特定の有機スルホン酸のニッケル、マンガン及びバリウムから選ばれる金属塩を共重合することにより、最終的に得られる共重合ポリエステルの防汚性のレベル及びその耐久性がともに向上すると共に、それらの機能性の日光暴露に伴う低下が著しく防止され、上述の課題が達成できることを見出した。本発明は、これらの知見に基づいてさらに研究を重ねた結果、完成したものである。
かくして、本発明によれば、以下の如き新規なポリエステル共重合体、その繊維及び繊維製品が提供される。
In order to achieve the above-mentioned object, the present inventors made various studies by paying attention to the antifouling polyester obtained by copolymerizing the above-mentioned one-end-capped polyethylene glycol at the terminal of the polyester main chain. As a result, the polyester obtained by copolymerizing one end-capped polyethylene glycol constituting the antifouling polyester is further copolymerized with a metal salt selected from nickel, manganese and barium of a specific organic sulfonic acid, thereby finally It has been found that the level of antifouling property and durability of the resulting copolyester are improved, and that the functional degradation is significantly prevented by exposure to sunlight, and the above-mentioned problems can be achieved. The present invention has been completed as a result of further research based on these findings.
Thus, according to the present invention, the following novel polyester copolymer, its fiber and fiber product are provided.
〔1〕ポリアルキレンテレフタレートを主たる構成単位とするポリエステルであって、該ポリエステルの末端にポリエーテル成分が共重合されていると共に、該ポリエステル中に下記一般式(1)で表わされる有機スルホン酸金属塩が共重合されていることを特徴とする共重合ポリエステル。
〔4〕有機スルホン酸金属塩の共重合量が、末端共重合型ポリエステルを構成する二官能性カルボン酸成分に対して0.2〜5モルであることを特徴とする上記〔1〕から〔3〕のいずれかに記載の共重合ポリエステル。
〔5〕ポリエステルの分子鎖中に有機スルホン酸金属塩がランダムに共重合されている上記〔1〕から〔4〕のいずれかに記載の共重合ポリエステル。
〔6〕上記〔1〕から〔5〕のいずれかに記載の共重合ポリエステルからなることを特徴とする防汚性、耐久性の改善された共重合ポリエステル繊維。
〔7〕上記〔6〕に記載の共重合ポリエステル繊維を少なくとも一部に含んでなる繊維製品。
[1] A polyester having polyalkylene terephthalate as a main structural unit, wherein a polyether component is copolymerized at the terminal of the polyester, and an organic sulfonic acid metal represented by the following general formula (1) in the polyester A copolymerized polyester, wherein a salt is copolymerized.
[4] The copolymerization amount of the organic sulfonic acid metal salt is 0.2 to 5 mol with respect to the bifunctional carboxylic acid component constituting the terminal copolymerized polyester. [3] The copolyester according to any one of [3].
[5] The copolyester according to any one of [1] to [4] above, wherein an organic sulfonic acid metal salt is randomly copolymerized in the molecular chain of the polyester.
[6] A copolyester fiber having improved antifouling properties and durability, comprising the copolyester according to any one of [1] to [5].
[7] A fiber product comprising at least a part of the copolyester fiber according to [6].
上述の如き本発明の共重合ポリエステルは、従来技術に比べて、繊維等にしたときの防汚性及びその洗濯耐久性が大幅に改良され、特に洗濯による再汚染防止性、黒ずみ防止性が格段に向上している。このため、該共重合ポリエステルからなる繊維は、例えば肌着、食品白衣等の白衣、レディス向けブラウス等のユニフォーム、テーブルクロス等リネン資材等の洗濯頻度の高い衣類になした場合に特にその利点が発揮され、洗濯を繰り返しても防汚性が保持されて、洗濯による黒ずみが起こらない。それ故、本発明の共重合ポリエステルからなる繊維は、レンタルユニフォーム等のリネンサプライ分野において特に有用である。 As described above, the copolyester of the present invention has significantly improved antifouling property and washing durability when made into fibers, etc., compared with the prior art, and particularly has excellent recontamination prevention property and darkening prevention property due to washing. Has improved. For this reason, the fiber made of the copolyester exhibits its advantages particularly when it is made into clothes having a high frequency of washing such as underwear, white coats such as food white coats, uniforms such as blouses for ladies, and linen materials such as table cloths. In addition, antifouling properties are maintained even after repeated washing, and blackening due to washing does not occur. Therefore, the fiber comprising the copolyester of the present invention is particularly useful in the field of linen supply such as rental uniforms.
さらに、本発明の共重合ポリエステルからなる繊維は、日光暴露に伴う上記の防汚性及びその洗濯耐久性の低下が著しく少ないという利点を有する。したがって、本発明の共重合ポリエステル繊維を含む織編物、不織布等の繊維構造物及び繊維製品は、特に屋外で使用するスポーツウェア分野や盛夏用ウェア分野等、洗濯頻度が高く、かつ日光干しする機会の多い衣料用途においても極めて有用である。
また、本発明の共重合ポリエステルからなる繊維以外の成形物、例えば、フィルム、テープ、その他の形態の成形物でも、同様の効果が期待できる。
Furthermore, the fiber made of the copolymerized polyester of the present invention has the advantage that the above-mentioned antifouling property and exposure to washing due to exposure to sunlight are significantly reduced. Therefore, fiber structures and textile products such as woven and knitted fabrics and nonwoven fabrics containing the copolymerized polyester fiber of the present invention are frequently washed and used in the sun, especially in outdoor sportswear fields and high-summer clothing fields. It is also extremely useful in apparel applications with a large amount of clothes.
Moreover, the same effect can be expected even in a molded product other than the fiber made of the copolymerized polyester of the present invention, for example, a molded product of a film, a tape, or other forms.
本発明でいうポリエステルは、テレフタル酸を主たる二官能性カルボン酸成分とし、少なくとも1種のアルキレングリコール、例えばエチレングリコール、トリメチレングリコール、テトラメチレングリコールから選ばれる少なくとも1種をグリコール成分とするポリエステル、すなわちアルキレンテレフタレートを主たる構成単位とするポリエステル(アルキレンテレフタレート系ポリエステル)を主たる対象とする。 The polyester referred to in the present invention is a polyester having terephthalic acid as a main difunctional carboxylic acid component and at least one alkylene glycol, for example, at least one selected from ethylene glycol, trimethylene glycol and tetramethylene glycol as a glycol component, That is, the main object is polyester (alkylene terephthalate-based polyester) having alkylene terephthalate as a main structural unit.
かかるポリエステルにおいて、テレフタル酸成分の一部(例えば20モル%以下)を他の二官能性カルボン酸成分で置換えたポリエステル及び/又はグリコール成分の一部を主成分以外の上記グリコール若しくは他のジオール成分で置換えたポリエステルであってもよい。 In such a polyester, a part of the terephthalic acid component (for example, 20 mol% or less) is substituted with another bifunctional carboxylic acid component and / or a part of the glycol component is the above-mentioned glycol or other diol component other than the main component. Polyester substituted with may be used.
ここで使用されるテレフタル酸以外の二官能性カルボン酸としては、例えばイソフタル酸、ナフタリンジカルボン酸、ジフェニルジカルボン酸、ジフェノ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如き芳香族、脂肪族、脂環族の二官能性カルボン酸を挙げることができる。 Examples of the bifunctional carboxylic acid other than terephthalic acid used here include isophthalic acid, naphthalene dicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, β-hydroxyethoxybenzoic acid, p-oxybenzoic acid, and adipic acid. And aromatic, aliphatic and alicyclic bifunctional carboxylic acids such as sebacic acid and 1,4-cyclohexanedicarboxylic acid.
また、上記グリコール以外の他のジオール化合物としては、例えばシクロヘキサン−1,4―ジメタノール、ネオペンチルグリコール、ビスフェノールA、ビスフェノールSの如き脂肪族、脂環族、芳香族ジオール化合物等を挙げることができる。これらの他のジオール化合物は20モル%以下で使用するのが好ましい。 Examples of the diol compound other than the glycol include aliphatic, alicyclic, and aromatic diol compounds such as cyclohexane-1,4-dimethanol, neopentyl glycol, bisphenol A, and bisphenol S. it can. These other diol compounds are preferably used in an amount of 20 mol% or less.
さらに、ポリエステルが実質的に線状である範囲で、トリメリット酸、ピロメリット酸の如きポリカルボン酸や、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如きポリオール等を使用することもできる。 Furthermore, polycarboxylic acids such as trimellitic acid and pyromellitic acid, polyols such as glycerin, trimethylolpropane, and pentaerythritol can be used as long as the polyester is substantially linear.
かかるポリエステルは任意の方法によって合成される。例えばポリエチレンテレフタレートについて説明すれば、通常テレフタル酸とエチレングリコールとを直接エステル化反応させるか、テレフタル酸ジメチルの如きテレフタル酸の低級アルキルエステルとエチレングリコールとをエステル交換反応させるか又はテレフタル酸とエチレンオキサイドとを反応させるかしてテレフタル酸のグリコールエステル及び/又はその低重合体を生成させる第一段階の反応と、第一段階の反応生成物を減圧下加熱して所望の重合度になるまで重縮合反応させる第二段階の反応によって製造される。 Such polyester is synthesized by any method. For example, for polyethylene terephthalate, terephthalic acid and ethylene glycol are usually esterified directly, terephthalic acid lower alkyl ester such as dimethyl terephthalate is transesterified with ethylene glycol, or terephthalic acid and ethylene oxide. In the first step to produce a glycol ester of terephthalic acid and / or its low polymer, and the reaction product in the first step is heated under reduced pressure until the desired degree of polymerization is reached. It is produced by a second stage reaction that causes a condensation reaction.
本発明の共重合ポリエステルにおいては、該ポリエステルの分子鎖の少なくとも一方の末端に、ポリエーテル成分、特に下記一般式(2)で表わされる片末端封鎖オキシアルキレングリコールが共重合されていることが必要である。ここで片末端封鎖とは、下記一般式(2)から明らかなようにオキシアルキレングリコールの一方の末端基が非官能性の炭化水素基で封鎖されているものを言う。 In the copolymerized polyester of the present invention, it is necessary that at least one end of the molecular chain of the polyester is copolymerized with a polyether component, in particular, one end-blocked oxyalkylene glycol represented by the following general formula (2). It is. As used herein, the term “one-end blocked” means that one end group of oxyalkylene glycol is blocked with a non-functional hydrocarbon group as is apparent from the following general formula (2).
上記一般式(2)中、R1は炭化水素基を示し、通常、炭素原子数1〜4のアルキル基、炭素原子数6〜12のシクロアルキル基、炭素原子数6〜12のアリール基又は炭素原子数8〜16のアルキルアリール基が好ましい。また、R2はアルキレン基であり、通常、炭素原子数2〜4のアルキレン基が好ましい。好適なアルキレン基としてはエチレン基、プロピレン基、テトラメチレン基が例示される。また、上記ポリオキシアルキレングリコールは、分子中に2種以上のアルキレン基が混在してもよく、例えばエチレン基とプロピレン基、もしくはエチレン基とテトラメチレン基とを持ったランダム共重合体やブロック共重合体であってもよい。上記一般式(2)中のnは重合度を示す正の整数であり、30〜140の範囲が好ましい。 In the general formula (2), R1 represents a hydrocarbon group, usually an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 6 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or carbon. An alkylaryl group having 8 to 16 atoms is preferred. R2 is an alkylene group, and usually an alkylene group having 2 to 4 carbon atoms is preferred. Suitable alkylene groups include an ethylene group, a propylene group, and a tetramethylene group. The polyoxyalkylene glycol may contain two or more kinds of alkylene groups in the molecule. For example, a random copolymer or block copolymer having an ethylene group and a propylene group, or an ethylene group and a tetramethylene group. It may be a polymer. N in the general formula (2) is a positive integer indicating the degree of polymerization, and is preferably in the range of 30 to 140.
かかる片末端封鎖ポリオキシアルキレングリコールの好ましい具体例としては、ポリオキシエチレングリコールモノメチルエーテル、ポリオキシエチレングリコールモノフェニルエーテル、ポリオキシエチレングリコールモノオクチルフェニルエーテル、ポリオキシエチレングリコールモノノニルフェニルエーテル、ポリオキシエチレングリコールモノセチルエーテル、ポリオキシプロピレングリコールモノメチルエーテル、ポリオキシプロピレングリコールモノフェニルエーテル、ポリオキシプロピレングリコールモノオクチルフェニルエーテル、ポリオキシプロピレングリコールモノノニルフェニルエーテル、ポリオキシテトラメチレングリコールモノメチルエーテル、ポリオキシエチレングリコール/ポリオキシプロピレングリコール共重合体のモノメチルエーテル、ポリオキシエチレングリコール/ポリオキシテトラメチレングリコール共重合体のモノメチルエーテル等を挙げることができる。なかでもポリオキシエチレングリコール誘導体が特に好ましい。
上記片末端封鎖ポリオキシアルキレングリコールは1種を単独で使用しても、また2種以上を併用してもよい。
Preferable specific examples of such one-end-capped polyoxyalkylene glycol include polyoxyethylene glycol monomethyl ether, polyoxyethylene glycol monophenyl ether, polyoxyethylene glycol monooctyl phenyl ether, polyoxyethylene glycol monononyl phenyl ether, polyoxyethylene glycol Ethylene glycol monocetyl ether, polyoxypropylene glycol monomethyl ether, polyoxypropylene glycol monophenyl ether, polyoxypropylene glycol monooctyl phenyl ether, polyoxypropylene glycol monononyl phenyl ether, polyoxytetramethylene glycol monomethyl ether, polyoxyethylene Glycol / polyoxypropylene glycol Monomethyl ether polymer, monomethyl ether of polyoxyethylene glycol / polyoxytetramethylene glycol copolymer and the like. Of these, polyoxyethylene glycol derivatives are particularly preferred.
The above single-end-capped polyoxyalkylene glycol may be used alone or in combination of two or more.
上記片末端封鎖ポリオキシアルキレングリコールをポリアルキレンテレフタレート系ポリエステルの少なくとも一方の末端に共重合するには、上述したポリエステルの合成が完了するまでの任意の段階、例えば第1段階の反応開始前、反応中、反応終了後、第2段階の反応中等の任意の段階で片末端封鎖ポリオキシアルキレングリコールを添加し、添加後重縮合反応を完結すればよい。この際、その使用量は、あまりに少ないと防汚性及びその洗濯耐久性が不充分になり、逆にあまりに多いと最早著しい防汚性及びその洗濯耐久性の改善効果の向上が見られず、かえって共重合ポリエステルの重合度が低下し、最終的に得られる共重合ポリエステル繊維の強度等の物理的特性が不充分になるという問題が顕在化するようになる。このため本発明における片末端封鎖ポリオキシアルキレングリコールの共重合量は生成する共重合ポリエステルに対して0.5〜10重量%の範囲であるのが好ましく、2〜7重量%の範囲であるのが特に好ましい。 In order to copolymerize the one-end-capped polyoxyalkylene glycol to at least one terminal of the polyalkylene terephthalate-based polyester, any stage until the synthesis of the above-described polyester is completed, for example, before the start of the first stage reaction, During the reaction, after the completion of the reaction, one-end-capped polyoxyalkylene glycol may be added at any stage such as during the second stage reaction, and the polycondensation reaction may be completed after the addition. At this time, if the amount used is too small, the antifouling property and its washing durability will be insufficient, and conversely if too large, the remarkable effect of improving the antifouling property and its washing durability will not be seen. On the contrary, the degree of polymerization of the copolyester is lowered, and the problem that physical properties such as strength of the copolyester fiber finally obtained becomes insufficient becomes apparent. For this reason, the copolymerization amount of the one-end-capped polyoxyalkylene glycol in the present invention is preferably in the range of 0.5 to 10% by weight, and in the range of 2 to 7% by weight, based on the copolymer polyester to be produced. Is particularly preferred.
本発明においては、さらに、上記共重合ポリエステルに下記一般式(1)で表される特定の有機スルホン酸金属塩が共重合されていることが必要である。すなわち、上記共重合ポリエステルでは、さらに該有機スルホン酸金属塩が共重合することによって、最終的に得られる共重合ポリエステルからなる繊維の防汚性及びその洗濯耐久性が改良され、かつ屋外日光暴露に伴う防汚性及びその洗濯耐久性の低下が抑制されるという格別の効果が見られる。 In the present invention, it is further necessary that a specific organic sulfonic acid metal salt represented by the following general formula (1) is copolymerized with the copolymer polyester. That is, in the above-described copolymer polyester, the organic sulfonic acid metal salt is further copolymerized to improve the antifouling property of the fiber obtained from the finally obtained copolymer polyester and its washing durability, and exposure to sunlight outdoors. The special effect that the antifouling property and the fall of the washing durability accompanying this are suppressed is seen.
上記一般式(1)式において、Rは芳香族炭化水素基又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又は炭素数10以下の脂肪族炭化水素基である。特に好ましいR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。また、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。これらのエステル形成性官能基としては、ポリエステルの主鎖又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 above general formula (1), R 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. is there. Particularly preferred R is an aromatic hydrocarbon group having 6 to 12 carbon atoms, particularly a benzene ring. X1 represents an ester-forming functional group, and X2 represents an ester-forming functional group that is the same as or different from X1, or represents a hydrogen atom, but is preferably an ester-forming functional group. These ester-forming functional groups may be any group that reacts with and bonds to the main chain or terminal of the polyester, and specific examples thereof include the following groups.
かかる一般式(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ニッケル、3,5−ジカルボメトキシベンゼンスルホン酸マンガン、3,5−ジカルボメトキシベンゼンスルホン酸バリウム、3,5−ジカルボキシベンゼンスルホン酸ニッケル、3,5−ジカルボキシベンゼンスルホン酸マンガン、3,5−ジカルボキシベンゼンスルホン酸バリウム、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ニッケル、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マンガン、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バリウム、2,6−ジカルボメトキシナフタレン−4−スルホン酸ニッケル、2,6−ジカルボメトキシナフタレン−4−スルホン酸マンガン、2,6−ジカルボメトキシナフタレン−4−スルホン酸バリウム、2,6−ジカルボキシナフタレン−4−スルホン酸ニッケル、2,6−ジカルボメトキシナフタレン−1−スルホン酸ニッケル、2,6−ジカルボメトキシナフタレン−3−スルホン酸ニッケル、2,6−ジカルボメトキシナフタレン−4,8−ジスルホン酸ニッケル、2,6−ジカルボキシナフタレン−4,8−ジスルホン酸ニッケル、2,5−ビス(ヒドロエトキシ)ベンゼンスルホン酸ニッケル等を挙げることができる。これらの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 nickel 3,5-dicarbomethoxybenzene sulfonate, manganese 3,5-dicarbomethoxybenzene sulfonate, 3,5-di Carbomethoxybenzene barium sulfonate, nickel 3,5-dicarboxybenzenesulfonate, manganese 3,5-dicarboxybenzenesulfonate, barium 3,5-dicarboxybenzenesulfonate, 3,5-di (β-hydroxyethoxy) Carbonyl) nickel benzenesulfonate, manganese 3,5-di (β-hydroxyethoxycarbonyl) manganese sulfonate, barium 3,5-di (β-hydroxyethoxycarbonyl) benzenesulfonate, 2,6-dicarbomethoxynaphthalene 4-sulphonic acid nickel, 2,6-di Rubomethoxynaphthalene-4-sulfonic acid manganese, 2,6-dicarbomethoxynaphthalene-4-barium sulfonic acid, nickel 2,6-dicarboxynaphthalene-4-sulfonic acid, 2,6-dicarbomethoxynaphthalene-1- Nickel sulfonate, nickel 2,6-dicarbomethoxynaphthalene-3-sulfonate, nickel 2,6-dicarbomethoxynaphthalene-4,8-disulfonate, 2,6-dicarboxynaphthalene-4,8-disulfonic acid Examples thereof include nickel and nickel 2,5-bis (hydroethoxy) benzenesulfonate. These organic sulfonic acid metal salts may be used alone or in combination of two or more.
上記有機スルホン酸金属塩の共重合量は該共重合ポリエステルを構成する二官能性カルボン酸成分全量に対して0.2〜5モル%の範囲が好ましく、より好ましくは0.5〜4.5モル%の範囲、さらに好ましくは1.0〜3.5モル%の範囲である。この有機スルホン酸金属塩の共重合量があまりに少ないと、得られる繊維の防汚性及びその洗濯耐久性並びに耐光性の改善効果が不充分なものとなる。一方、有機スルホン酸金属塩の共重合量が多すぎると、かえって共重合ポリエステルの融点が低下して耐熱性、耐加水分解性等が悪化するようになる。 The copolymerization amount of the organic sulfonic acid metal salt is preferably in the range of 0.2 to 5 mol%, more preferably 0.5 to 4.5, based on the total amount of the bifunctional carboxylic acid component constituting the copolymer polyester. It is the range of mol%, More preferably, it is the range of 1.0-3.5 mol%. If the copolymerization amount of the organic sulfonic acid metal salt is too small, the antifouling property of the resulting fiber and the effect of improving the washing durability and light resistance will be insufficient. On the other hand, when the copolymerization amount of the organic sulfonic acid metal salt is too large, the melting point of the copolymerized polyester is lowered, and the heat resistance, hydrolysis resistance and the like are deteriorated.
上記有機スルホン酸金属塩は、上記共重合ポリエステルのポリエステル分子鎖(主鎖)中にランダムに共重合されていることが好ましい。
上記有機スルホン酸金属塩を共重合するには、片末端封鎖ポリオキシアルキレングリコールを共重合する場合と同様に、上述したポリエステルの合成が完了するまでの任意の段階、例えば第1段階の反応開始前、反応中、反応終了後、第2段階の反応中等の任意の段階で添加し、添加後重縮合反応を完結すればよい。
The organic sulfonic acid metal salt is preferably randomly copolymerized in the polyester molecular chain (main chain) of the copolymerized polyester.
In order to copolymerize the organic sulfonic acid metal salt, in the same manner as in the case of copolymerization of one-end-capped polyoxyalkylene glycol, any stage until the synthesis of the polyester described above is completed, for example, the start of the first stage reaction It may be added at any stage such as before, during the reaction, after completion of the reaction, or during the second stage reaction, and the polycondensation reaction may be completed after the addition.
本発明の共重合ポリエステルを製造するにあたって、安定剤として従来公知のヒンダードフェノール系酸化防止剤やヒンダードアミン系光安定剤や紫外線吸収剤(ベンゾトリアゾール系、ベンゾトリアジン系、ベンゾフェノン系等)を添加することは、共重合ポリエステル又はその繊維等の使用時における熱劣化、酸化劣化、光劣化等を抑制する効果があるだけでなく、溶融時のポリマーの固有粘度の低下をも抑制する効果があるのでむしろ好ましいことである。 In producing the copolyester of the present invention, conventionally known hindered phenol antioxidants, hindered amine light stabilizers and ultraviolet absorbers (benzotriazole, benzotriazine, benzophenone, etc.) are added as stabilizers. This not only has the effect of suppressing thermal degradation, oxidation degradation, photodegradation, etc. during use of the copolyester or its fibers, but also has the effect of inhibiting a decrease in the intrinsic viscosity of the polymer at the time of melting. Rather, it is preferable.
本発明の共重合ポリエステルの好適な分子量はその用途によって異なるが、繊維製造に用いる場合は、O−クロロフェノール中35℃で測定される固有粘度にして0.55〜0.85の範囲が好適である。 The preferred molecular weight of the copolyester of the present invention varies depending on its use, but when used for fiber production, the intrinsic viscosity measured at 35 ° C. in O-chlorophenol is preferably in the range of 0.55 to 0.85. It is.
本発明の共重合ポリエステルには、上記安定剤のほか、必要に応じて任意の添加剤、例えば着色防止剤、耐熱剤、難燃剤、艶消剤、着色剤、無機微粒子等が含まれていても差し支えない。 In addition to the stabilizer, the copolymerized polyester of the present invention contains optional additives as necessary, such as anti-coloring agents, heat-resistant agents, flame retardants, matting agents, coloring agents, inorganic fine particles and the like. There is no problem.
このようにして得られた共重合ポリエステルを繊維にするには、格別の方法を採る必要はなく、通常のポリエステル繊維の製造方法が任意に適用される。例えば、上記共重合ポリエステルを溶融紡糸して巻き取った後、必要に応じて延伸や熱処理を施す方法等によって製造される。紡出される繊維は、中空部を有しない中実繊維であっても、中空部を有する中空繊維であってもよい。また、紡出される繊維の横断面における外形や中空部の形状は円形であっても異形(非円形)であってもよい。さらには、異形断面でかつ1個又は複数個の中空部を有する異形中空繊維としてもよい。 In order to make the copolyester thus obtained into a fiber, it is not necessary to adopt a special method, and a normal method for producing a polyester fiber is arbitrarily applied. For example, the copolymerized polyester is produced by melt spinning and winding, and then stretching or heat treatment as necessary. The spun fiber may be a solid fiber having no hollow part or a hollow fiber having a hollow part. Moreover, the outer shape and the shape of the hollow part in the cross section of the spun fiber may be circular or irregular (non-circular). Furthermore, a modified hollow fiber having a modified cross section and having one or a plurality of hollow portions may be used.
製糸方法としては、500〜2500m/分の速度で溶融紡糸し、延伸・熱処理する方法、2500〜5000m/分の速度で紡糸し、延伸・仮撚加工を同時に又は逐次的に行う方法、5000/分以上の高速で紡糸し、用途によっては延伸工程を省略する方法等を任意に採用することができる。 As a spinning method, a method of melt spinning at a speed of 500 to 2500 m / min and drawing and heat treatment, a method of spinning at a speed of 2500 to 5000 m / min and performing drawing and false twisting simultaneously or sequentially 5000 / A method of spinning at a high speed of more than a minute and omitting the stretching step can be arbitrarily adopted depending on the application.
かくして得られる共重合ポリエステル繊維は長繊維であっても短繊維であってもよく、その単糸繊度や総繊度は用途に応じて任意に選択することができる。
かくして得られる共重合ポリエステル繊維は、長繊維であっても、短繊維であってもよく、それらの単糸繊度及び総繊度は任意に選択できる。
The copolyester fiber thus obtained may be either a long fiber or a short fiber, and the single yarn fineness and the total fineness can be arbitrarily selected according to the application.
The copolyester fiber thus obtained may be either a long fiber or a short fiber, and their single yarn fineness and total fineness can be arbitrarily selected.
さらに、本発明の共重合ポリエステル繊維は必要に応じて、綿、羊毛等の天然繊維、レーヨン、アセテート等の再生繊維及び本発明のポリエステル以外の合繊との混紡、交織等に使用される。
本発明の共重合ポリエステル繊維を少なくとも一部に含んでなる繊維製品の具体例としては、次のようなものを挙げることができる。
Furthermore, the copolymerized polyester fiber of the present invention is used for blending, interweaving and the like with natural fibers such as cotton and wool, regenerated fibers such as rayon and acetate, and synthetic fibers other than the polyester of the present invention, as necessary.
Specific examples of the fiber product comprising at least a part of the copolyester fiber of the present invention include the following.
(1)衣料用途
ファッション用途としてシャツ、ブラウス、パンツ、ブルゾン、コート、和装品等、インナー・レッグ用途として肌着、ブラジャー、ガードル、ボディーファー、キャミソール、ショーツ、パンティーストッキング、ストッキング、靴下、ハイソックス、ショートソックス等、スポーツ用途として競技用のゲームシャツやゲームパンツ(テニス、バスケット、卓球、バレーボール、陸上、ゴルフ、サッカー、ラグビー等)、スェットスーツ、ウィンドブレーカー、アスレチックウェア、トレーニングウェア、ショーツ、水着、プールサイドウェア、アンダーウェア、タイツ、スパッツ、レオタード、レッグ衣料、ウェットスーツ、ドライスーツ等、食品白衣等の白衣、レディス向けブラウス等のユニフォーム用途、寝衣用途、学生服用途、帽子、ショール等の衣料付帯品、裏地、カップ、パッド等の衣料資材、スポーツシューズ等
(2)インテリア・寝具用途
カーテン(ドレープカーテン、レースカーテン、シャワーカーテン、ロールカーテン、ブラインド等)、カーペット、テーブルクロス、椅子張り、間仕切り、壁紙、寝装品(掛けふとん、敷き布団、布団用側地、布団用詰め物、毛布、毛布用側地、タオルケット、シーツ等)、スリッパ、マット等
(3)自動車内装材用途
カーシート、カーマット、天井材、トリム等
(4)産業資材用途
テント類(レジャー用、イベント用等)
(1) Clothing use Shirts, blouses, pants, blousons, coats, Japanese clothing, etc. for fashion use, underwear, bras, girdles, body fur, camisole, shorts, pantyhose, stockings, socks, high socks, short for use as inner legs Game shirts and game pants for sports use such as socks (tennis, basketball, table tennis, volleyball, track, golf, soccer, rugby, etc.), suits, windbreakers, athletic wear, training wear, shorts, swimwear, swimming pool Sidewear, underwear, tights, spats, leotards, leg clothing, wet suits, dry suits, white coats such as food white coats, uniforms such as ladies' blouses, nightwear use, School clothes, hats, shawls and other clothing accessories, linings, cups, pads and other clothing materials, sports shoes, etc. (2) Interior / bedding applications Curtains (draping curtains, lace curtains, shower curtains, roll curtains, blinds, etc.) , Carpets, tablecloths, upholstered chairs, partitions, wallpaper, bedding (comforters, mattresses, futon lining, blankets, blankets, blankets, towels, sheets, etc.), slippers, mats, etc. (3) Automobiles Interior material use Car seat, car mat, ceiling material, trim, etc. (4) Industrial material use Tents (for leisure, for events, etc.)
上記の用途なかでも、肌着、食品白衣等の白衣、レディス向けブラウス等のユニフォーム、テーブルクロス等リネン資材等の洗濯頻度の高い衣類になした場合に特にその利点が発揮され、レンタルユニフォーム等のリネンサプライ分野において特に有用である。
さらに、屋外で使用するスポーツウェア分野や盛夏用ウェア分野等、洗濯頻度が高く、かつ日光干しする機会の多い衣料用途において極めて有用である。
以上は、繊維について詳述したが、本発明の共重合ポリエステルをフィルム、テープあるいはその他の成形体にした場合にも同様の効果が期待できる。
Among the above-mentioned uses, it is especially effective when used in clothes such as underwear, food lab coats, uniforms such as blouse for ladies, and linen materials such as table cloths. Linen such as rental uniforms It is particularly useful in the supply field.
Furthermore, it is extremely useful in clothing applications that are frequently washed and frequently sun-dried, such as the field of sportswear used outdoors and the field of midsummer clothing.
Although the fiber has been described in detail above, the same effect can be expected when the copolymerized polyester of the present invention is formed into a film, tape, or other molded body.
以下、実施例及び比較例を挙げて本発明を具体的に説明する。ただし、本発明はこれらによって何ら限定されるものではない。なお、実施例、比較例中の部及び%は、特に断らない限り、それぞれ重量部及び重量%を示す。また、共重合ポリエステル繊維中の金属含有量はICP発光分光分析法により定量した。さらに、防汚処理及び防汚性評価並びに紫外線照射は下記の方法によった。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. However, the present invention is not limited by these. In addition, unless otherwise indicated, the part and% in an Example and a comparative example show a weight part and weight%, respectively. The metal content in the copolymerized polyester fiber was quantified by ICP emission spectroscopic analysis. Furthermore, antifouling treatment, antifouling property evaluation and ultraviolet irradiation were performed by the following methods.
<汚染処理>
10cm×10cmの平織物試料を、下記表1に示す組成の洗濯再汚染液が入った処理ポットに浴比が1:260になるように負荷布(綿100%精錬布)で調整して入れ、50℃で60分間攪拌処理した。
<Contamination treatment>
A 10 cm × 10 cm plain woven fabric sample is placed in a treatment pot containing a laundry re-contamination liquid having the composition shown in Table 1 below with a load cloth (100% cotton scouring cloth) so that the bath ratio is 1: 260. The mixture was stirred at 50 ° C. for 60 minutes.
軽く水洗した後、試料を濾紙の間に挟み余分の汚染液を除いた。次いで汚染した試料を家庭洗濯機で洗濯用合成洗剤の標準使用量を用い、JIS L 0217付表1番号103の規定されている洗濯操作を1サイクル(1回)とし、これに従って25回の洗濯を繰り返した。洗濯温度は55℃で行い、乾燥は室内自然乾燥で行った。
次いで下記の方法により防汚性と白度を評価した。
After lightly washing with water, the sample was sandwiched between filter papers to remove excess contaminants. Next, the contaminated sample was washed in a household washing machine using the standard amount of synthetic detergent for washing, and the washing operation specified in JIS L 0217 Attached Table 1 No. 103 was defined as one cycle (one time). Repeated. The washing temperature was 55 ° C., and the drying was performed by indoor natural drying.
Subsequently, antifouling property and whiteness were evaluated by the following methods.
<防汚性評価>
ミノルタ色彩色差計CR―200(ミノルタカメラ販売(株))を用い、試料のCIE 表色系のL*、a*、b*値を測定し、下記数式により防汚性(△E*)を求めた。
L1、a1、b1はそれぞれ汚染処理前の試料のL*、a*、b*値を示し、L2、a2、b2はそれぞれ洗濯後の試料のL*、a*、b*値を示す。
<Anti-fouling evaluation>
Using a Minolta Color Difference Meter CR-200 (Minolta Camera Sales Co., Ltd.), measure the LIE, C *, and L * values of the CIE color system of the sample. Asked.
L1, a1, and b1 respectively indicate L *, a *, and b * values of the sample before the contamination treatment, and L2, a2, and b2 indicate L *, a *, and b * values of the sample after washing, respectively.
<紫外線照射>
スガ試験機(株)製の紫外線オートフェードメーターを用い、編地試料を大型ホルダーにセットして、ブラックパネル温度設定63℃、試験槽湿球温度設定33℃の条件下で20時間、紫外線カーボンアークによる紫外線照射を施した。
<UV irradiation>
Using a UV auto fade meter manufactured by Suga Test Instruments Co., Ltd., place the knitted fabric sample in a large holder, and set the black carbon panel temperature to 63 ° C and the test bath wet bulb temperature to 33 ° C for 20 hours. Ultraviolet irradiation by arc was performed.
[実施例1]
テレフタル酸ジメチル100部、3,5−ジカルボメトキシベンゼンスルホン酸ニッケル4部(テレフタル酸ジメチルに対して1.3モル%)、エチレングリコール60部、酢酸カルシウム1水塩0.06部(テレフタル酸ジメチルに対して0.066モル%)及び整色剤として酢酸コバルト4水塩0.009部(テレフタル酸ジメチルに対して0.007モル%)をエステル交換缶に仕込み、窒素ガス雰囲気下4時間かけて140℃から220℃まで昇温して生成するメタノールを系外に留去しながらエステル交換反応を行った。エステル交換反応終了後、安定剤としてリン酸トリメチル0.058部(テレフタル酸ジメチルに対して0.080モル%)を加えた。次いで10分後に三酸化アンチモン0.04部(テレフタル酸ジメチルに対して0.027モル%)を添加し、同時に過剰のエチレングリコールを追出しながら240℃まで昇温した後重合缶に移した。
[Example 1]
100 parts of dimethyl terephthalate, 4 parts of nickel 3,5-dicarbomethoxybenzenesulfonate (1.3 mol% with respect to dimethyl terephthalate), 60 parts of ethylene glycol, 0.06 part of calcium acetate monohydrate (terephthalic acid) 0.066 mol% with respect to dimethyl) and 0.009 part of cobalt acetate tetrahydrate (0.007 mol% with respect to dimethyl terephthalate) as a color adjuster were charged in a transesterification can and placed in a nitrogen gas atmosphere for 4 hours. The ester exchange reaction was carried out while distilling out the methanol produced by heating from 140 ° C. to 220 ° C. over the system. After completion of the transesterification reaction, 0.058 part of trimethyl phosphate (0.080 mol% based on dimethyl terephthalate) was added as a stabilizer. Then, 10 minutes later, 0.04 part of antimony trioxide (0.027 mol% with respect to dimethyl terephthalate) was added, and the temperature was raised to 240 ° C. while expelling excess ethylene glycol.
重合缶に平均の分子量が4000(n=90)のポリオキシエチレングリコールモノメチルエーテル5部(共重合ポリエステルに対して4.6%)を添加した後、1時間かけて760Torrから1Torrまで減圧し、同時に1時間30分かけて240℃から280℃まで昇温した。1Torr以下の減圧下、重合温度280℃でさらに2時間重合した時点で酸化防止剤としてイルガノックス1010(チバ・スペシャルティ・ケミカルズ社製)0.8部を真空添加し、その後さらに30分間重合した。得られたポリマーを常法に従ってチップ化した。このポリマーの固有粘度は0.65であった。 After adding 5 parts of polyoxyethylene glycol monomethyl ether having an average molecular weight of 4000 (n = 90) to the polymerization can (4.6% with respect to the copolyester), the pressure was reduced from 760 Torr to 1 Torr over 1 hour, At the same time, the temperature was raised from 240 ° C. to 280 ° C. over 1 hour 30 minutes. When further polymerizing at a polymerization temperature of 280 ° C. for 2 hours under a reduced pressure of 1 Torr or less, 0.8 part of Irganox 1010 (manufactured by Ciba Specialty Chemicals) was added in vacuo as an antioxidant, and then polymerized for another 30 minutes. The obtained polymer was chipped according to a conventional method. The intrinsic viscosity of this polymer was 0.65.
このチップを常法に従って乾燥後、孔径0.3mmの円形紡糸孔を24個穿設した紡糸口金を使用して285℃で溶融紡糸した。次いで、得られた未延伸糸を、最終的に得られる延伸糸の伸度が30%になるような延伸倍率にて84℃の加熱ローラーと180℃のプレートヒーターを使って延伸熱処理して84デシテックス/24フィラメントの延伸糸を得た。得られた延伸糸を用いて平織物を製織し、常法により精錬・熱処理を行った。 This chip was dried according to a conventional method, and then melt-spun at 285 ° C. using a spinneret having 24 circular spinning holes having a hole diameter of 0.3 mm. Next, the obtained undrawn yarn was drawn and heat-treated using a heating roller at 84 ° C. and a plate heater at 180 ° C. at a draw ratio such that the elongation of the drawn yarn finally obtained was 30%. A drawn yarn of decitex / 24 filament was obtained. A plain woven fabric was woven using the obtained drawn yarn, and refining and heat treatment were performed by a conventional method.
このようにして作製した平織物を試験試料として金属の定量分析を行った。また、該平織物試料の一部を用いて所定の紫外線照射を施した。この「紫外線照射あり」の試料と該紫外線照射を施していない「紫外線照射なし」の試料(対照試料)とに汚染処理を施し、防汚性を評価した。結果は表2に示す通りであった。 The plain woven fabric thus produced was used as a test sample for quantitative metal analysis. Moreover, predetermined ultraviolet irradiation was given using a part of this plain fabric sample. The sample with “ultraviolet irradiation” and the sample without “ultraviolet irradiation” (control sample) not subjected to the ultraviolet irradiation were subjected to contamination treatment to evaluate the antifouling property. The results were as shown in Table 2.
[比較例1]
実施例1で有機スルホン酸金属塩として使用した3,5−ジカルボメトキシベンゼンスルホン酸ニッケル4部を使用しない以外は実施例1と同様にしてエステル交換反応、重合反応、チップ化、チップ乾燥、紡糸、延伸熱処理、製織、精錬、熱処理を行った。得られた平織物試料の測定結果は表2に示す通りであった。
[Comparative Example 1]
Transesterification reaction, polymerization reaction, chip formation, chip drying, in the same manner as in Example 1 except that 4 parts of nickel 3,5-dicarbomethoxybenzenesulfonate used as the organic sulfonic acid metal salt in Example 1 was not used. Spinning, drawing heat treatment, weaving, refining, and heat treatment were performed. The measurement results of the obtained plain woven fabric samples were as shown in Table 2.
[実施例2〜5]
実施例1で有機スルホン酸金属塩として用いた3,5−ジカルボメトキシベンゼンスルホン酸ニッケルの使用量を表2に記載した量とする以外は実施例1と同様に行った。結果は表2に示す通りであった。
[Examples 2 to 5]
The same procedure as in Example 1 was performed except that the amount of nickel 3,5-dicarbomethoxybenzenesulfonate used as the organic sulfonic acid metal salt in Example 1 was changed to the amount shown in Table 2. The results were as shown in Table 2.
[実施例6〜9]
実施例1で有機スルホン酸金属塩として使用した3,5−ジカルボメトキシベンゼンスルホン酸ニッケル4部に代えて、3,5−ジカルボメトキシベンゼンスルホン酸マンガンを表2に記載した量用いる以外は実施例1と同様に行った。結果は表2に示す通りであった。
[Examples 6 to 9]
Instead of using 4 parts of nickel 3,5-dicarbomethoxybenzenesulfonate used as the organic sulfonic acid metal salt in Example 1, manganese 3,5-dicarbomethoxybenzenesulfonate was used in the amount described in Table 2. The same operation as in Example 1 was performed. The results were as shown in Table 2.
[実施例10〜13]
実施例1で有機スルホン酸金属塩として使用した3,5−ジカルボメトキシベンゼンスルホン酸ニッケル4部に代えて、3,5−ジカルボメトキシベンゼンスルホン酸バリウムを表2に記載した量用いる以外は実施例1と同様に行った。結果は表2に示す通りであった。
[Examples 10 to 13]
Instead of using 4 parts of nickel 3,5-dicarbomethoxybenzenesulfonate used as the organic sulfonate metal salt in Example 1, barium 3,5-dicarbomethoxybenzenesulfonate was used in the amount shown in Table 2. The same operation as in Example 1 was performed. The results were as shown in Table 2.
[比較例2]
実施例1で有機スルホン酸金属塩として使用した3,5−ジカルボメトキシベンゼンスルホン酸ニッケル4部に代えて、3,5−ジカルボメトキシベンゼンスルホン酸ナトリウム4部(テレフタル酸ジメチルに対して2.6モル%)及びエーテル副生防止剤として酢酸ナトリウム3水塩0.11部(テレフタル酸ジメチルに対して0.16モル%)を表2に記載した量用いる以外は実施例1と同様に行った。結果は表2に示す通りであった。
[Comparative Example 2]
Instead of 4 parts of nickel 3,5-dicarbomethoxybenzenesulfonate used as the organic sulfonate metal salt in Example 1, 4 parts of sodium 3,5-dicarbomethoxybenzenesulfonate (2 parts per 2 parts of dimethyl terephthalate) .6 mol%) and 0.11 part of sodium acetate trihydrate (0.16 mol% based on dimethyl terephthalate) as an ether by-product inhibitor was used in the same manner as in Example 1 except that the amounts shown in Table 2 were used. went. The results were as shown in Table 2.
本発明の共重合ポリエステルは上述のような特性を有するため、該共重合ポリエステルからなる繊維は、従来のものに比べて防汚性及びその洗濯耐久性が改良され、特に洗濯による再汚染防止性、黒ずみ防止性が大幅に改良されるので、例えば肌着、食品白衣等の白衣、レディス向けブラウス等のユニフォーム、テーブルクロス等リネン資材等の洗濯頻度の高い衣類やその他の繊維製品になした場合に特にその利点が発揮され、洗濯を繰り返しても、防汚性が保持されて洗濯による黒ずみが起こらない。このため、本発明の共重合ポリエステル繊維はレンタルユニフォーム等のリネンサプライ分野において特に有用である。さらに、該繊維は日光暴露に伴う上記の防汚性及びその洗濯耐久性の低下が著しく少ないという利点も有している。 Since the copolyester of the present invention has the above-mentioned properties, the fiber made of the copolyester has improved antifouling properties and washing durability compared to conventional ones, and is particularly resistant to recontamination by washing. As a result, the anti-darkening property will be greatly improved.For example, when clothes are used for clothes such as underwear, food lab coats, uniforms such as blouse for ladies, linen materials such as table cloths, and other textile products. The advantage is exhibited especially, and even if washing is repeated, antifouling property is maintained and blackening due to washing does not occur. For this reason, the copolyester fiber of the present invention is particularly useful in the field of linen supply such as rental uniforms. Further, the fiber has an advantage that the above-mentioned antifouling property and its washing durability due to sun exposure are remarkably reduced.
したがって、本発明の共重合ポリエステル繊維を含む織編物、不織布等の繊維構造物及び繊維製品は、特に屋外で使用するスポーツウェア分野や盛夏用ウェア分野のような洗濯頻度が高くかつ日光干しする機会の多い衣料用途においても極めて有用である。
また、本発明の共重合ポリエステルは繊維のほか、上記と同様の特性・機能が要求されるフィルム、テープ等の分野でも有用である。
Therefore, textile structures and textile products such as woven and knitted fabrics and nonwoven fabrics containing the copolymerized polyester fiber of the present invention have a high frequency of washing, particularly in outdoor sportswear and high-summer wear fields, and are opportunities to be sun-dried. It is also extremely useful in apparel applications with a large amount of clothes.
In addition to fibers, the copolymerized polyester of the present invention is also useful in fields such as films and tapes that require the same properties and functions as described above.
Claims (7)
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JP2016222802A (en) * | 2015-05-29 | 2016-12-28 | 東レ株式会社 | Terminal modified copolymer polyester resin and manufacturing method therefor |
WO2018016468A1 (en) * | 2016-07-19 | 2018-01-25 | 東レ株式会社 | Copolymer polyester and composite fiber containing same |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2016222802A (en) * | 2015-05-29 | 2016-12-28 | 東レ株式会社 | Terminal modified copolymer polyester resin and manufacturing method therefor |
WO2018016468A1 (en) * | 2016-07-19 | 2018-01-25 | 東レ株式会社 | Copolymer polyester and composite fiber containing same |
CN109476832A (en) * | 2016-07-19 | 2019-03-15 | 东丽株式会社 | Copolyester and composite fibre comprising the copolyester |
JPWO2018016468A1 (en) * | 2016-07-19 | 2019-05-09 | 東レ株式会社 | Copolymerized polyester and composite fiber containing the same |
JP7009995B2 (en) | 2016-07-19 | 2022-02-10 | 東レ株式会社 | Copolymerized polyester and composite fibers containing it |
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