JPH01162822A - Modified polyester fiber - Google Patents
Modified polyester fiberInfo
- Publication number
- JPH01162822A JPH01162822A JP63063692A JP6369288A JPH01162822A JP H01162822 A JPH01162822 A JP H01162822A JP 63063692 A JP63063692 A JP 63063692A JP 6369288 A JP6369288 A JP 6369288A JP H01162822 A JPH01162822 A JP H01162822A
- Authority
- JP
- Japan
- Prior art keywords
- salt
- acid
- intrinsic viscosity
- fiber
- modified 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.)
- Granted
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 75
- 239000000835 fiber Substances 0.000 title claims abstract description 38
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 125000000524 functional group Chemical group 0.000 claims abstract description 9
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 6
- 239000012153 distilled water Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 1
- -1 sulfonic acid phosphonium salt Chemical class 0.000 abstract description 45
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 31
- 125000002091 cationic group Chemical group 0.000 abstract description 13
- 238000002074 melt spinning Methods 0.000 abstract description 7
- MMJOUBUIEZZWDJ-UHFFFAOYSA-M 3,5-bis(methoxycarbonyl)benzenesulfonate;tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC.COC(=O)C1=CC(C(=O)OC)=CC(S([O-])(=O)=O)=C1 MMJOUBUIEZZWDJ-UHFFFAOYSA-M 0.000 abstract description 4
- 238000004043 dyeing Methods 0.000 abstract description 3
- 238000009998 heat setting Methods 0.000 abstract description 2
- 229920006240 drawn fiber Polymers 0.000 abstract 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 abstract 1
- 238000009987 spinning Methods 0.000 description 58
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 45
- 239000000243 solution Substances 0.000 description 37
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 35
- 229920000642 polymer Polymers 0.000 description 32
- 238000000034 method Methods 0.000 description 28
- 150000003839 salts Chemical class 0.000 description 23
- 238000006116 polymerization reaction Methods 0.000 description 18
- 150000004714 phosphonium salts Chemical group 0.000 description 17
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 16
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 14
- 239000002253 acid Substances 0.000 description 11
- 239000000975 dye Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000002585 base Substances 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- XVHQFGPOVXTXPD-UHFFFAOYSA-M tetraphenylphosphanium;hydroxide Chemical compound [OH-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 XVHQFGPOVXTXPD-UHFFFAOYSA-M 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 5
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 4
- BWLOPTUNEMCWSZ-UHFFFAOYSA-K 5-sulfonatobenzene-1,3-dicarboxylate tetraphenylphosphanium Chemical compound [O-]C(=O)c1cc(cc(c1)S([O-])(=O)=O)C([O-])=O.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1 BWLOPTUNEMCWSZ-UHFFFAOYSA-K 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000003457 sulfones Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical class CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 3
- RHWJSEPZWWXCNE-UHFFFAOYSA-N 3,5-dicarboxybenzenesulfonate;tributylphosphanium Chemical compound CCCC[PH+](CCCC)CCCC.OC(=O)C1=CC(C(O)=O)=CC(S([O-])(=O)=O)=C1 RHWJSEPZWWXCNE-UHFFFAOYSA-N 0.000 description 2
- CARJPEPCULYFFP-UHFFFAOYSA-N 5-Sulfo-1,3-benzenedicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(S(O)(=O)=O)=C1 CARJPEPCULYFFP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- 238000004364 calculation method Methods 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000012668 chain scission Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- JHYNXXDQQHTCHJ-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 JHYNXXDQQHTCHJ-UHFFFAOYSA-M 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 235000011007 phosphoric acid Nutrition 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
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 2
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 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
- 239000000052 vinegar Substances 0.000 description 2
- 235000021419 vinegar Nutrition 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-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
- YTVQIZRDLKWECQ-UHFFFAOYSA-N 2-benzoylcyclohexan-1-one Chemical compound C=1C=CC=CC=1C(=O)C1CCCCC1=O YTVQIZRDLKWECQ-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- QMDROCCPGIIEOM-UHFFFAOYSA-N 2-icosylphosphanylethane-1,1-diol Chemical compound CCCCCCCCCCCCCCCCCCCCPCC(O)O QMDROCCPGIIEOM-UHFFFAOYSA-N 0.000 description 1
- XCSGHNKDXGYELG-UHFFFAOYSA-N 2-phenoxyethoxybenzene Chemical compound C=1C=CC=CC=1OCCOC1=CC=CC=C1 XCSGHNKDXGYELG-UHFFFAOYSA-N 0.000 description 1
- WLPLZSMVVXVBNF-UHFFFAOYSA-M 3,5-bis(2-hydroxyethoxycarbonyl)benzenesulfonate;tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC.OCCOC(=O)C1=CC(C(=O)OCCO)=CC(S([O-])(=O)=O)=C1 WLPLZSMVVXVBNF-UHFFFAOYSA-M 0.000 description 1
- YRUPCSWZCGCUJC-UHFFFAOYSA-M 3,5-bis(2-hydroxyethoxycarbonyl)benzenesulfonate;tetraphenylphosphanium Chemical compound OCCOC(=O)C1=CC(C(=O)OCCO)=CC(S([O-])(=O)=O)=C1.C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 YRUPCSWZCGCUJC-UHFFFAOYSA-M 0.000 description 1
- ITIJITVUYUUZMA-UHFFFAOYSA-N 3,5-bis(methoxycarbonyl)benzenesulfonate;dibutyl(phenyl)phosphanium Chemical compound CCCC[PH+](CCCC)C1=CC=CC=C1.COC(=O)C1=CC(C(=O)OC)=CC(S([O-])(=O)=O)=C1 ITIJITVUYUUZMA-UHFFFAOYSA-N 0.000 description 1
- IJDCBDUZWZUMFK-UHFFFAOYSA-M 3,5-bis(methoxycarbonyl)benzenesulfonate;ethyl(triphenyl)phosphanium Chemical compound COC(=O)C1=CC(C(=O)OC)=CC(S([O-])(=O)=O)=C1.C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 IJDCBDUZWZUMFK-UHFFFAOYSA-M 0.000 description 1
- AORSDIVQVWZDNS-UHFFFAOYSA-M 3,5-bis(methoxycarbonyl)benzenesulfonate;tetraphenylphosphanium Chemical compound COC(=O)C1=CC(C(=O)OC)=CC(S([O-])(=O)=O)=C1.C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 AORSDIVQVWZDNS-UHFFFAOYSA-M 0.000 description 1
- MUYBAIDXGIMHTM-UHFFFAOYSA-N 3,5-bis(methoxycarbonyl)benzenesulfonate;tribenzylphosphanium Chemical compound COC(=O)C1=CC(C(=O)OC)=CC(S([O-])(=O)=O)=C1.C=1C=CC=CC=1C[PH+](CC=1C=CC=CC=1)CC1=CC=CC=C1 MUYBAIDXGIMHTM-UHFFFAOYSA-N 0.000 description 1
- QUWCTZLAYFKKMZ-UHFFFAOYSA-M 3,5-bis(methoxycarbonyl)benzenesulfonate;tributyl(phenyl)phosphanium Chemical compound COC(=O)C1=CC(C(=O)OC)=CC(S([O-])(=O)=O)=C1.CCCC[P+](CCCC)(CCCC)C1=CC=CC=C1 QUWCTZLAYFKKMZ-UHFFFAOYSA-M 0.000 description 1
- KJALZYXICRRPAH-UHFFFAOYSA-N 3,5-bis(methoxycarbonyl)benzenesulfonate;tricyclohexylphosphanium Chemical compound COC(=O)C1=CC(C(=O)OC)=CC(S([O-])(=O)=O)=C1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1 KJALZYXICRRPAH-UHFFFAOYSA-N 0.000 description 1
- BTNMSTDHEBOVMW-UHFFFAOYSA-N 3,5-bis(methoxycarbonyl)benzenesulfonate;trioctylphosphanium Chemical compound COC(=O)C1=CC(C(=O)OC)=CC(S([O-])(=O)=O)=C1.CCCCCCCC[PH+](CCCCCCCC)CCCCCCCC BTNMSTDHEBOVMW-UHFFFAOYSA-N 0.000 description 1
- RTOYDLKCCYQSAW-UHFFFAOYSA-N 3,5-bis(methoxycarbonyl)benzenesulfonate;triphenylphosphanium Chemical compound COC(=O)C1=CC(C(=O)OC)=CC(S([O-])(=O)=O)=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RTOYDLKCCYQSAW-UHFFFAOYSA-N 0.000 description 1
- LJBXTAHSWIRDDK-UHFFFAOYSA-N 3,5-bis(methoxycarbonyl)benzenesulfonate;tripropylphosphanium Chemical compound CCC[PH+](CCC)CCC.COC(=O)C1=CC(C(=O)OC)=CC(S([O-])(=O)=O)=C1 LJBXTAHSWIRDDK-UHFFFAOYSA-N 0.000 description 1
- PSSLSYUSSXRMAK-UHFFFAOYSA-N 3,5-dicarboxybenzenesulfonate;triethylphosphanium Chemical compound CC[PH+](CC)CC.OC(=O)C1=CC(C(O)=O)=CC(S([O-])(=O)=O)=C1 PSSLSYUSSXRMAK-UHFFFAOYSA-N 0.000 description 1
- PXQRVOCHISUSCC-UHFFFAOYSA-M 3-(2-hydroxyethoxycarbonyl)benzenesulfonate;tetrabutylphosphanium Chemical compound OCCOC(=O)C1=CC=CC(S([O-])(=O)=O)=C1.CCCC[P+](CCCC)(CCCC)CCCC PXQRVOCHISUSCC-UHFFFAOYSA-M 0.000 description 1
- KIINLFFTVAGQMM-UHFFFAOYSA-M 3-(2-hydroxyethoxycarbonyl)benzenesulfonate;tetraphenylphosphanium Chemical compound OCCOC(=O)C1=CC=CC(S([O-])(=O)=O)=C1.C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 KIINLFFTVAGQMM-UHFFFAOYSA-M 0.000 description 1
- KCTFVMYOPINVSK-UHFFFAOYSA-M 3-methoxycarbonylbenzenesulfonate;tetrabutylphosphanium Chemical compound COC(=O)C1=CC=CC(S([O-])(=O)=O)=C1.CCCC[P+](CCCC)(CCCC)CCCC KCTFVMYOPINVSK-UHFFFAOYSA-M 0.000 description 1
- MAZBWEMFCXPKGH-UHFFFAOYSA-M 3-methoxycarbonylbenzenesulfonate;tetraphenylphosphanium Chemical compound COC(=O)C1=CC=CC(S([O-])(=O)=O)=C1.C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 MAZBWEMFCXPKGH-UHFFFAOYSA-M 0.000 description 1
- BSELDXNAHWCMLH-UHFFFAOYSA-L 3-sulfonatobenzoate tetrabutylphosphanium Chemical compound [O-]C(=O)c1cccc(c1)S([O-])(=O)=O.CCCC[P+](CCCC)(CCCC)CCCC.CCCC[P+](CCCC)(CCCC)CCCC BSELDXNAHWCMLH-UHFFFAOYSA-L 0.000 description 1
- SDGNNLQZAPXALR-UHFFFAOYSA-N 3-sulfophthalic acid Chemical compound OC(=O)C1=CC=CC(S(O)(=O)=O)=C1C(O)=O SDGNNLQZAPXALR-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
- JYQJLVPMTBJMTI-UHFFFAOYSA-M 4-(2-hydroxyethoxy)benzenesulfonate;tetrabutylphosphanium Chemical compound OCCOC1=CC=C(S([O-])(=O)=O)C=C1.CCCC[P+](CCCC)(CCCC)CCCC JYQJLVPMTBJMTI-UHFFFAOYSA-M 0.000 description 1
- GXUFEDNPWYCYLX-UHFFFAOYSA-N 4-(2-hydroxyethoxy)benzenesulfonate;triphenylphosphanium Chemical compound OCCOC1=CC=C(S([O-])(=O)=O)C=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 GXUFEDNPWYCYLX-UHFFFAOYSA-N 0.000 description 1
- FBYJOCBDWDVDOJ-UHFFFAOYSA-M 4-methylbenzenesulfonate;tetrabutylphosphanium Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1.CCCC[P+](CCCC)(CCCC)CCCC FBYJOCBDWDVDOJ-UHFFFAOYSA-M 0.000 description 1
- YRZZSISQPWXIPF-UHFFFAOYSA-N 5-phenylmethoxysulfonylbenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(S(=O)(=O)OCC=2C=CC=CC=2)=C1 YRZZSISQPWXIPF-UHFFFAOYSA-N 0.000 description 1
- QCSIRLGSMWDFMF-UHFFFAOYSA-K 5-sulfonatobenzene-1,3-dicarboxylate tetrabutylphosphanium Chemical compound [O-]C(=O)c1cc(cc(c1)S([O-])(=O)=O)C([O-])=O.CCCC[P+](CCCC)(CCCC)CCCC.CCCC[P+](CCCC)(CCCC)CCCC.CCCC[P+](CCCC)(CCCC)CCCC QCSIRLGSMWDFMF-UHFFFAOYSA-K 0.000 description 1
- FQVMIQKRLZHUDJ-UHFFFAOYSA-K 5-sulfonatobenzene-1,3-dicarboxylate tributyl(ethyl)phosphanium Chemical compound CCCC[P+](CC)(CCCC)CCCC.CCCC[P+](CC)(CCCC)CCCC.CCCC[P+](CC)(CCCC)CCCC.[O-]C(=O)c1cc(cc(c1)S([O-])(=O)=O)C([O-])=O FQVMIQKRLZHUDJ-UHFFFAOYSA-K 0.000 description 1
- DALNSBKXJGCIGM-UHFFFAOYSA-K 5-sulfonatobenzene-1,3-dicarboxylate tributyl(phenyl)phosphanium Chemical compound [O-]C(=O)c1cc(cc(c1)S([O-])(=O)=O)C([O-])=O.CCCC[P+](CCCC)(CCCC)c1ccccc1.CCCC[P+](CCCC)(CCCC)c1ccccc1.CCCC[P+](CCCC)(CCCC)c1ccccc1 DALNSBKXJGCIGM-UHFFFAOYSA-K 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- PIDTVICNRUCZHQ-UHFFFAOYSA-N C(C1=CC=CC=C1)[PH+](CC1=CC=CC=C1)CC1=CC=CC=C1.C(=O)([O-])C=1C=C(C=C(C1)C(=O)[O-])S(=O)(=O)[O-].C(C1=CC=CC=C1)[PH+](CC1=CC=CC=C1)CC1=CC=CC=C1.C(C1=CC=CC=C1)[PH+](CC1=CC=CC=C1)CC1=CC=CC=C1 Chemical compound C(C1=CC=CC=C1)[PH+](CC1=CC=CC=C1)CC1=CC=CC=C1.C(=O)([O-])C=1C=C(C=C(C1)C(=O)[O-])S(=O)(=O)[O-].C(C1=CC=CC=C1)[PH+](CC1=CC=CC=C1)CC1=CC=CC=C1.C(C1=CC=CC=C1)[PH+](CC1=CC=CC=C1)CC1=CC=CC=C1 PIDTVICNRUCZHQ-UHFFFAOYSA-N 0.000 description 1
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
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- 239000005977 Ethylene Substances 0.000 description 1
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- 208000032843 Hemorrhage Diseases 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
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- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
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- 239000000654 additive Substances 0.000 description 1
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- 239000003513 alkali Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
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- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- IKNWWJMESJSJDP-UHFFFAOYSA-N benzyl(tributyl)phosphanium Chemical class CCCC[P+](CCCC)(CCCC)CC1=CC=CC=C1 IKNWWJMESJSJDP-UHFFFAOYSA-N 0.000 description 1
- BNQRPLGZFADFGA-UHFFFAOYSA-N benzyl(triphenyl)phosphanium Chemical class C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 BNQRPLGZFADFGA-UHFFFAOYSA-N 0.000 description 1
- BUDPGRUUAXTNRB-UHFFFAOYSA-K benzyl(triphenyl)phosphanium 5-sulfonatobenzene-1,3-dicarboxylate Chemical compound [O-]C(=O)c1cc(cc(c1)S([O-])(=O)=O)C([O-])=O.C(c1ccccc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.C(c1ccccc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.C(c1ccccc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1 BUDPGRUUAXTNRB-UHFFFAOYSA-K 0.000 description 1
- USFRYJRPHFMVBZ-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 USFRYJRPHFMVBZ-UHFFFAOYSA-M 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
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- 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 1
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- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 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
- 238000004040 coloring Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- VBVCYAZECWLFHP-UHFFFAOYSA-N dodecyl benzenesulfonate;tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC.CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 VBVCYAZECWLFHP-UHFFFAOYSA-N 0.000 description 1
- 230000005489 elastic deformation Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- SLAFUPJSGFVWPP-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;iodide Chemical compound [I-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 SLAFUPJSGFVWPP-UHFFFAOYSA-M 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 1
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 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
- QHVUZLUPVYICJZ-UHFFFAOYSA-M octadecanoate;tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC.CCCCCCCCCCCCCCCCCC([O-])=O QHVUZLUPVYICJZ-UHFFFAOYSA-M 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000035515 penetration Effects 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
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- 150000003003 phosphines Chemical class 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002954 polymerization reaction product Substances 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
- 230000002265 prevention Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000008054 sulfonate salts Chemical class 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- WALNCKJQTNNUDQ-UHFFFAOYSA-M tetra(propan-2-yl)azanium;chloride Chemical compound [Cl-].CC(C)[N+](C(C)C)(C(C)C)C(C)C WALNCKJQTNNUDQ-UHFFFAOYSA-M 0.000 description 1
- CPOUUWYFNYIYLQ-UHFFFAOYSA-M tetra(propan-2-yl)azanium;hydroxide Chemical compound [OH-].CC(C)[N+](C(C)C)(C(C)C)C(C)C CPOUUWYFNYIYLQ-UHFFFAOYSA-M 0.000 description 1
- GFZMLBWMGBLIDI-UHFFFAOYSA-M tetrabutylphosphanium;acetate Chemical compound CC([O-])=O.CCCC[P+](CCCC)(CCCC)CCCC GFZMLBWMGBLIDI-UHFFFAOYSA-M 0.000 description 1
- NYHGQGKRPTYCBV-UHFFFAOYSA-K tetrabutylphosphanium;phosphate Chemical compound [O-]P([O-])([O-])=O.CCCC[P+](CCCC)(CCCC)CCCC.CCCC[P+](CCCC)(CCCC)CCCC.CCCC[P+](CCCC)(CCCC)CCCC NYHGQGKRPTYCBV-UHFFFAOYSA-K 0.000 description 1
- UBYSUBPDYKNKFA-UHFFFAOYSA-N tetrabutylphosphanium;phosphite Chemical compound [O-]P([O-])[O-].CCCC[P+](CCCC)(CCCC)CCCC.CCCC[P+](CCCC)(CCCC)CCCC.CCCC[P+](CCCC)(CCCC)CCCC UBYSUBPDYKNKFA-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- UQFSVBXCNGCBBW-UHFFFAOYSA-M tetraethylammonium iodide Chemical compound [I-].CC[N+](CC)(CC)CC UQFSVBXCNGCBBW-UHFFFAOYSA-M 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- YIEDHPBKGZGLIK-UHFFFAOYSA-L tetrakis(hydroxymethyl)phosphanium;sulfate Chemical compound [O-]S([O-])(=O)=O.OC[P+](CO)(CO)CO.OC[P+](CO)(CO)CO YIEDHPBKGZGLIK-UHFFFAOYSA-L 0.000 description 1
- BALCYVFFDOBQPW-UHFFFAOYSA-M tetraphenylazanium;chloride Chemical compound [Cl-].C1=CC=CC=C1[N+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BALCYVFFDOBQPW-UHFFFAOYSA-M 0.000 description 1
- ZJKOMXZUJBYOOK-UHFFFAOYSA-M tetraphenylazanium;hydroxide Chemical compound [OH-].C1=CC=CC=C1[N+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 ZJKOMXZUJBYOOK-UHFFFAOYSA-M 0.000 description 1
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 1
- FBEVECUEMUUFKM-UHFFFAOYSA-M tetrapropylazanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CCC FBEVECUEMUUFKM-UHFFFAOYSA-M 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- HOMONHWYLOPSLL-UHFFFAOYSA-N tributyl(ethyl)phosphanium Chemical class CCCC[P+](CC)(CCCC)CCCC HOMONHWYLOPSLL-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical class CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- 208000016261 weight loss Diseases 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明はカチオン染料に染色可能な改質ポリエステル繊
維に関するものであり、更に詳しくは、カチオン染料に
染色可能であると共に充分な強力を有し且つ白変に優れ
た改質ポリエステルにＩ維に関するものである。[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a modified polyester fiber that is dyeable with cationic dyes, and more specifically, a modified polyester fiber that is dyeable with cationic dyes and has sufficient strength. It also relates to modified polyester I fibers that are excellent in white discoloration.
〈従来技術〉
ポリエステルは多くの優れた特性を有するがゆえに繊維
やフィルムとして広く用いられているが、染色性が低く
、特に分散染料以外の染料には染色困難である。この染
色性を改良するために種々の提案がなされている。その
一つとして従来からスルホン酸金属塩基を含有するイソ
フタル酸成分、例えば５−ナトリウムスルホイソフタル
酸成分をポリエステルに共重合することによりカチオン
染料で染色可能にする方法が知られている（特公昭３４
〜１０４９７号公報）。<Prior Art> Polyester has many excellent properties and is therefore widely used as fibers and films, but it has low dyeability and is particularly difficult to dye with dyes other than disperse dyes. Various proposals have been made to improve this dyeability. One of the methods is to copolymerize polyester with an isophthalic acid component containing a sulfonic acid metal base, for example, a 5-sodium sulfoisophthalic acid component, thereby making it dyeable with cationic dyes (Japanese Patent Publication No. 1989-1983).
- No. 10497).
しかしながら、この方法では、スルホン酸金属塩基を含
有するイソフタル酸成分の増粘作用のため、重合反応物
の溶融粘度が著しく増大し、重合度を充分にあげること
が困難になると同時に、紡糸をも困難にならしめていた
。従って、かかる田のスルホン酸金属塩基を含有するイ
ソフタル酸成分を共重合した改質ポリエステルの溶融粘
度を、重合が容易で且つ溶融紡糸ができる範囲にまで低
下させるために、改質ポリエステルの重合度を低くして
おく必要がある。その結果前られる糸の強度が低下し、
これが得られるカチオン染料可染型ポリエステル繊維の
用途を著しく制限している。However, in this method, due to the thickening effect of the isophthalic acid component containing the sulfonic acid metal base, the melt viscosity of the polymerization reaction product increases significantly, making it difficult to sufficiently increase the degree of polymerization, and at the same time making it difficult to spin. It was making things difficult. Therefore, in order to reduce the melt viscosity of a modified polyester copolymerized with an isophthalic acid component containing such a sulfonic acid metal base to a range where polymerization is easy and melt spinning is possible, the polymerization degree of the modified polyester is need to be kept low. As a result, the strength of the thread being threaded decreases,
This significantly limits the uses of the resulting cationic dye-dyeable polyester fibers.
一方、カチオン染料可染化剤としてスルホン酸ホスホニ
ウムｍＷを有するイソフタル酸成分を用いる方法が知ら
れている（持分Ｔｌａ４７−２２３３４号公報、米国特
許第３７３２１８３号明細書）。この方法によれば重合
反応中での増粘作用が小さいので、改質ポリエステルの
重合度を高くしても、溶融粘度が通常の溶融紡糸ができ
る範囲におさえるられる。このため高強度のカチオン染
料可染型ポリエステル繊維が容易に得られる。On the other hand, a method is known in which an isophthalic acid component having phosphonium sulfonate mW is used as a cationic dye dyeing agent (Kihan Tla47-22334, US Pat. No. 3,732,183). According to this method, the thickening effect during the polymerization reaction is small, so even if the degree of polymerization of the modified polyester is increased, the melt viscosity can be kept within the range that allows normal melt spinning. Therefore, high-strength cationic dye-dyeable polyester fibers can be easily obtained.
しかしながら、この方法においては使用するスルホン酸
ホスホニウム塩基を有するイソフタル酸成分の耐熱性が
、スルホン酸金属塩基を含有するイソフタル酸成分に比
べて劣るために、改質ポリエステルの重合反応過程や溶
融紡糸過程等の高熱条件下で自ら分解したり、ポリマー
の分解を促進して生成ポリエステルや成形品を黄褐色に
着色させ、且つ改質ポリエステルの重合度を著しく低下
させるという重大な欠点があり、更にこの着色が染色し
た際に色調を悪化さぼることになる。このため、この方
法が工業的に採用されることは従来皆無であった。However, in this method, the heat resistance of the isophthalic acid component containing a phosphonium sulfonate base used is inferior to that of the isophthalic acid component containing a metal sulfonate base, so it is necessary to It has the serious disadvantage that it decomposes by itself under high heat conditions such as, accelerates the decomposition of the polymer, colors the produced polyester and molded products yellowish brown, and significantly lowers the degree of polymerization of the modified polyester. When dyed, the color tone deteriorates and becomes dull. For this reason, this method has never been industrially adopted.
〈発明が解決しようとする問題点〉
本発明者は、前記したスルホン酸ホスホニウム塩を共重
合した改質ポリエステルの長所に鑑み、上記欠点を克服
すべく鋭意検討し、その方策としてポリマー中に特定量
の第４級オニウム塩を添加することにより耐熱性が大幅
に向上し、高白度で高強力なカチオン可染ポリエステル
ｔｈｅｆｔが得られることを見出した。本発明はかかる
知見に基いて更に検討した結果完成したものである。<Problems to be Solved by the Invention> In view of the advantages of the modified polyester copolymerized with the aforementioned sulfonic acid phosphonium salt, the present inventors have made extensive studies to overcome the above-mentioned drawbacks, and as a measure to do so, the present inventors have investigated It has been found that by adding a certain amount of quaternary onium salt, heat resistance is greatly improved, and a cationically dyeable polyester theft with high whiteness and high strength can be obtained. The present invention was completed as a result of further studies based on this knowledge.
〈発明の構成〉
即ち、本発明は下記一般式（Ｉ＞
Ｘ＋ −Ａ−Ｘ２ ”−−（Ｉ ）（Ｓ
Ｏ３’Ｐ０ＲＩ Ｒ２Ｒ３Ｒ４）
（式中、△は芳香族基又は脂肪族基、ｘｌはエステル形
成性官能基、×２は×１と同−若しくは異なるエステル
形成性官能基又は水素原子、Ｒ＋。<Structure of the invention> That is, the present invention is based on the following general formula (I>
O3'P0RI R2R3R4) (In the formula, Δ is an aromatic group or an aliphatic group, xl is an ester-forming functional group, x2 is the same or different ester-forming functional group or hydrogen atom as x1, and R+.
Ｒｚ 、Ｒ３及びＲ４はアルキル基及びアリール基より
選ばれた同−又は異なる基、ｎは正の整数を示す。）で
表わされるスルホン酸ホスホニウム塩を０１〜１０モル
％共重合した極限粘度０．５以上の改質ポリエステルか
らなり、シルクファクターが２５以上で且つ酢酸０．４
ａ／μを含有する蒸溜水中１３０℃で６０分間湿熱処
理した際のポリエステル主鎖切断数が１４Ｑｘ １０
／ １０’ ｇ繊維以下である改質ポリエステル繊維
に係るものである。Rz, R3 and R4 are the same or different groups selected from alkyl groups and aryl groups, and n represents a positive integer. ) is made of a modified polyester having an intrinsic viscosity of 0.5 or more and having a silk factor of 25 or more and acetic acid of 0.4.
The number of polyester main chain breaks is 14Qx 10 when subjected to moist heat treatment at 130°C for 60 minutes in distilled water containing a/μ.
/10'g fiber or less.
本発明でいうポリエステルは、テレフタル酸を主たる酸
成分とし、少なくとも１種のグリコール、好ましくはエ
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種のアルキ
レングリコールをグリコール成分とするポリエステルを
主たる対象とする。The polyester used in the present invention is a polyester whose main acid component is terephthalic acid and whose glycol component is at least one type of glycol, preferably at least one alkylene glycol selected from ethylene glycol, trimethylene glycol, and tetramethylene glycol. set to target.
また、テレフタル酸成分の一部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であってもよく、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。It may also be a polyester in which part of the terephthalic acid component is replaced with another difunctional carboxylic acid component, and/
Alternatively, it may be a polyester in which part of the glycol component is replaced with the above-mentioned glycol or other diol component other than the main component.
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あげることができる。更に本発
明の効果を実質的に秦する範囲で５−ナトリウムスルホ
イソフタル酸等のスルホン酸金属塩基を有するイソフタ
ル酸を共重合成分として用いてもよい。Examples of difunctional carboxylic acids other than terephthalic acid used here include isophthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenoxyethane dicarboxylic acid, β-hydroxyethoxybenzoic acid, p-oxybenzoic acid, and adipic acid. Examples include aromatic, aliphatic, and alicyclic difunctional carboxylic acids such as sebacic acid and 1,4-cyclohexanedicarboxylic acid. Furthermore, isophthalic acid having a sulfonic acid metal base such as 5-sodium sulfoisophthalic acid may be used as a copolymerization component within a range that substantially reduces the effects of the present invention.
また、上記グリコール以外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Ａ１ビスフエノール
Ｓの如き脂肪族、脂環族、芳香族のジオール化合物及び
ポリオキシアルキレングリコール等をあげることができ
る。In addition, as diol compounds other than the above glycols,
Examples include aliphatic, alicyclic and aromatic diol compounds such as cyclohexane-1,4-dimethanol, neopentyl glycol, bisphenol A1 and bisphenol S, and polyoxyalkylene glycols.
更に、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、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を使用することができる。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。Such polyesters can be synthesized by any method.
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上加熱
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。For example, in the case of polyethylene terephthalate, usually terephthalic acid and ethylene glycol are directly esterified, a lower alkyl ester of terephthalic acid such as dimethyl terephthalate is transesterified with ethylene glycol, or terephthalic acid and ethylene oxide are transesterified. The first stage reaction is to react with the glycol ester of terephthalic acid and/or its low polymer, and the first stage reaction product is heated under reduced pressure to polymerize until the desired degree of polymerization is reached. It is produced by a second step of condensation reaction.
本発明の方法において共重合成分として使用するスルホ
ン酸ホスホニウム塩は下記一般式（Ｉ）Ｘ＋−Ａ−Ｘ２
・・・・・・・・・（Ｉ）（ＳＯ３’
ＰｅＲＩ Ｒ２Ｒ３Ｒ４）で表わされる。式中、Ａは
芳香族基又は脂肪族基を示し、なかでも芳香族基が好ま
しい。×１はエステル形成性官能基を示し、具体例とし
てＯＯ○
＋ ＣＨ２＋ ａ ＯＨ１
−〇イＣＨ２セー廿０（ＣＨ２セ−６−ｔ、ＯＨ１−Ｃ
ｆＯ＋ＣＨ２＋−Ｔ−＋、ＯＨ
（但し、Ｒ′は低級アルキル基又はフェニル基、ａ及び
ｄは１以上の整数、ｂは２以上の整数である）等をあげ
ることができる。×２は×１と同−若しくは異なるエス
テル形成性官能基又は水素原子を示し、なかでもエステ
ル形成性官能基であることが好ましい。Ｒ＋ 、Ｒ２、
Ｒ３及びＲ４はアルキル基及びアリール基よりなる群れ
から選ばれた同−又は異なる基を示す。ｎは正の整数で
ある。The sulfonic acid phosphonium salt used as a copolymerization component in the method of the present invention has the following general formula (I)
・・・・・・・・・(I)(SO3'
PeRI R2R3R4). In the formula, A represents an aromatic group or an aliphatic group, and among them, an aromatic group is preferable. ×1 indicates an ester-forming functional group, and specific examples include OO○ + CH2+ a OH1 -〇iiCH2Se廿0(CH2Se-6-t, OH1-C
Examples include fO+CH2+-T-+, OH (wherein R' is a lower alkyl group or phenyl group, a and d are an integer of 1 or more, and b is an integer of 2 or more). x2 represents the same or different ester-forming functional group or hydrogen atom as x1, and is preferably an ester-forming functional group. R+, R2,
R3 and R4 represent the same or different groups selected from the group consisting of alkyl groups and aryl groups. n is a positive integer.
かかるスルホン酸ホスホニウム塩は、一般に対応するス
ルホン酸とホスフィン類との反応、又は対応するスルホ
ン酸金属塩とホスホニウムハライド類との反応により容
易に合成できる。Such sulfonic acid phosphonium salts can generally be easily synthesized by reacting the corresponding sulfonic acid with phosphines or by reacting the corresponding sulfonic acid metal salt with phosphonium halides.
上記スルホン酸ホスホニウム塩の好ましい具体例として
は、３，５−ジカルボキシベンゼンスルホン酸テトラブ
チルホスホニウム塩、３，５−ジカルボキシベンゼンス
ルホン酸エチルトリブチルホスホニウム塩、３，５−ジ
カルボキシベンゼンスルホン酸ベンジルトリブチルホス
ホニウム塩、３，５−ジカルボキシベンゼンスルホン酸
フェニルトリブチルホスホニウム塩、３．５−ジカルボ
キシベンゼンスルホン酸テトラフェニルホスホニウム塩
、３．５−ジカルボキシベンゼンスルホン酸ブチルトリ
フェニルホスホニウム塩、３，５−ジカルボキシベンゼ
ンスルホン酸ベンジルトリフェニルホスホニウム塩、３
，５−ジカルボメトキシベンゼンスルホン酸テトラブチ
ルホスホニウム塩、３．５−ジカルボメトキシベンゼン
スルホン酸エチルトリブチルホスホニウム塩、３゜５−
ジカルボメトキシベンゼンスルホン酸ベンジルトリブチ
ルホスホニウム塩、３，５−ジカルボメトキシベンゼン
スルホン酸フェニルトリブチルホスホニウム塩、３，５
−ジカルボメトキシベンゼンスルホン酸テトラフェニル
ホスホニウム塩、３，５−ジカルボメトキシベンゼンス
ルホン酸エチルトリフェニルホスホニウム塩、３．５−
ジカルボメトキシベンゼンスルホン酸ブチルトリフェニ
ルホスホニウム塩、３．５−ジカルボメトキシベンゼン
スルホン酸ベンジルトリフェニルホスホニウム塩、３−
カルボキシベンゼンスルホン酸テトラブチルホスホニウ
ム塩、３−カルボキシベンゼンスルホン酸テトラフェニ
ルホスホニウム塩、３−カルボメトキシベンゼンスルホ
ン酸テトラブチルホスボニウム塩、３−カルボメトキシ
ベンゼンスルホン酸テトラフェニルポスホニウム塩、３
，５−ジ（β−ヒドロキシエトキシカルボニル）ベンゼ
ンスルホン酸テトラブチルホスホニウム塩、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
ン酸テトラフェニルポスホニウム塩、３−（β−ヒドロ
キシエトキシカルボニル）ベンゼンスルホン酸テトラブ
チルホスホニウム塩、３−（β−ヒドロキシエトキシカ
ルボニル）ベンゼンスルホン酸テトラフェニルホスホニ
ウム塩、４−ヒドロキシエトキベンゼンスルホン酸テト
ラブチルホスホニウム塩、２．６−ジカルポキシナフタ
レンー４−スルホン酸テトラブチルホスホニウム塩、α
−テトラブチルホスホニウムスルホコハク酸等をあげる
ことができる。上記スルホン酸ホスホニウム塩は１種の
みを単独で用いても、２種以上併用してもよい。Preferred specific examples of the sulfonic acid phosphonium salts include 3,5-dicarboxybenzenesulfonic acid tetrabutylphosphonium salt, 3,5-dicarboxybenzenesulfonic acid ethyltributylphosphonium salt, and benzyl 3,5-dicarboxybenzenesulfonate. Tributylphosphonium salt, 3,5-dicarboxybenzenesulfonic acid phenyltributylphosphonium salt, 3,5-dicarboxybenzenesulfonic acid tetraphenylphosphonium salt, 3,5-dicarboxybenzenesulfonic acid butyltriphenylphosphonium salt, 3,5 -dicarboxybenzenesulfonic acid benzyltriphenylphosphonium salt, 3
, 5-dicarbomethoxybenzenesulfonic acid tetrabutylphosphonium salt, 3.5-dicarbomethoxybenzenesulfonic acid ethyltributylphosphonium salt, 3゜5-
Dicarbomethoxybenzenesulfonic acid benzyltributylphosphonium salt, 3,5-dicarbomethoxybenzenesulfonic acid phenyltributylphosphonium salt, 3,5
-Dicarbomethoxybenzenesulfonic acid tetraphenylphosphonium salt, 3,5-dicarbomethoxybenzenesulfonic acid ethyltriphenylphosphonium salt, 3.5-
Dicarbomethoxybenzenesulfonic acid butyltriphenylphosphonium salt, 3.5-Dicarbomethoxybenzenesulfonic acid benzyltriphenylphosphonium salt, 3-
Carboxybenzenesulfonic acid tetrabutylphosphonium salt, 3-carboxybenzenesulfonic acid tetraphenylphosphonium salt, 3-carbomethoxybenzenesulfonic acid tetrabutylphosphonium salt, 3-carbomethoxybenzenesulfonic acid tetraphenylphosphonium salt, 3
, 5-di(β-hydroxyethoxycarbonyl)benzenesulfonic acid tetrabutylphosphonium salt, 3,5-di(β-hydroxyethoxycarbonyl)benzenesulfonic acid tetraphenylphosphonium salt, 3-(β-hydroxyethoxycarbonyl) Benzenesulfonic acid tetrabutylphosphonium salt, 3-(β-hydroxyethoxycarbonyl)benzenesulfonic acid tetraphenylphosphonium salt, 4-hydroxyethoxybenzenesulfonic acid tetrabutylphosphonium salt, 2,6-dicarpoxynaphthalene-4-sulfonic acid tetra Butylphosphonium salt, alpha
-Tetrabutylphosphonium sulfosuccinic acid and the like can be mentioned. The above sulfonic acid phosphonium salts may be used alone or in combination of two or more.
上記スルホン酸ホスホニウム塩をポリエステルに共重合
するには、前述したポリエステルの合成が完了する以前
の任意の段階で、好ましくは第２段階の反応の初期以前
の任意の段階で添加すればよい。スルホン酸ホスホニウ
ム塩をポリエステルに共重合させる割合いは、ポリエス
テルを構成する二官能性カルボン酸成分（スルホン酸塩
を除く）に対して０１〜１０モル％の範囲であり、０．
５〜５モル％の範囲が好ましい。共重合割合いが０．１
モル％より少ないと、得られる改質ポリエステル繊維の
カチオン染料に対する染色性が不十分になり、１０モル
％より多くなるとカチオン染色性は最早著しい向上を示
さず、かえってポリエステルの物性が低下し、本発明の
目的を達成し難くなる。In order to copolymerize the sulfonic acid phosphonium salt into a polyester, it may be added at any stage before the synthesis of the polyester described above is completed, preferably at any stage before the beginning of the second stage reaction. The proportion of the sulfonic acid phosphonium salt copolymerized with the polyester is in the range of 0.1 to 10 mol% based on the bifunctional carboxylic acid component (excluding the sulfonate) constituting the polyester.
A range of 5 to 5 mol% is preferred. Copolymerization ratio: 0.1
If it is less than 10% by mole, the dyeability of the resulting modified polyester fiber with cationic dyes will be insufficient, and if it is more than 10% by mole, the cationic dyeability will no longer show any significant improvement, and on the contrary, the physical properties of the polyester will deteriorate, and It becomes difficult to achieve the purpose of the invention.
また、上記改質ポリエステルを製造する際に、前記一般
式（Ｉ）で表されるスルホン酸３級ホスホニウム塩と共
に少量の下記一般式（ＩＩ）で表されるスルホンＰＩ３
３級ホスホニウム塩を併用すると、その重合過程におけ
る分解反応が抑制され、（ｑられる改質ポリエステル及
びそれよりなる成形物の色調が極めて良好になるので、
好ましい。In addition, when producing the modified polyester, a small amount of sulfone PI3 represented by the following general formula (II) is added together with a sulfonic acid tertiary phosphonium salt represented by the general formula (I).
When a tertiary phosphonium salt is used in combination, the decomposition reaction during the polymerization process is suppressed, and the color tone of the modified polyester and molded products made from it becomes extremely good.
preferable.
ここで使用するスルホン酸３級ホスホニウム塩は下記一
般式（ＩＩ）
Ｘａ −Ｂ−Ｘａ −・＝−（ＩＩ ）
■
（８０３■ＰｅＨＲｓ Ｒｓ Ｒ７）
で表わされ、式中、Ｂは前記一般式（Ｉ＞におけるＡと
同様に定義され、Ｘａは前記一般式（Ｉ＞における×１
と同様に定義され、×４は前記一般式（Ｉ）における×
２と同様に定義され、Ｒｓ。The sulfonic acid tertiary phosphonium salt used here has the following general formula (II) Xa -B-Xa -・=-(II)
■ (803■PeHRs Rs R7) In the formula, B is defined in the same way as A in the general formula (I>), and Xa is ×1 in the general formula (I>).
and ×4 is defined as × in the general formula (I) above.
2 and Rs.
Ｒ６及びＲ７は前記一般式（Ｉ）におけるＲ＋。R6 and R7 are R+ in the general formula (I).
Ｒ２及びＲ３と同様に定義され、ｎは正の整数である。Defined similarly to R2 and R3, n is a positive integer.
かかるスルホン酸３級ホスホニウム塩は、例えば対応す
るスルホン酸金属塩と３級ホスホニウムハライド類との
反応により容易に合成できる。Such tertiary phosphonium sulfonic acid salts can be easily synthesized, for example, by reacting the corresponding metal sulfonic acid salts with tertiary phosphonium halides.
上記スルホン酸３級ホスホニウム塩の好ましい具体例と
しては、３．５−ジカルボキシベンゼンスルホン酸トリ
ブチルホスホニウム塩、３．５−ジカルボキシベンゼン
スルホン酸トリエチルホスホニウム塩、３．５−ジカル
ボキシベンゼンスルホン酸トリプロピル小スホニウム塩
、３，５−ジカルボキシベンゼンスルホン酸トリフェニ
ルホスホニウム塩、３．５−ジカルボキシベンゼンスル
ホン酸トリベンジルホスホニウム塩、３．５−ジカルボ
キシベンゼンスルホン酸１〜リヘキシルホスホニウム塩
、３，５−ジカルボキシベンゼンスルホン酸トリオクチ
ルホスホニウム塩、３，５−ジカルボキシベンゼンスル
ホンシクロへキシルホスホニウム塩、３．５−ジカルボ
キシベンゼンスルホン酸ブチルジフェニルホスホニウム
塩、３．５−ジカルボキシベンゼンスルホン酸フエニル
ジブチルホスホニウム塩、３．５−ジカルボメトキシベ
ンゼンスルホン酸トリブチルホスホニウム塩、３．５−
ジカルボメトキシベンゼンスルホン酸トリエチルホスホ
ニウム塩、３，５−ジカルボメトキシベンゼンスルホン
酸トリプロピルホスホニウム塩、３．５−ジカルボメト
キシベンゼンスルホン酸トリフェニルホスホニウム塩、
３，５−ジカルボメトキシベンゼンスルホン酸トリベン
ジルホスホニウム塩、３．５−ジカルボメトキシベンゼ
ンスルホン酸トリオクチルホスホニウム塩、３．５−ジ
カルボメトキシベンゼンスルホン酸トリシクロへキシル
ホスホニウム塩、３□５−ジカルボメトキシベンゼンス
ルホン酸ブチルジフェニルホスホニウム塩、３，５−ジ
カルボメトキシベンゼンスルホン酸フエニルジブチルホ
スホニウム塩、ｍ−カルボメトキシベンゼンスルホン酸
トリブチルホスホニウム塩、ｍ−カルボメトキシベンゼ
ンスルホン酸トリフェニルホスホニウム塩、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
ン酸トリブチルホスホニウム塩、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トリフ
ェニルホスホニウム塩、ｍ−（β−ヒドロキシエトキシ
カルボニル）ベンゼンスルホン酸トリブチルホスホニウ
ム塩、ｍ−（β−ヒドロキシエトキシカルボニル）ベン
ゼンスルホン酸トリフェニルホスホニウム塩、叶ヒドロ
キシエトキシベンゼンスルホン酸トリブチルホスホニウ
ム塩、ｐ−ヒドロキシエトキシベンゼンスルホン酸トリ
フェニルホスホニウム塩、２．６−ジカルポキシナフタ
レンー４−スルホン酸トリブチルホスホニウム塩、α−
トリブチルホスホニウムスルホコハク酸等をあげること
ができる。Preferred specific examples of the tertiary phosphonium sulfonic acid salts include tributylphosphonium 3.5-dicarboxybenzenesulfonate, triethylphosphonium 3.5-dicarboxybenzenesulfonate, and tributylphosphonium 3.5-dicarboxybenzenesulfonic acid. Propyl small sulfonium salt, 3,5-dicarboxybenzenesulfonic acid triphenylphosphonium salt, 3,5-dicarboxybenzenesulfonic acid tribenzylphosphonium salt, 3,5-dicarboxybenzenesulfonic acid 1-lyhexylphosphonium salt, 3 , 5-dicarboxybenzenesulfonic acid trioctylphosphonium salt, 3,5-dicarboxybenzenesulfonecyclohexylphosphonium salt, 3,5-dicarboxybenzenesulfonic acid butyldiphenylphosphonium salt, 3,5-dicarboxybenzenesulfonic acid Phenyldibutylphosphonium salt, 3.5-dicarbomethoxybenzenesulfonic acid tributylphosphonium salt, 3.5-
Dicarbomethoxybenzenesulfonic acid triethylphosphonium salt, 3,5-dicarbomethoxybenzenesulfonic acid tripropylphosphonium salt, 3,5-dicarbomethoxybenzenesulfonic acid triphenylphosphonium salt,
3,5-dicarbomethoxybenzenesulfonic acid tribenzylphosphonium salt, 3,5-dicarbomethoxybenzenesulfonic acid trioctylphosphonium salt, 3,5-dicarbomethoxybenzenesulfonic acid tricyclohexylphosphonium salt, 3□5- Dicarbomethoxybenzenesulfonic acid butyldiphenylphosphonium salt, 3,5-dicarbomethoxybenzenesulfonic acid phenyldibutylphosphonium salt, m-carbomethoxybenzenesulfonic acid tributylphosphonium salt, m-carbomethoxybenzenesulfonic acid triphenylphosphonium salt, 3.5-di(β-hydroxyethoxycarbonyl)benzenesulfonic acid tributylphosphonium salt, 3,5-di(β-hydroxyethoxycarbonyl)benzenesulfonic acid triphenylphosphonium salt, m-(β-hydroxyethoxycarbonyl)benzenesulfone acid tributylphosphonium salt, m-(β-hydroxyethoxycarbonyl)benzenesulfonic acid triphenylphosphonium salt, hydroxyethoxybenzenesulfonic acid tributylphosphonium salt, p-hydroxyethoxybenzenesulfonic acid triphenylphosphonium salt, 2,6-dicarpoxy Naphthalene-4-sulfonic acid tributylphosphonium salt, α-
Examples include tributylphosphonium sulfosuccinate.
かかるスルホン酸３級ホスホニウム塩の使用量は、あま
りに少ないと改質ポリエステルが黄褐色に４！７色する
ことを防止する効果が不十分になり、あまりに多くして
も、着色防止効果は飽和し、かえって物性特に耐熱性を
悪化させることがあるので、前記スルホン酸４級ホスホ
ニウム塩に対して０．５〜１０モル％の範囲が適当であ
り、特に１〜４モル％の範囲が好ましい。このスルホン
酸３級ホスホニウム塩の添加時期はスルホンＲ４級ホス
ホニウム塩と同様に、ポリエステルの合成が完了する以
前の任意の段階で添加すればよく、スルホン酸４級ホス
ホニウム塩と同時に添加しても、別々に添加しても良い
。また、前記スルホン酸４級ホスホニウム塩の製造段階
において、スルホン酸３級ホスホニウ塩が副生して、生
成スルホン！！２４級ホスホニウム塩の中に一部残存す
ることがある。If the amount of the tertiary phosphonium sulfonic acid salt used is too small, the effect of preventing the modified polyester from turning yellowish brown will be insufficient; if it is too large, the coloring prevention effect will be saturated. However, since the physical properties, particularly heat resistance, may be deteriorated, the amount is preferably in the range of 0.5 to 10 mol%, and particularly preferably in the range of 1 to 4 mol%, based on the quaternary phosphonium sulfonic acid salt. As with Sulfone R quaternary phosphonium salt, this sulfonic acid tertiary phosphonium salt may be added at any stage before the synthesis of the polyester is completed, or it may be added at the same time as the sulfonic acid quaternary phosphonium salt. They may be added separately. In addition, in the production step of the quaternary phosphonium sulfonic acid salt, tertiary phosphonium sulfonic acid salt is produced as a by-product, resulting in sulfone! ! A portion of it may remain in the 24th class phosphonium salt.
この場合特製条件を制御して残存するスルホン酸３級ホ
スホニウ塩の澁を上記範囲にすれば、別に使用しなくて
もよい。In this case, if the special conditions are controlled so that the amount of the remaining tertiary phosphoniu salt of sulfonic acid is within the above range, there is no need to use it separately.
改質ポリエステルを製造するに当たって、第４級オニウ
ム塩を添加する。第４級オニウム塩としては第４級アン
モニウム塩、第４級ホスホニウム塩等があり、具体的に
は第４級アンモニウム塩としては水酸化テトラメチルア
ンモニウム、塩化テトラメチルアンモニウム、水酸化テ
トラエチルアンモニウム、塩化テトラエチルアンモニウ
ム、臭化テトラエチルアンモニウム、沃化テトラエチル
アンモニウム、水酸化テトラプロピルアンモニウム、塩
化テトラプロピルアンモニウム、水酸化テトライソプロ
ピルアンモニウム、塩化テトライソプロピルアンモニウ
ム、水酸化テトラブチルアンモニウム、塩化テトラブチ
ルアンモニウム、水酸化テトラフェニルアンモニウム、
化テトラフェニルアンモニウム等が例示される。第４級
ホスホニウム塩としてはクロルベンジルホスホニウムク
ロライド、ステアリルエチルジヒドロキシエチルホスホ
ニウムエトサルフェート、テトラブチルホスホニウムア
セテート、テトラブチルホスホニウムドデシルベンゼン
スルホネート、テトラブチルホスホニウムトシレート、
テトラブチルホスホニウムステアレート、テトラブチル
ホスホニウムオレエート、テトラブチルホスホニウムホ
スフェート、テトラブチルホスホニウムホスファイト、
エチルトリフェニルホスホニウムブロマイド、テトラブ
チルホスホニウムブロマイド、テトラフェニルホスホニ
ウムブロマイド、エチルトリフェニルホスホニウムアイ
オダイド、エチルトリフェニルホスホニウムブロマイド
、ベンジルトリフェニルホスホニウムクロライド、トリ
ブチルアリルホスホニウムブロマイド、エチレンビスト
リス（２−シアンエチル）ホスホニウムブロマイド、ト
リス−２−シアンエチルアリルホスホニウムクロライド
、テトラキス（ヒドロキシメチル）ホスホニウムサルフ
ェート、テトラキス（ヒドロキシメチル）ホスホニウム
クロライド等が例示される。In producing the modified polyester, a quaternary onium salt is added. Quaternary onium salts include quaternary ammonium salts, quaternary phosphonium salts, etc. Specifically, quaternary ammonium salts include tetramethylammonium hydroxide, tetramethylammonium chloride, tetraethylammonium hydroxide, and chloride. Tetraethylammonium, Tetraethylammonium bromide, Tetraethylammonium iodide, Tetrapropylammonium hydroxide, Tetrapropylammonium chloride, Tetraisopropylammonium hydroxide, Tetraisopropylammonium chloride, Tetrabutylammonium hydroxide, Tetrabutylammonium chloride, Tetraphenyl hydroxide ammonium,
Examples include tetraphenylammonium chloride. Examples of quaternary phosphonium salts include chlorobenzylphosphonium chloride, stearylethyldihydroxyethylphosphonium ethosulfate, tetrabutylphosphonium acetate, tetrabutylphosphonium dodecylbenzenesulfonate, tetrabutylphosphonium tosylate,
Tetrabutylphosphonium stearate, tetrabutylphosphonium oleate, tetrabutylphosphonium phosphate, tetrabutylphosphonium phosphite,
Ethyltriphenylphosphonium bromide, tetrabutylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tributylarylphosphonium bromide, ethylene bistris(2-cyanoethyl)phosphonium Examples include bromide, tris-2-cyanoethylallylphosphonium chloride, tetrakis(hydroxymethyl)phosphonium sulfate, and tetrakis(hydroxymethyl)phosphonium chloride.
上記第４級オニウム塩の使用」はあまりに少ないと耐熱
性を改善する効果が不十分になり、逆にあまりに多くな
ると、かえって耐熱性が悪化するようになり、その上生
成ポリエステルや成形物が黄褐色に着色する傾向が顕著
になる。このため第４級オニウム塩の使用量は、前記ス
ルホン酸ホスホニウム塩に対して０．１〜２０モル％の
範囲が好ましく、なかでも１〜１０モル％の範囲が特に
好ましい。If the use of the above quaternary onium salt is too small, the effect of improving heat resistance will be insufficient, and if it is too large, the heat resistance will worsen, and the resulting polyester and molded products will turn yellow. There is a noticeable tendency to turn brown. Therefore, the amount of the quaternary onium salt to be used is preferably in the range of 0.1 to 20 mol%, particularly preferably in the range of 1 to 10 mol%, based on the sulfonic acid phosphonium salt.
かかる第４級オニウム塩の添加時期は前記ポリエステル
の合成が完了するまでの任意の段階でよく、例えばポリ
エステルの原料中に添加しても、第１段階の反応中に添
加しても、第１段階の反応終了後から第２段階の反応開
始までの間に添加しても、第２段階の反応中に添加して
もよい。The quaternary onium salt may be added at any stage until the synthesis of the polyester is completed; for example, it may be added into the polyester raw material, during the first stage reaction, or during the first stage reaction. It may be added between the end of the first stage reaction and the start of the second stage reaction, or it may be added during the second stage reaction.
第４級オニウム塩と前記スルホン酸ホスホニウム塩との
添加順序は任意でよく、両者を予め混合した後に添加す
ることもできる。また、スルホン酸ホスホニウム塩の製
造に際して、第４級ホスホニウムハライド等の第４級ホ
スホニウム塩とスルホン酸金属塩との反応による合成方
法を採用することがあり、その場合原料の第４級ホスホ
ニウム塩が反応生成物であるスルホン酸ホスホニウム塩
の中に残存することがある。かかる場合には別に第４級
ホスホニウム塩を使用することを要さず、この残存第４
級ホスホニウム塩を利用することもできる。The quaternary onium salt and the sulfonic acid phosphonium salt may be added in any order, and they may be added after being mixed in advance. In addition, when producing a sulfonic acid phosphonium salt, a synthesis method may be adopted in which a quaternary phosphonium salt such as a quaternary phosphonium halide is reacted with a sulfonic acid metal salt, in which case the quaternary phosphonium salt as a raw material is It may remain in the reaction product, sulfonic acid phosphonium salt. In such a case, it is not necessary to use a quaternary phosphonium salt separately, and the remaining quaternary phosphonium salt
Grade phosphonium salts can also be utilized.
こうすることにより高強力に必要である極限粘度が０．
５３以上、好ましくは０．６以上、更に好ましくは０．
６４以上で、黄色の少ない白変に優れた改質ポリエステ
ルが得られる。By doing this, the intrinsic viscosity required for high strength can be reduced to 0.
53 or more, preferably 0.6 or more, more preferably 0.
When it is 64 or more, a modified polyester with little yellow color and excellent white discoloration can be obtained.
こうして得られた改質ポリエステルを溶融紡糸する。こ
の溶融紡糸には通常の紡糸方法が採用される。一般に溶
融紡糸は、ポリマーをその融点より３０〜５０℃高い温
度で溶融し、紡糸口金より吐出する。上記改質ポリエス
テルにこの紡糸方法を適用すると、紡糸時に分解して着
色したり、重合度が低下したりすることがある。このよ
うな時には、２８０℃を下回る温度で紡糸するのが好ま
しい。しかしながら、かかる紡糸温度は改質ポリエステ
ルの融点に接近するため、得られる繊維の物性が低下す
るようになる。そのため、かかる低温で紡糸するには下
記の方法を採用するのが好ましい。The modified polyester thus obtained is melt-spun. A normal spinning method is used for this melt spinning. Generally, in melt spinning, a polymer is melted at a temperature 30 to 50° C. higher than its melting point and discharged from a spinneret. If this spinning method is applied to the above-mentioned modified polyester, it may decompose and become colored during spinning, or the degree of polymerization may decrease. In such cases, it is preferable to spin at a temperature below 280°C. However, since such a spinning temperature approaches the melting point of the modified polyester, the physical properties of the resulting fibers deteriorate. Therefore, it is preferable to employ the following method for spinning at such low temperatures.
即ち、改質ポリエステルを（融点＋３０）°Ｃ以上の温
度で完全に溶融した後、紡糸液導入孔とそれに連なる紡
糸液吐出孔からなる紡糸孔を１個以上有する紡糸口金板
において、下部を針状になした紡糸液案内棒が各紡糸孔
に嵌入されており、この案内棒はその軸が少なくとも紡
糸液導入孔下部から吐出孔を経て、先端に至る範囲に亘
って導入孔及び吐出孔の軸と一致しており、しかもこの
案内棒が吐出孔を経て吐出面より下方に突出せしめられ
ている紡糸口金を用いて、紡糸口金温度Ｔ （℃）を（
融点＋５）℃以上にする方法である（特開昭６０−２５
９６１９号公報）。That is, after the modified polyester is completely melted at a temperature of (melting point + 30°C) or higher, the lower part of the spinneret plate has one or more spinning holes consisting of a spinning solution introduction hole and a spinning solution discharge hole connected to the spinning solution introduction hole. A shaped spinning solution guide rod is fitted into each spinning hole, and the shaft of this guide rod extends from the bottom of the spinning solution introduction hole through the discharge hole to the tip of the introduction hole and the discharge hole. Using a spinneret that is aligned with the shaft and whose guide rod protrudes below the discharge surface through the discharge hole, the spinneret temperature T (°C) is determined by (
This is a method of increasing the melting point to +5)°C or higher (Japanese Patent Laid-Open No. 60-25
Publication No. 9619).
この溶融紡糸方法において第一に重要なことは、紡糸口
金が通常の紡糸口金と異なり、針状をなす紡糸液案内棒
を吐出孔を通過して吐出面下流まで突出するように配置
した紡糸口金であることが必要である。以下図を用いて
紡糸口金の特徴を説明する。The first important thing in this melt spinning method is that the spinneret is different from a normal spinneret in that the spinneret is arranged so that a needle-shaped spinning solution guide rod passes through the discharge hole and protrudes downstream from the discharge surface. It is necessary that The characteristics of the spinneret will be explained below using the drawings.
第１図は紡糸口金の要部！断面図、第２図は紡糸口金に
嵌入する紡糸液の案内棒の一例を示す斜視図、第３図は
第２図に示す紡糸液案内棒を嵌入した紡糸口金の要部縦
断面図（イ）及び要部横断面図（ロ）である。Figure 1 shows the main parts of the spinneret! 2 is a perspective view showing an example of a spinning solution guide rod fitted into the spinneret, and FIG. 3 is a longitudinal sectional view of the main part of the spinneret (I) in which the spinning solution guide rod shown in FIG. 2 is fitted. ) and a cross-sectional view of the main part (b).
紡糸口金は、第１図に示す如く上部を大径になし下部を
漸次小径となした紡糸液導入孔１とそれに連なる紡糸液
吐出孔２とからなる紡糸孔３を１個以上有する紡糸口金
板４において、第２図に示す如く上部の円周方向に複数
（本例では４個）の羽根５を等間隔に設け、下部６を−
様な針状に（本例では円柱状になした）紡糸液案内棒７
が第３図に示す如く各紡糸孔３に嵌入され、案内棒７の
羽根５を含む上部が紡糸液導入孔１の大径の上部に固着
されている。更に第３図に示す如く案内棒７の軸は少な
くとも紡糸液導入孔１の下部８から吐出孔２を経て、先
端６に至る範囲に亘って導入孔１及び吐出孔２を経て吐
出面９より下方に突出せしめられている。As shown in FIG. 1, the spinneret is a spinneret plate having one or more spinning holes 3 consisting of a spinning solution introduction hole 1 with a large diameter in the upper part and a gradually smaller diameter in the lower part and a spinning solution discharge hole 2 connected to the spinning solution introduction hole 1, as shown in FIG. 4, a plurality of (four in this example) blades 5 are provided at equal intervals in the circumferential direction of the upper part, and the lower part 6 is
The spinning solution guide rod 7 has a needle-like shape (in this example, it has a cylindrical shape).
are fitted into each spinning hole 3 as shown in FIG. Furthermore, as shown in FIG. 3, the axis of the guide rod 7 extends from the discharge surface 9 through the introduction hole 1 and the discharge hole 2 over a range from at least the lower part 8 of the spinning solution introduction hole 1 through the discharge hole 2 to the tip 6. It is made to protrude downward.
かかる構造の紡糸口金によれば紡糸液は各紡糸孔３に嵌
入固着された紡糸液案内棒７の上部羽根５と導入孔１の
大径部の内壁１０とで囲まれ、且つ等間隔に形成される
複数の通路１１を通って、次に案内棒７の先端６の上部
１２と導入孔１の下部８及び吐出孔２とによって形成さ
れる環状通路１３に入り、この環状通路１３の先端より
紡糸液案内棒７の柱状部１２の外周に沿って流れ、先端
６より引出されてＩＩＩ状に紡糸される。According to the spinneret having such a structure, the spinning solution is surrounded by the upper blade 5 of the spinning solution guide rod 7 that is fitted and fixed in each spinning hole 3 and the inner wall 10 of the large diameter part of the introduction hole 1, and is formed at regular intervals. It passes through a plurality of passages 11 , and then enters an annular passage 13 formed by the upper part 12 of the tip 6 of the guide rod 7 , the lower part 8 of the introduction hole 1 and the discharge hole 2 , and from the tip of this annular passage 13 . The spinning solution flows along the outer periphery of the columnar part 12 of the spinning solution guide rod 7, is pulled out from the tip 6, and is spun into a III-shape.
紡糸口金において、第１図に示す紡糸孔３の形状は、通
常の口金のそれと相似しているが、寸法的には通常口金
の寸法より一般に大きい値（０８〜５ｍｍ程度）が採用
される。In the spinneret, the shape of the spinning hole 3 shown in FIG. 1 is similar to that of a normal spinneret, but the dimensions are generally larger (about 0.8 to 5 mm) than the dimensions of the normal spinneret.
第１図に示す紡糸液導入孔１の大径部の径は、第２図に
示す紡糸液案内棒７が嵌入可能な寸法が必要であり、案
内棒７の工作上の難易度から約３ｍｍ以上が好ましく、
紡糸液吐出孔２の径は、案内棒７の柱状部１２の径より
約０．１ｎｕｎＪｙ、上大きい値が好ましいが、紡糸液
の粘度、吐出糸の繊度等によって吐出孔２の径と柱状部
の径の組合せは任意に調整可能である。The diameter of the large diameter part of the spinning solution introduction hole 1 shown in FIG. 1 needs to be large enough to fit the spinning solution guide rod 7 shown in FIG. The above is preferable,
The diameter of the spinning solution discharge hole 2 is preferably approximately 0.1 nunJy larger than the diameter of the columnar portion 12 of the guide rod 7, but the diameter of the discharge hole 2 and the columnar portion may vary depending on the viscosity of the spinning solution, the fineness of the discharged yarn, etc. The combination of diameters can be arbitrarily adjusted.
次に第２図に示す紡糸液案内棒７の上部形状は、４枚羽
根型で示しであるが、この部分の動きは案内棒７を紡糸
孔３にしっかりと固着させること、及び紡糸液を吐出孔
２へ導く通路を形成するか、あるいは保持していること
にあり、上部形状は何等限定されるものではなく、案内
棒７の上部の周方向に複数の小円形の紡糸流入孔を等間
隔に設けた形状でも差支えない、。Next, the shape of the upper part of the spinning solution guide rod 7 shown in FIG. The purpose is to form or hold a passage leading to the discharge hole 2, and the shape of the upper part is not limited in any way. There is no problem with the shape provided at intervals.
また、第２図に示す紡糸液案内棒７の下部柱状部１２か
ら先＠ｉ６に至る形状は、本例では円柱状に示しである
が、特に特定されるものではなく、先端が尖鋭な錐状を
なした円錐状でもよく、楕円柱（錐）、三角柱（錐）、
五角柱（錐）、等の多角柱（錐）、その他各種の異形断
面柱（錐）であっても差支えない。The shape from the lower columnar part 12 to the tip @i6 of the spinning solution guide rod 7 shown in FIG. It may be a conical shape, such as an elliptical cylinder (cone), a triangular cylinder (cone),
It may be a polygonal prism (pyramid) such as a pentagonal prism (pyramid), or any other type of irregular cross-section pillar (pyramid).
更に円管、多角管、その他各種の異形断面の中空管の形
状をなした案内棒を用いることによって中空糸条の紡出
も可能であり、さらには紡糸孔３の紡糸液入口から吐出
孔２の先端に至る範囲をほぼ二分割する如く配置される
形状の案内棒７を用いれば、サイド・パイ・サイド型複
合糸が得られるし、通常のシース・コア型複合紡糸口金
に紡糸液案内棒を適用することも可能である。Furthermore, it is possible to spin hollow fibers by using guide rods in the shape of circular tubes, polygonal tubes, and other hollow tubes with various irregular cross sections. By using the guide rod 7, which is arranged so as to roughly divide the area up to the tip of 2, a side-pie-side type composite yarn can be obtained, and the spinning solution can be guided to a normal sheath-core type composite spinneret. It is also possible to apply rods.
第３図に示す紡糸口金で紡糸孔３と紡糸液案内棒７との
組合せ構造において大切なことは、まず案内棒７の軸が
少なくとも紡糸液導入孔１の下部８から吐出孔２を経て
、先端６に至る範囲に亘って、導入孔１及び吐出孔２の
軸と実質的に一致していることである。案内棒の軸が極
端に偏心していると紡糸液が第３図に示す通路１３を通
過する過程で流速に斑が生じ、吐出面９を出た直後にベ
ンディング等を起こし好ましくない。次に大切なことは
、第３図に示す如く案内棒７の柱状部１２の下部から先
端６が吐出面９より突出していることである。この突出
の程度は、吐出孔２の径、紡糸液の粘度、吐出Φ、紡糸
口金温度等に依存するが、通常１〜３０ｍｍ、好ましく
は２〜２０ｍｍ程度である。What is important in the combined structure of the spinning hole 3 and the spinning solution guide rod 7 in the spinneret shown in FIG. The range extending to the tip 6 is substantially aligned with the axes of the introduction hole 1 and the discharge hole 2. If the axis of the guide rod is extremely eccentric, unevenness will occur in the flow velocity while the spinning solution passes through the passage 13 shown in FIG. 3, and bending will occur immediately after exiting the discharge surface 9, which is undesirable. The next important thing is that the lower end 6 of the columnar part 12 of the guide rod 7 protrudes from the discharge surface 9, as shown in FIG. The degree of this protrusion depends on the diameter of the discharge hole 2, the viscosity of the spinning solution, the discharge Φ, the spinneret temperature, etc., but is usually about 1 to 30 mm, preferably about 2 to 20 mm.
突出の程度が小さい場合、通常口金と同様に吐出面９直
後の紡糸液の応力変形が急激になり、紡糸口金温度を通
常より下げていくと、さほど下げていない条件下でも弱
糸や断糸発生が起こり安定紡糸が難しく、低温紡糸の効
果が充分に得られなくなる。一方、突出の程度が極端に
大であると、紡糸液が案内棒７の柱状部１２から先端６
に沿って流下する過程で紡糸液の冷却が進み、極端な場
合紡糸液が固化してしまい曳糸できなくなることがある
ので好ましくない。If the degree of protrusion is small, the stress deformation of the spinning solution immediately after the discharge surface 9 will be rapid, similar to a normal spinneret, and if the spinneret temperature is lowered than normal, weak yarn or yarn breakage will occur even under conditions where the temperature is not lowered that much. This occurs, making stable spinning difficult and making it impossible to obtain the full effect of low-temperature spinning. On the other hand, if the degree of protrusion is extremely large, the spinning solution will flow from the columnar part 12 of the guide rod 7 to the tip 6.
The cooling of the spinning solution progresses in the process of flowing down along the , and in extreme cases, the spinning solution may solidify and become unable to be threaded, which is not preferable.
この低温紡糸法においても、紡糸口金温度はおのずと限
界（下限）があり、案内棒を流下する過程でポリマー流
れが固化してしまう口金温度では、伸張応力による弾性
変形から脆性破壊に至り、紡糸不能になるので口金温度
を改質ポリエステルの融点より５℃以上高い温度にすべ
きである。Even in this low-temperature spinning method, there is a natural limit (lower limit) to the spinneret temperature, and at the spinneret temperature at which the polymer flow solidifies during the process of flowing down the guide rod, elastic deformation due to extensional stress leads to brittle fracture, making spinning impossible. Therefore, the cap temperature should be set at least 5°C higher than the melting point of the modified polyester.
上述したように、第４級オニウム塩を添加することによ
って、更に好ましくは第４級オニウム塩を添加したうえ
上記の低温紡糸法を採用することによって改質ポリエス
テルの重合度の低下や黄変を大幅に減少させることがで
きたため、その極限粘度が０．５以上、好ましくは０．
６以上、特に好ましくは０．６３以上のカチオン可染改
質ポリエステル繊維の提供をはじめて可能にし、またこ
の繊維はシルクファクター（繊維の強度×ｆ伸度）が２
５以上、好ましくは２８以上の高強度を示すことができ
、且つ酢Ｍ １．４ａ ／ρを含有する蒸溜水中で１３
０℃で６０分間湿熱処理した時に生じるポリエステル主
鎖の切断数が
１４０Ｘ１０ ／１０６ａ ４１維
以下という優れた耐熱性を示す値が得られ、高白度を呈
し、染色した際に優れた鮮明性を示す。As mentioned above, by adding a quaternary onium salt, more preferably by adding a quaternary onium salt and employing the above-mentioned low-temperature spinning method, it is possible to reduce the degree of polymerization and yellowing of the modified polyester. Since the intrinsic viscosity was able to be significantly reduced, the intrinsic viscosity was 0.5 or more, preferably 0.5 or more.
For the first time, it is possible to provide a cationically dyeable modified polyester fiber of 6 or more, particularly preferably 0.63 or more, and this fiber has a silk factor (fiber strength x f elongation) of 2.
13 in distilled water containing vinegar M 1.4a /ρ.
When subjected to moist heat treatment at 0°C for 60 minutes, the number of breaks in the polyester main chain was less than 140 x 10 /106a 41 fibers, which indicates excellent heat resistance, and it exhibits high whiteness and excellent clarity when dyed. show.
最近、スポーツ衣料においては、鮮明に染色され、耐光
堅牢性に優れたポリエステル繊維が要求され、更に布帛
における高引裂強力が要求されている。布帛の引裂強力
は、その布帛のａｌｉＡ組織に依存する部分があるもの
の、大きくは極限粘度さらにはシルクファクターに依存
する。スポーツ衣料においては、その用途からもわかる
ように高シルクファクターが要求され、シルクファクタ
ーとして２５以上、好ましくは２８以上が必要であり、
本発明によってはじめて高シルクファクターで且つ耐熱
性に優れたカチオン染料可染のポリエステル繊維が得ら
れるようになった。Recently, in sports clothing, polyester fibers that are vividly dyed and have excellent light fastness are required, and high tear strength of the fabric is also required. The tearing strength of a fabric partly depends on the aliA structure of the fabric, but it largely depends on the intrinsic viscosity and silk factor. As can be seen from its use, sports clothing requires a high silk factor, with a silk factor of 25 or more, preferably 28 or more.
The present invention has made it possible for the first time to obtain polyester fibers dyeable with cationic dyes that have a high silk factor and excellent heat resistance.
本発明でいうポリエステル主鎖切断数とは、本発明の改
質ポリエステル繊維の耐熱性に係るパラメーターであり
、特定の熱処理条件下での繊維の分解による極限粘度低
下に対応するものである。The polyester main chain scission number as used in the present invention is a parameter related to the heat resistance of the modified polyester fiber of the present invention, and corresponds to a decrease in the intrinsic viscosity due to fiber decomposition under specific heat treatment conditions.
即ち、酢酸０．４ｇ／塁を含有する蒸溜水中１３０℃で
６０分間湿熱処理する前後で測定した改質ポリエステル
繊維の極限粘度の値より、処理前後の改質ポリエステル
ＩＩＩＩの数平均分子黴を求め、これらの値より繊維１
０ＧΩ中のポリマー分子鎖数を算出し、該ポリマー分子
鎖数の湿熱処理による増加がｌｌｆｆ１０６０当たりの
ポリエステル主鎖切断数に該当するとして定義されるも
のである。That is, from the intrinsic viscosity values of the modified polyester fibers measured before and after the moist heat treatment at 130°C for 60 minutes in distilled water containing 0.4 g of acetic acid/base, the number average molecular mold of the modified polyester III before and after the treatment was determined. , from these values fiber 1
The number of polymer molecular chains in 0 GΩ is calculated, and the increase in the number of polymer molecular chains due to moist heat treatment is defined as corresponding to the number of polyester main chain breaks per llff1060.
ここで、極限粘度低下そのものではなく、ポリエステル
主鎖切断点数を耐熱性のパラメーターとして導入した理
由は、主鎖切断数が繊維の初期極限粘度の大小によらな
いユニバーサルなパラメーターであるからである。極限
粘度の場合には、同一の主鎖切断数であっても、初期極
限粘度が大きい程極限粘度低下が大きくなるという不都
合が生じる。Here, the reason why the number of polyester main chain breakage points was introduced as a heat resistance parameter rather than the reduction in the intrinsic viscosity itself is that the number of main chain breakage points is a universal parameter that does not depend on the initial intrinsic viscosity of the fiber. In the case of the limiting viscosity, even if the number of main chain breaks is the same, a disadvantage arises in that the larger the initial limiting viscosity, the greater the reduction in the limiting viscosity.
本発明者らは、本発明における改質ポリエステル繊維の
耐熱性の重要性に鑑み、その評価方法について種々検討
した結果、本評価方法を確立したものであり、本方法に
よれば評価値が再現性良く、高精度で求めることができ
るのみならず、該繊維の各種処理、例えば仮撚加工や強
撚加工等の如き加工処理、染色処理、アルカリ減量処理
、樹脂コーティング等の後加工処理に伴う熱処理での繊
維物性低下の度合と極めて良く相関するため、耐熱性の
パラメーターとして工業的に非常に有用である。In view of the importance of the heat resistance of the modified polyester fiber in the present invention, the present inventors have established this evaluation method as a result of various studies on evaluation methods. Not only can it be determined with good quality and high precision, but it can also be used in various treatments of the fiber, such as false twisting and hard twisting, dyeing, alkali weight loss treatment, and post-processing such as resin coating. Since it correlates extremely well with the degree of deterioration of fiber physical properties during heat treatment, it is industrially very useful as a parameter for heat resistance.
以下に主鎖切断数の具体的な求め方を示す。A specific method for determining the number of main chain breaks is shown below.
（１）ｉａ維試料の前処理 常法に従って精練、風乾する。(1) Pretreatment of ia fiber sample Scour and air dry according to conventional methods.
（２） ＩＩ維、試料の湿熱処理
試料を酢ｌ Ｏ，４Ｑ／１含有の蒸溜水中１３０℃で６
０分間振盪下湿熱処理する（浴比１：５０）。(2) Moist heat treatment of the sample of II fiber and sample at 130°C in distilled water containing 1 O, 4Q/1 vinegar.
Treat with moist heat under shaking for 0 minutes (bath ratio 1:50).
（３）極限粘度の測定
上記湿熱処理前後の繊維試料の極限粘度［η］、及び［
η］、を下記の方法で測定する。(3) Measurement of intrinsic viscosity The intrinsic viscosity [η] and [
η] is measured by the following method.
試料ｏ、 ｅｏｏｇを精秤し、溶解管に入れる。含有水
分率を０．０３重量％以下とした精留０−クロロフェノ
ールを２５℃の恒温にして５０１１１１ホールピペツト
で採取して加える。１００℃で６０分間３５０〜４ｓｏ
ｒｐｍで撹拌しながら試料を溶解し、溶解終了後密栓し
て冷却する。該溶液の粘度をオストワルト粘度計を用い
て３５±０．１℃で測定し、下式により極限粘度［η］
を求める。Precisely weigh samples o and eoog and put them into a dissolution tube. Rectified 0-chlorophenol with a moisture content of 0.03% by weight or less is kept at a constant temperature of 25° C., collected using a 501111-hole pipette, and added. 350-4so at 100℃ for 60 minutes
The sample is dissolved while stirring at rpm, and after dissolution is completed, the sample is tightly capped and cooled. The viscosity of the solution was measured at 35±0.1°C using an Ostwald viscometer, and the intrinsic viscosity [η] was determined by the following formula:
seek.
ｋＧ ηｓｐ＝ηｒｅｌ −１ Ｌ Ｃ１ｔ−０２／ｌ ηｓｐ＝ −＝ ＬＯＣ１ｊＯ−０２／ｌ。kG ηsp=ηrel −1 L C1t-02/l ηsp= -= LOC1jO-02/l.
但し Ｌ ：溶液の動粘度
ＬＯ：溶媒の動粘度
Ｃ１：粘度計定数（ｉ比法ハＪＩｓ Ｚ−８８０３に基
づく）
Ｃ２：粘度計係数（算出法はＪＩＳ ２−８８０３に基
づく）
ｔ ：試料溶液の測定秒数
ｔｏ＝空試験の測Ｔ秒数
ｋ ： ０．２４７（ハギンス定数）Ｃ： １．
２００（ｇ／１００ｍ１）（４）主鎖切断数の計算
下記式〇及び■により［η］、及び［η］。However, L: Kinematic viscosity of the solution LO: Kinematic viscosity of the solvent C1: Viscometer constant (i ratio method based on JIS Z-8803) C2: Viscometer coefficient (calculation method is based on JIS 2-8803) t: Sample solution Measurement seconds to = Measurement T seconds of blank test k: 0.247 (Huggins constant) C: 1.
200 (g/100m1) (4) Calculation of the number of main chain breaks [η] and [η] using the following formulas ○ and ■.
に対応する数平均分子量「−及び稲を夫々計重 ｎする。Weigh the number average molecular weight corresponding to ``- and rice respectively. Do n.
□り、７７
［η］ （＝ ３．０７ Ｘ １０− Ｍ 、１
町・・■これらの値より、Ｉ８８試料１０Ｇ（ｌ当たり
の湿熱処理によるポリエステル主鎖切断数［ＮＳ］（Ｎ
ｕｍｂｅｒ ｏｆ ５ｃｉｓｓｉｏｎ）は下記のように
求まる。□ri, 77 [η] (= 3.07 X 10- M, 1
Town... ■From these values, the number of polyester main chain breaks [NS] (N
umber of 5 cission) is determined as follows.
ＮＳ＝ １０６（−−−） ｘ ６ｘ １０”（但し、
６Ｘ１０”はアボガドロ数を意味する）ちなみに、ポリ
エステル主鎖切断数が
１４０ｘ１０ ／１０６ｇ繊維
の湿熱処理による極限粘度の低下は
［η ］ 、 ＝ ０．６２０ → ［η コ
、 ＝ ０．４６４［η ］ 、 ＝
０．５００ → ［η コ 、 ＝ ０．３９４で
ある。NS= 106(---) x 6x 10" (However,
(6X10" means Avogadro's number) By the way, the decrease in intrinsic viscosity due to moist heat treatment of polyester main chain scission number of 140x10 /106g fiber is [η ], = 0.620 → [η co
, = 0.464[η] , =
0.500 → [η ko , = 0.394.
〈発明の作用効果〉
本発明のスルホン酸ホスホニウム塩を共重合した改質ポ
リエステルｕＡ雑は、従来のスルホン酸金属塩共重合型
の改質ポリエステルｒｊ＆雑に比して次のような利点を
有する。<Actions and Effects of the Invention> The modified polyester uA miscellaneous copolymerized with the sulfonic acid phosphonium salt of the present invention has the following advantages over the conventional modified polyester rj & miscellaneous of the sulfonic acid metal salt copolymerization type. .
（１）スルホン酸金属塩の金属イオンに比べて、スルホ
ン酸ホスホニウム塩のホスホニウム塩の方がバルキーで
あるためか、カチオン染料の拡散速度が大きく、そのた
めスルホン酸ホスホニウム塩の場合にはより少量の使用
でスルホン酸金Ｂ塩と同程度のカチオン染色性が得られ
る。(1) Compared to the metal ion of the sulfonate metal salt, the phosphonium salt of the sulfonate salt is bulkier, and the diffusion rate of the cationic dye is higher, so in the case of the sulfonate phosphonium salt, a smaller amount of the phosphonium salt is used. When used, cationic dyeing properties comparable to those of sulfonic acid gold B salt can be obtained.
（２）スルホン酸金属塩に固有の増粘作用が起こらない
ため、高重合度のポリマーが容易に得られ、また低温溶
融紡糸も容易に行うことができ、高強度のカチオン染料
可染型ポリエステル１ｉＩｎが容易に得られる。(2) Since the thickening effect inherent to sulfonic acid metal salts does not occur, polymers with a high degree of polymerization can be easily obtained, and low-temperature melt spinning can be easily performed, making it a high-strength cationic dye-dyeable polyester. 1iIn is easily obtained.
（３）更に、本発明によれば金属塩の代りにホスホ二マ
クム塩を使用するので、車台反応中にｉｔｌ生する異物
ｍが少なく、成形時、特に紡糸時のパック圧上昇や得ら
れる糸品位の低下が小さいという効果が得られる。(3) Furthermore, according to the present invention, since a phosphodimacum salt is used instead of a metal salt, it is possible to reduce the amount of foreign matter m generated during the undercarriage reaction, thereby reducing the increase in pack pressure during molding, especially during spinning, and the resulting yarn. The effect is that the deterioration in quality is small.
（４）上記（２）、（３）に関連して、本発明における
改質ポリエステルは曳糸性に極めて優れており、引取速
度が３０００１／分以上、特に５’ＯＯＯＩｌｌ／分以
上の超高速においても紡糸が可能である。また、１デニ
ール以下、更には０．５デニール以下の極細繊維の紡糸
が可能である。(4) In relation to (2) and (3) above, the modified polyester of the present invention has extremely excellent spinnability, and has an ultra-high take-up speed of 30001/min or more, especially 5'OOOIll/min or more. Spinning is also possible in Further, it is possible to spin ultrafine fibers of 1 denier or less, and even 0.5 denier or less.
（５）更に、本発明の改質ポリエステルｍ雑は、耐熱性
に優れているので、高温における仮撚加工においても、
強度低下や融着の問題を生ずることなく、優れた加工糸
を与えることができる。(5) Furthermore, the modified polyester m miscellaneous material of the present invention has excellent heat resistance, so even during false twisting at high temperatures,
Excellent textured yarn can be provided without causing problems of strength loss or fusion.
（６）スルホン酸金属塩を共重合した改質ポリエステル
！！紐が極めて静電気を発生し易いのとは逆に、本発明
の改質ポリエステル繊維は優れた訓電性を呈する。(6) Modified polyester copolymerized with sulfonic acid metal salt! ! On the contrary, the modified polyester fiber of the present invention exhibits excellent electrostatic properties, contrary to the fact that strings are extremely prone to generating static electricity.
（７）更に、本発明の改質ポリエステル繊維はホスホニ
ウム塩を含有するために難燃性と抗菌性に優れる。(7) Furthermore, since the modified polyester fiber of the present invention contains a phosphonium salt, it has excellent flame retardancy and antibacterial properties.
最近、スポーツ衣料においては、鮮明に染色され、耐光
堅牢性に優れたポリエステル繊維が要求されているが、
特に（１）、 （２）、 （３）、 （４）、 （５）
の特徴ゆえに、高白度であり、染色したとき発色性の優
れた鮮かな色彩を持ち、高強度のカチオン可染ポリエス
テル布帛を提供することができ、その有用性を一段と高
めた商品を開発することができるようになった。Recently, polyester fibers that are vividly dyed and have excellent light fastness are required for sports clothing.
Especially (1), (2), (3), (4), (5)
Because of its characteristics, we are able to provide high-strength cationically dyeable polyester fabrics that have high whiteness, vivid colors with excellent color development when dyed, and develop products that further enhance their usefulness. Now I can do it.
なお、本発明の改質ポリエステル繊維には必要に応じて
任意の添加剤、例えば触媒、着色防止剤、耐熱剤、難燃
剤、酸化防止剤、艶消剤、着色剤、無機微粒子等が含ま
れていてもよい。The modified polyester fiber of the present invention may contain optional additives such as catalysts, color inhibitors, heat resistant agents, flame retardants, antioxidants, matting agents, coloring agents, inorganic fine particles, etc. as necessary. You can leave it there.
〈実施例〉
以下に実施例をあげて更に説明する。実施例中の部及び
％は夫々重量部及び型Ｏ％を示す。ポリマーの極限粘度
［η］は２５℃のオルソクロルフェノール溶液で測定し
た値から求めた。軟化点（ｓｐ）はペネレーション法で
測定した。ポリマー中のジエチレングリコール含有１ｉ
（ＤＥＣ含有量〉は、ポリエステル試料を抱水ヒドラ
ジンで熱分解し、上澄液をガスクロマトグラフィーにか
けて定はした（内部標準として１，４−ブタンジオール
を使用）。<Example> Examples will be given below for further explanation. Parts and % in the examples indicate parts by weight and type O%, respectively. The intrinsic viscosity [η] of the polymer was determined from the value measured in an orthochlorophenol solution at 25°C. The softening point (sp) was measured by the penetration method. Diethylene glycol content in polymer 1i
(DEC content) was determined by thermally decomposing a polyester sample with hydrazine hydrate and subjecting the supernatant to gas chromatography (using 1,4-butanediol as an internal standard).
ポリマーの耐熱性は、共重合ポリマーの重合反応終了後
、重合鎖からのポリマー押出し窒素ガス圧を調整し、ポ
リマー取出しに要する時間を６０分以上とし、ポリマー
取出し開始１０分後と６０分後のポリマーの極限粘度［
η］の差をもって評価した。The heat resistance of the polymer is determined by adjusting the nitrogen gas pressure for extruding the polymer from the polymer chain after the completion of the polymerization reaction of the copolymer, and setting the time required for polymer extraction to be at least 60 minutes. Intrinsic viscosity of polymer [
Evaluation was made based on the difference in η].
ポリマーの色調はハンター型色差計によるＬｍとｂ値で
示した。Ｌ値は値が大きくなる程白変が良好なことを示
し、ｂ値は＋側に大きくなる程黄味が強いことを示す。The color tone of the polymer was indicated by the Lm and b values determined by a Hunter color difference meter. The larger the L value, the better the whitening, and the larger the b value on the + side, the stronger the yellowness.
なお、ポリマーの軟化点（ｓｐ）、色相及びＤＥＧ含有
量はポリマー取出し開始３０分後のポリマーについて測
定した。Note that the softening point (sp), hue, and DEG content of the polymer were measured for the polymer 30 minutes after the start of taking out the polymer.
実施例１及び比較例１
テレフタル酸ジメチル１００部、エチレングリコール６
０部、酢酸マンガン４水塩０．０３部（テレフタル酸ジ
メチルに対して０．０２４モル％）、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％）、テレフタル酸ジメチルに対
して １．７モル％の量の３，５−ジカルボメトキシベ
ンゼンスルホン酸テトラ−ｎ−ブチルホスホニウム塩及
びテレフタル酸ジメチルに対して０．０５０モル％の量
のテトラ−ｎ−ブチルホスホニウムブロマイドをエステ
ル交換色に仕込み、窒素ガス雰囲気１３時間かけて １
４０℃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させた。続いて得
られた生成物に、安定剤として正リン酸の５６％水溶液
００３部（テレフタル酸ジメチルに対して０．０３３モ
ル％）を添加し、同時に過剰のエチレングリコール昇温
追出しを開始した。１０分後重縮合触媒として三酸化ア
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％）を添加した。内温が２４０℃に達した
時点でエチレングリコールの追出しを終了し、反応生成
物を重合化に移した。Example 1 and Comparative Example 1 100 parts of dimethyl terephthalate, 6 parts of ethylene glycol
0 parts, 0.03 parts of manganese acetate tetrahydrate (0.024 mol % based on dimethyl terephthalate), 0.009 parts of cobalt acetate tetrahydrate as a coloring agent (0.007 mol based on dimethyl terephthalate) %), 3,5-dicarbomethoxybenzenesulfonic acid tetra-n-butylphosphonium salt in an amount of 1.7 mol % based on dimethyl terephthalate and tetra-n-butylphosphonium salt in an amount of 0.050 mol % based on dimethyl terephthalate. -N-Butylphosphonium bromide was prepared for transesterification, and the process was carried out in a nitrogen gas atmosphere for 13 hours.
The temperature was raised from 40° C. to 220° C., and the resulting methanol was distilled out of the system to carry out the transesterification reaction. Subsequently, 0.03 parts of a 56% aqueous solution of orthophosphoric acid (0.033 mol % based on dimethyl terephthalate) was added to the resulting product as a stabilizer, and at the same time, expulsion of excess ethylene glycol at elevated temperature was started. After 10 minutes, 0.04 part of antimony trioxide (0.04 parts based on dimethyl terephthalate) was added as a polycondensation catalyst.
．． 027 mol%) was added. When the internal temperature reached 240°C, expulsion of ethylene glycol was completed, and the reaction product was transferred to polymerization.
次いで昇温しなから内温が２６０℃に到達するまで常圧
反応させた後、１時間かけて７６０ｍｍＨｇからｌｍｍ
Ｈｇまで減圧し、同時に１時間３０分かけて内温を２８
０℃まで昇温した。ｌｌｌｌｍＨｇ以下の減圧下、重合
温度２８０℃で更に２時間重合した時点で窒素ガスで真
空を破って重合反応を終了し、窒素ガス加圧下に２８０
℃でポリマーの吐出を行った。Next, without raising the temperature, the reaction was carried out at normal pressure until the internal temperature reached 260°C, and then the temperature was increased from 760 mmHg to 1 mm over 1 hour.
The pressure was reduced to Hg, and at the same time the internal temperature was lowered to 28°C over 1 hour and 30 minutes.
The temperature was raised to 0°C. After further polymerization for 2 hours at a polymerization temperature of 280° C. under reduced pressure of 110 mHg or less, the vacuum was broken with nitrogen gas to terminate the polymerization reaction, and the polymerization reaction was completed at 280° C. under nitrogen gas pressure.
Polymer dispensing was carried out at °C.
得られたポリマーの軟化点（ｓｐ）は２５３５℃、ジエ
チレングリコール含有ｆｉ （ＤＥＧ含但）は１．６８
、吐出１０分後の極限粘度（［η］１ｏ）は０．６７２
、吐出６０分後の極限粘度（［η］６ｏ）は０．６４８
であった。The softening point (sp) of the obtained polymer was 2535°C, and the diethylene glycol content fi (including DEG) was 1.68.
, the intrinsic viscosity ([η]1o) after 10 minutes of discharge is 0.672
, the intrinsic viscosity ([η]6o) after 60 minutes of discharge is 0.648
Met.
このポリマーを２９０℃で溶融し、直径０．３ｍｍ、長
さ０． ｅｍｍの紡糸孔を２４個設けた紡糸口金を用い
て紡出した。紡出糸の延伸後の単糸繊度が約３デニール
、破断伸度が３０％になるように吐出量を調整し、１０
００ ｍ７分で引取った。得られた紡出糸の極限粘度（
［η］、）は０．６２５であった。次いで、破断伸度が
３０％になる延伸倍率で予熱温度８０℃で延伸し、１３
０℃の熱板で熱セットした。This polymer was melted at 290°C and had a diameter of 0.3 mm and a length of 0.3 mm. Spinning was performed using a spinneret with 24 emm spinning holes. The discharge amount was adjusted so that the single yarn fineness after drawing of the spun yarn was approximately 3 denier and the elongation at break was 30%.
00 m7 minutes later. The intrinsic viscosity of the obtained spun yarn (
[η], ) was 0.625. Next, it was stretched at a preheating temperature of 80°C at a stretching ratio that gave a breaking elongation of 30%.
Heat setting was performed on a 0°C hot plate.
得られた延伸糸の単糸繊度は３．０デニール、強度は５
．０ ｇ／ｄｅ１シルクファクターは２７．６、Ｌ値は
８４．７、ｂ値は６．８、主査切断数は６７であった。The single yarn fineness of the obtained drawn yarn was 3.0 denier and the strength was 5.
．． The 0 g/del silk factor was 27.6, the L value was 84.7, the b value was 6.8, and the main cut number was 67.
比較のため、テトラ−ｎ−ブチルホスホニウムブロマイ
ドを使用しない以外は実施例１と同様に行った。For comparison, the same procedure as Example 1 was carried out except that tetra-n-butylphosphonium bromide was not used.
得られたポリマーの軟化点（ｓｐ）は２５３．５℃、ジ
エチレングリコール含有ｆｉ （ＤＥＧ含は）は１．６
７、吐出１０分後の極限粘度（［ηコ、。）は０．５７
６、吐出６０分後の極限粘度（［ηコ。。）は０．５２
１であり、紡出糸の極限粘度（［η］、）は０．４８０
、延伸糸の単糸繊度は３０デニール、強度は３．８ ｇ
／ｄｅ、シルクファクターは２１．３、Ｌ値は７９．８
、ｂ値は１４．９、主査切断数は１５２であった。The softening point (sp) of the obtained polymer was 253.5°C, and the diethylene glycol content fi (including DEG) was 1.6.
7. Intrinsic viscosity ([η,.) after 10 minutes of discharge is 0.57
6. Intrinsic viscosity ([η ko...) after 60 minutes of discharge is 0.52
1, and the intrinsic viscosity ([η],) of the spun yarn is 0.480
, the single yarn fineness of the drawn yarn is 30 denier, and the strength is 3.8 g.
/de, silk factor is 21.3, L value is 79.8
, the b value was 14.9, and the number of cuts by the main examiner was 152.
実施例２及び比較例２
実施例１で使用した３、５−ジカルボメトキシベンゼン
スルホン酸テトラ−ｎ−ブチルホスホニウム塩及びテト
ラ−ｎ−ブチルホスホニウムブロマイドに代えて、テレ
フタル酸ジメチルに対して１．７モル％の最の３．５−
ジカルボキシベンゼンスルホン酸テトラフェニルホスホ
ニウム塩及びテレフタル酸ジメチルに対して０．０５０
モル％の最のテトラフェニルホスホニウムハイドロオキ
サイドを使用し、これらの添加時期をエステル交換反応
終了後圧リン酸添加前にする以外は実施例１と同様に行
った。Example 2 and Comparative Example 2 In place of 3,5-dicarbomethoxybenzenesulfonic acid tetra-n-butylphosphonium salt and tetra-n-butylphosphonium bromide used in Example 1, 1. 7 mol% of the most 3.5-
0.050 for dicarboxybenzenesulfonic acid tetraphenylphosphonium salt and dimethyl terephthalate
The same procedure as in Example 1 was carried out except that the highest mol% of tetraphenylphosphonium hydroxide was used and the timing of addition was after the end of the transesterification reaction and before the addition of pressurized phosphoric acid.
得られたポリマーの軟化点（ｓｐ）は２５３４℃、ジエ
チレングリコ−ル含有’Ｔ （ＤＥＣ含ω）は１６５、
吐出１０分後の極−限粘度（［η］１ｏ）は０．６７４
、吐出６０分後の極限粘度（［η］、６ｏ）は０．６５
３であり、紡出糸の極限粘度（［η］、）は０．６３０
、延伸糸の単糸繊度は３．０デニール、強度は５．２
ｑ／ｄｅ。The obtained polymer had a softening point (sp) of 2534°C, a diethylene glycol content 'T (DEC content ω) of 165,
Intrinsic viscosity ([η]1o) after 10 minutes of discharge is 0.674
, the intrinsic viscosity ([η], 6o) after 60 minutes of discharge is 0.65
3, and the intrinsic viscosity ([η],) of the spun yarn is 0.630.
, the single yarn fineness of the drawn yarn is 3.0 denier, and the strength is 5.2
q/de.
シルクファクターは２８，４、Ｌ値は８４．９、ｂ値は
７．６、主査切断数は６５であった。The silk factor was 28.4, the L value was 84.9, the b value was 7.6, and the number of main cuts was 65.
比較のため、テトラフェニルホスホニウムハイドロオキ
サイドを使用しない以外は実施例２と同様に行った。For comparison, the same procedure as Example 2 was carried out except that tetraphenylphosphonium hydroxide was not used.
得られたポリマーの軟化点（ｓｐ）は２５３．１℃、ジ
エチレングリコール含有ｌ （ＤＥＧ含借）は１．６７
、吐出１０分後の極限粘度（［ηコ、。）は０．５８３
、吐出６０分後の極限粘度（［η］６ｏ）は０．５３２
であり、紡出糸の極限粘度（［η］、）は０．４９５、
延伸糸の単糸繊度は３．０デニール、強度は３．７ ｇ
／ｄｅ。The softening point (sp) of the obtained polymer was 253.1°C, and the diethylene glycol content (DEG content) was 1.67.
, the intrinsic viscosity ([η, .) after 10 minutes of discharge is 0.583
, the intrinsic viscosity ([η]6o) after 60 minutes of discharge is 0.532
The intrinsic viscosity ([η], ) of the spun yarn is 0.495,
The single yarn fineness of the drawn yarn is 3.0 denier and the strength is 3.7 g.
/de.
シルクファクターは２０，９、Ｌ値は７８．８、ｂ値は
１５．５、主査切断数は１４５であった。The silk factor was 20.9, the L value was 78.8, the b value was 15.5, and the number of main cuts was 145.
実施例３
実施例２で使用した３、５−ジカルボキシベンゼンスル
ホン酸テ１〜ラフェニルホスホニウム塩及びテトラフェ
ニルホスホニウムハイドロオキサイドに代えて、テレフ
タル酸ジメチルに対して １７モル％の最の３．５−ジ
カルボキシベンゼンスルホン酸テトラ−０−プチルボス
ホニウム塩及びテレフタル酸ジメチルに対して０００３
モル％の量の水酸化テトラ−ｎ−ブチルアンモニウムを
使用する以外は実施例２と同様に行った。Example 3 In place of the 3,5-dicarboxybenzenesulfonic acid tetra-raphenylphosphonium salt and tetraphenylphosphonium hydroxide used in Example 2, 17 mol % of the most 3.5% based on dimethyl terephthalate was added. -0003 for dicarboxybenzenesulfonic acid tetra-0-butylbosphonium salt and dimethyl terephthalate
Example 2 was carried out as in Example 2, except that a mole % amount of tetra-n-butylammonium hydroxide was used.
得られたポリマーの軟化点（ｓｐ）は２５３．３℃、ジ
エチレングリコール含有量（ＤＥＧ含ｍ）は１．６３、
吐出１０分後の極限粘度（［η］１ｏ）は０．６７３、
吐出６０分後め極限粘度（［η］６ｏ）は０．６５１で
あり、紡出糸の極限粘度（［η］、）は０．６２３、延
伸糸の単糸繊度は３．０デニール、強度は５．３ Ｑ／
ｄｅ、シルクファクターは２９．０、Ｌ値は８５．３、
ｂ値は１．５、主査切断数は９６であった。The resulting polymer had a softening point (sp) of 253.3°C, a diethylene glycol content (DEG content) of 1.63,
The intrinsic viscosity ([η]1o) after 10 minutes of discharge is 0.673,
The intrinsic viscosity ([η]6o) after 60 minutes of discharge was 0.651, the intrinsic viscosity ([η], ) of the spun yarn was 0.623, the single yarn fineness of the drawn yarn was 3.0 denier, and the strength is 5.3 Q/
de, silk factor is 29.0, L value is 85.3,
The b value was 1.5 and the number of main cuts was 96.
実施例４
実施例３で使用した水酸化テトラ−ｎ−ブチルアンモニ
ウムに代えて、テレフタル酸ジメチルに対して０．０５
０モル％の四の塩化テトラ−ｎ−ブチルアンモニウムを
使用する以外は実施例３と同様に行った。Example 4 In place of the tetra-n-butylammonium hydroxide used in Example 3, 0.05% of dimethyl terephthalate was used.
Example 3 was carried out in the same manner as in Example 3, except that 0 mol % of tetra-tetra-n-butylammonium chloride was used.
得られたポリマーの軟化点（’ｓ ｐ ）は２５４．０
℃、ジエチレングリコール含有ｆｆ１（ＤＥＧ含量）は
１．７０、吐出１０分後の極限粘度（［ηコ、。）は０
．６７５、吐出６０分後の極限粘度（［η］６ｏ）はＯ
，，６４６であり、紡出糸の極限粘度（［η］、）は０
．６１５、延伸糸の単糸繊度ｆ、ｔ ３．０７”ニール
、強度は４．８ ｇ／ｄｅ、シルクファクターは２６．
８、Ｌ値は８５．４、ｂ値は７．３、主査切断数は７２
であった。The softening point ('s p ) of the obtained polymer was 254.0
°C, diethylene glycol content ff1 (DEG content) is 1.70, and the intrinsic viscosity ([η, .) after 10 minutes of discharge is 0.
．． 675, the intrinsic viscosity ([η]6o) after 60 minutes of discharge is O
,,646, and the intrinsic viscosity ([η],) of the spun yarn is 0
．． 615, the single yarn fineness of the drawn yarn is f, t 3.07” neel, the strength is 4.8 g/de, and the silk factor is 26.
8, L value is 85.4, b value is 7.3, number of chief cuts is 72
Met.
実施例５
実施例３で使用した水酸化テトラ−ｎ−ブチルアンモニ
ウムの使用温をテレフタル酸ジメチルに対して０１００
モル％にする以外は実施例３と同様に行った。Example 5 The working temperature of tetra-n-butylammonium hydroxide used in Example 3 was 0.10% relative to dimethyl terephthalate.
The same procedure as in Example 3 was carried out except that the values were changed to mol%.
得られたポリマーの軟化点（ｓｐ）は２５２．５℃、ジ
エチレングリコール含有ｆｆｌ （ＤｒＧ含は）は１８
５、吐出１０分後の極限粘度（［η］１ｏ）は０．６４
８、吐出６０分後の極限粘度（［η］６ｏ）は０．６１
７であり、紡出糸の極限粘度（［η］、）は０．６００
、延伸糸の単糸繊度は３．０デニール、強度は５．０ｇ
／ｄｃ、シルクファクターは２７．６、Ｌ値は８６，３
、ｂ値は７５、主査切断数は６４であった。The softening point (sp) of the obtained polymer was 252.5°C, and the diethylene glycol-containing ffl (including DrG) was 18
5. Intrinsic viscosity ([η]1o) after 10 minutes of discharge is 0.64
8. Intrinsic viscosity ([η]6o) after 60 minutes of discharge is 0.61
7, and the intrinsic viscosity ([η],) of the spun yarn is 0.600
, the single yarn fineness of the drawn yarn is 3.0 denier, and the strength is 5.0 g.
/dc, silk factor is 27.6, L value is 86.3
, the b value was 75, and the number of cuts by the main examiner was 64.
実施例６
実施例２で使用したテトラフェニルホスホニウムハイド
ロオキサイドに代えて、テレフタル酸ジメチルに対して
ｏ、 ｏｓｏモル％の量の水酸化テトラフェニルアンモ
ニウムを使用する以外は実施例２と同様に行った。Example 6 The same procedure as in Example 2 was carried out except that in place of the tetraphenylphosphonium hydroxide used in Example 2, tetraphenylammonium hydroxide was used in an amount of o, oso mol % based on dimethyl terephthalate. .
得られたポリマーの軟化点（ｓｐ）は２５３．２℃、ジ
エチレングリコール含有量（ＤＥＧ含旦）は１．８５、
吐出１０分後の極限粘度（［ηコ、。）は０．６７３、
吐出６０分後の極限粘度（［η］６ｏ）は０．６５２で
あり、紡出糸の極限粘度（［ηコ、）は０．６００、延
伸糸の単糸繊度は３０デニール、強度は５＝２ Ｑ／ｄ
ｅ。The resulting polymer had a softening point (sp) of 253.2°C, a diethylene glycol content (DEG content) of 1.85,
The intrinsic viscosity ([η,.) after 10 minutes of discharge is 0.673,
The intrinsic viscosity ([η]6o) after 60 minutes of discharge is 0.652, the intrinsic viscosity ([η]6o) of the spun yarn is 0.600, the single yarn fineness of the drawn yarn is 30 denier, and the strength is 5 =2 Q/d
e.
シルクファクターは２８．９、Ｌ値は８４．８、ｂ値は
７３、主査切断数は８２であった。The silk factor was 28.9, the L value was 84.8, the b value was 73, and the number of main cuts was 82.
実施例７
実施例１で使用したテトラ−ｎ−プチルボスホニウムブ
ロマイドに代えて、テレフタル酸ジメチルに対してｏ、
ｏｓｏモル％の量の塩化テトラブチルアンモニウムを
使用する以外は実施例１と同様に行った。Example 7 In place of the tetra-n-butylbosphonium bromide used in Example 1, o,
Example 1 was carried out as in Example 1, except that an amount of oso mol % of tetrabutylammonium chloride was used.
得られたポリマーの軟化点（ＳＰ）は２５２．７℃、ジ
エチレングリコール含有ｆｆｉ （ＤＥＧ含量）は１．
８４、吐出１０分後の極限粘度（［η］１ｏ）は０．６
８３、吐出６０分後の極限粘度（［η］６ｏ）は０．６
５６であり、紡出糸の極限粘度（ｒηコ、）は０．６２
０、延伸糸の単糸繊度は３．０デニール、強度は５．３
（Ｊ／ｄｅ、シルクファクターは２９．３、Ｌ値は８
４．９、ｂ値は７．２、主査切断数は６８であった。The resulting polymer had a softening point (SP) of 252.7°C and a diethylene glycol content ffi (DEG content) of 1.
84, the intrinsic viscosity ([η]1o) after 10 minutes of discharge is 0.6
83, the intrinsic viscosity ([η]6o) after 60 minutes of discharge is 0.6
56, and the intrinsic viscosity (rη) of the spun yarn is 0.62.
0, single yarn fineness of drawn yarn is 3.0 denier, strength is 5.3
(J/de, silk factor is 29.3, L value is 8
4.9, the b value was 7.2, and the number of cuts by the chief examiner was 68.
実施例８
実施例２で使用した３、５−ジカルボキシベンゼンスル
ホン酸テトラフェニルホスホニウム塩に代えて、テレフ
タル酸ジメチルに対して １．７モル％の硲の３，５−
ジカルボキシベンゼンスルホン酸テトラ−ｎ−ブチルホ
スホニウム塩及びテレフタル酸ジメチルに対して０．０
１７モル％の市の３．５−ジカルボキシベンゼンスルホ
ン酸トリー〇−ブチルホスホニウム塩の混合物を使用し
、更にテトラフェニルホスホニウムハイドロオキサイド
に代えて、テレフタル酸ジメチルに対して０．２モル％
の岳のテトラ−ｎ−ブチルホスホニウムクロライドを使
用する以外は実施例２と同様に行った。Example 8 In place of the 3,5-dicarboxybenzenesulfonic acid tetraphenylphosphonium salt used in Example 2, 1.7 mol % of 3,5- dimethyl terephthalate was used.
0.0 for dicarboxybenzenesulfonic acid tetra-n-butylphosphonium salt and dimethyl terephthalate
A mixture of 17 mol % of tri-butylphosphonium 3.5-dicarboxybenzenesulfonic acid salt was used and 0.2 mol % of dimethyl terephthalate was used instead of tetraphenylphosphonium hydroxide.
The same procedure as in Example 2 was carried out except that Nodake's tetra-n-butylphosphonium chloride was used.
得られたポリマーの軟化点（ｓｐ）は２５３．９℃、ジ
エチレングリコール含有１（ＤＥＣ含量）は１．５４、
吐出１０分後の極限粘度（［ηコ、。）は０．６７８、
吐出６０分後の極限粘度（Ｌηコ。。）は０．６５６で
あり、紡出糸の極限粘度（［η］、）は０．６２６、延
伸糸の単糸繊度は３．０デニール、強度は５．１ Ｑ／
ｄｅ。The softening point (sp) of the obtained polymer was 253.9°C, diethylene glycol content 1 (DEC content) was 1.54,
The intrinsic viscosity ([η,.) after 10 minutes of discharge is 0.678,
The intrinsic viscosity (Lη) after 60 minutes of discharge is 0.656, the intrinsic viscosity ([η], ) of the spun yarn is 0.626, the single yarn fineness of the drawn yarn is 3.0 denier, and the strength is is 5.1 Q/
de.
シルクファクターは２７，９、Ｌ値は７２，５、ｂ値は
６．２、主査切断数は６３であった。The silk factor was 27.9, the L value was 72.5, the b value was 6.2, and the number of main cuts was 63.
実施例９
実施例２で使用した３、５−ジカルボキシベンゼンスル
ホン酸テトラフェニルホスホニウム塩及びテトラフェニ
ルホスホニウムハイドロオキサイドに代えて、テレフタ
ル酸ジメチルに対して １，７モル％の母の３，５−ジ
カルボキシベンゼンスルホン酸テトラ−ｎ−ブチルホス
ホニウム塩及びテレフタル酸ジメチルに対して０．０２
モル％の最のテトラ−ｎ−ブチルホスホニウムクロライ
ドを使用する以外は実施例２と同様に重合し、ポリ７−
吐出を行った。Example 9 In place of the 3,5-dicarboxybenzenesulfonic acid tetraphenylphosphonium salt and tetraphenylphosphonium hydroxide used in Example 2, 1.7 mol% of the parent 3,5-dimethyl terephthalate was used. 0.02 for dicarboxybenzenesulfonic acid tetra-n-butylphosphonium salt and dimethyl terephthalate
Polymerization was carried out in the same manner as in Example 2, except that the highest mol% of tetra-n-butylphosphonium chloride was used, and poly7-
Discharge was performed.
得られたポリマーの軟化点（ＳＰ）は２５３６℃、ジエ
チレングリコール含有ｆｆｉ （ＤＥＧ含量）は１．６
５、吐出１０分後の極限粘度（［η］１ｏ）は０６６０
、吐出６０分後の極限粘度（［ηコ。。）は０．６２８
であった。The softening point (SP) of the obtained polymer was 2536°C, and the diethylene glycol content ffi (DEG content) was 1.6.
5. The intrinsic viscosity ([η]1o) after 10 minutes of discharge is 0660
, the intrinsic viscosity ([η ko...) after 60 minutes of discharge is 0.628
Met.
Ｍ１図に示す紡糸口金板４（導入孔１の大径５ｍ１１１
、吐出孔２の径１．３ｎｕｎ、長さ１．０ｍｍ、吐出孔
２の数２４）と第２図に示す紡糸液案内棒７（柱状部１
２の径１．０ｍｍ、長さ５ｍｍ）を組合せた第３図に示
す紡糸口金（吐出面９より下方に突出している案内棒の
長さ３ｍｍ）を用いて、上記ポリマーを２９０℃で完全
に溶融した後、２６０℃に保持した口金温度にまで降温
せしめて紡出した。紡出糸の弧伸後の単糸繊度が約３デ
ニール、破断伸度が３０％になるように叶出伍を調整し
、１０００ ＩＩＩ／分で引取った。Spinneret plate 4 shown in diagram M1 (large diameter of introduction hole 1 5 m111
, the diameter of the discharge hole 2 is 1.3nun, the length is 1.0mm, the number of discharge holes 2 is 24) and the spinning solution guide rod 7 (columnar part 1
Using the spinneret shown in Fig. 3 (with a guide rod length of 3 mm protruding downward from the discharge surface 9), which is a combination of spinnerets (diameter 1.0 mm, length 5 mm), the above polymer is completely heated at 290°C. After melting, the temperature was lowered to a spinneret temperature maintained at 260° C. and spun. The spun yarn was adjusted to have a single yarn fineness of about 3 denier and a breaking elongation of 30% after arc elongation, and was taken off at 1000 III/min.
得られた紡出糸の極限粘度（［η］、）は０．６３０で
あった。次いで、破断伸度が３０％になる延伸倍率で予
熱温度８０℃で延伸し、１３０℃の熱板で熱セットした
。The intrinsic viscosity ([η], ) of the obtained spun yarn was 0.630. Next, the film was stretched at a preheating temperature of 80° C. at a stretching ratio such that the elongation at break was 30%, and heat set using a hot plate at 130° C.
得られた延伸糸の単糸繊度は３．０デニール、強度は５
．３ｇ／ｄｅ、シルクファクターは２９．３、Ｌ値ハ９
２．ＯＳｂ値ハ５．８、主査切ｒ！ｆＩ数ハ４５テアツ
タ。The single yarn fineness of the obtained drawn yarn was 3.0 denier and the strength was 5.
．． 3g/de, silk factor is 29.3, L value is 9
2. OSb value ha 5.8, chief inspection r! The fI number is 45 tears.
実施例１０
実施例９における紡糸時の口金の保持温度を２７０℃に
変える以外は、全て実施例９と同様に行った。Example 10 Everything was carried out in the same manner as in Example 9 except that the holding temperature of the spinneret during spinning was changed to 270°C.
紡出糸の極限粘度（［ηコ、）は０．６１０、延伸糸の
単糸繊度は２．８デニール、強度は５．５ ｇ／ｄｅ、
シルクファクターは２９．５、Ｌ値は９０．１、ｂ値は
６０１主査切断数は５３であった。The intrinsic viscosity ([η,) of the spun yarn is 0.610, the single yarn fineness of the drawn yarn is 2.8 denier, and the strength is 5.5 g/de.
The silk factor was 29.5, the L value was 90.1, the b value was 601, and the number of cuts by the main examiner was 53.
第１図は本発明の改質ポリエステル繊維の製造に適した
紡糸口金の要部縦断面図、第２図はこの紡糸口金におけ
る紡糸液案内棒の一例を示す斜視図、第３図は第２図に
示す紡糸液案内棒を嵌入した紡糸口金の要部縦断面図（
イ）及び（イ）の八−Δ′面での要部横断面図（ロ）で
ある。
１：紡糸液導入孔 ２：ｖＪ糸液液吐出孔３紡糸孔
４：紡糸口金板
５：羽根 ６：案内棒先端
７：案内棒 ８；）９人孔下部９：吐出血
１０：導入孔大径部内壁１１：通路
１２：案内棒柱状部１３：環状通路
第７回
ざ
第３回
（イノ
第、２．図
グ
（ロ）
ｆ乙FIG. 1 is a longitudinal cross-sectional view of essential parts of a spinneret suitable for producing the modified polyester fiber of the present invention, FIG. 2 is a perspective view showing an example of a spinning solution guide rod in this spinneret, and FIG. Longitudinal cross-sectional view of the main part of the spinneret fitted with the spinning solution guide rod shown in the figure (
Fig. 3 is a cross-sectional view (b) of the main part of (a) and (a) taken along the 8-Δ' plane. 1: Spinning liquid introduction hole 2: VJ yarn liquid discharge hole 3 Spinning hole
4: Spinneret metal plate 5: Vane 6: Guide rod tip 7: Guide rod 8;) 9 Lower part of the manhole 9: Hemorrhage
10: Inner wall of large diameter introduction hole 11: Passage
12: Guide rod columnar part 13: Circular passage 7th za 3rd (Ino No. 2. Figure (b) f B)
Claims (1)
（ I ） （式中、Ａは芳香族基又は脂肪族基、Ｘ１はエステル形
成性官能基、Ｘ２はＸ１と同一若しくは異なるエステル
形成性官能基又は水素原子、Ｒ１、Ｒ２、Ｒ３及びＲ４
はアルキル基及びアリール基より選ばれた同一又は異な
る基、ｎは正の整数を示す。）で表わされるスルホン酸
ホスホニウム塩を０．１〜１０モル％共重合した極限粘
度０．５以上の改質ポリエステルからなり、シルクファ
クターが２５以上で且つ酢酸０．４ｇ／ｌを含有する蒸
溜水中１３０℃で６０分間湿熱処理した際のポリエステ
ル主鎖切断数が１４０×１０＾２＾３／１０＾６ｇ繊維
以下である改質ポリエステル繊維。[Claims] The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
(I) (wherein A is an aromatic group or aliphatic group, X1 is an ester-forming functional group, X2 is the same or different ester-forming functional group or hydrogen atom as X1, R1, R2, R3 and R4
are the same or different groups selected from alkyl groups and aryl groups, and n represents a positive integer. ) in distilled water containing a modified polyester having an intrinsic viscosity of 0.5 or more and having a silk factor of 25 or more and containing 0.4 g/l of acetic acid. A modified polyester fiber whose number of polyester main chain breaks is 140 x 10^2^3/10^6g fiber or less when subjected to moist heat treatment at 130°C for 60 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63063692A JPH01162822A (en) | 1987-03-20 | 1988-03-18 | Modified polyester fiber |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6439087 | 1987-03-20 | ||
| JP62-64390 | 1987-03-20 | ||
| JP62-113639 | 1987-05-12 | ||
| JP62-121034 | 1987-05-20 | ||
| JP63063692A JPH01162822A (en) | 1987-03-20 | 1988-03-18 | Modified polyester fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01162822A true JPH01162822A (en) | 1989-06-27 |
| JPH0361766B2 JPH0361766B2 (en) | 1991-09-20 |
Family
ID=26404822
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63063692A Granted JPH01162822A (en) | 1987-03-20 | 1988-03-18 | Modified polyester fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01162822A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0364547A (en) * | 1989-07-28 | 1991-03-19 | Teijin Ltd | Water repellent durable fabric |
| JPH0364548A (en) * | 1989-07-28 | 1991-03-19 | Teijin Ltd | Water repellent durable fabric |
| JPH04289219A (en) * | 1991-03-18 | 1992-10-14 | Teijin Ltd | Light-weight and vividly dyeable polyester multifilament yarn |
| JP2007031863A (en) * | 2005-07-25 | 2007-02-08 | Teijin Fibers Ltd | Profiled polyester multifilament for separation |
| WO2009088008A1 (en) | 2008-01-08 | 2009-07-16 | Teijin Fibers Limited | Normal pressure cation dyeable polyester and fiber |
| JP2009161694A (en) * | 2008-01-09 | 2009-07-23 | Teijin Fibers Ltd | Ordinary-pressure cation-dyeable polyester |
| JP2009161670A (en) * | 2008-01-08 | 2009-07-23 | Teijin Fibers Ltd | Cation-dyeable polyester |
| JP2010018926A (en) * | 2008-07-14 | 2010-01-28 | Teijin Fibers Ltd | Method for producing polyester nanofiber |
| JP2010059583A (en) * | 2008-09-05 | 2010-03-18 | Teijin Fibers Ltd | Fabric and textile product |
| JP2010255128A (en) * | 2009-04-22 | 2010-11-11 | Teijin Fibers Ltd | Circular knitted fabric and fiber product |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7892993B2 (en) * | 2003-06-19 | 2011-02-22 | Eastman Chemical Company | Water-dispersible and multicomponent fibers from sulfopolyesters |
| JP2012001828A (en) * | 2010-06-14 | 2012-01-05 | Teijin Fibers Ltd | Polyester fiber |
| JP2012001827A (en) * | 2010-06-14 | 2012-01-05 | Teijin Fibers Ltd | Polyester fiber |
-
1988
- 1988-03-18 JP JP63063692A patent/JPH01162822A/en active Granted
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0364547A (en) * | 1989-07-28 | 1991-03-19 | Teijin Ltd | Water repellent durable fabric |
| JPH0364548A (en) * | 1989-07-28 | 1991-03-19 | Teijin Ltd | Water repellent durable fabric |
| JPH04289219A (en) * | 1991-03-18 | 1992-10-14 | Teijin Ltd | Light-weight and vividly dyeable polyester multifilament yarn |
| JP2007031863A (en) * | 2005-07-25 | 2007-02-08 | Teijin Fibers Ltd | Profiled polyester multifilament for separation |
| WO2009088008A1 (en) | 2008-01-08 | 2009-07-16 | Teijin Fibers Limited | Normal pressure cation dyeable polyester and fiber |
| JP2009161670A (en) * | 2008-01-08 | 2009-07-23 | Teijin Fibers Ltd | Cation-dyeable polyester |
| US8297035B2 (en) | 2008-01-08 | 2012-10-30 | Teijin Fibers Limited | Normal pressure cationic dyeable polyester and fiber |
| JP2009161694A (en) * | 2008-01-09 | 2009-07-23 | Teijin Fibers Ltd | Ordinary-pressure cation-dyeable polyester |
| JP2010018926A (en) * | 2008-07-14 | 2010-01-28 | Teijin Fibers Ltd | Method for producing polyester nanofiber |
| JP2010059583A (en) * | 2008-09-05 | 2010-03-18 | Teijin Fibers Ltd | Fabric and textile product |
| JP2010255128A (en) * | 2009-04-22 | 2010-11-11 | Teijin Fibers Ltd | Circular knitted fabric and fiber product |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0361766B2 (en) | 1991-09-20 |
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