JP3530900B2 - Polyester composition and method for producing the same - Google Patents
Polyester composition and method for producing the sameInfo
- Publication number
- JP3530900B2 JP3530900B2 JP27756295A JP27756295A JP3530900B2 JP 3530900 B2 JP3530900 B2 JP 3530900B2 JP 27756295 A JP27756295 A JP 27756295A JP 27756295 A JP27756295 A JP 27756295A JP 3530900 B2 JP3530900 B2 JP 3530900B2
- Authority
- JP
- Japan
- Prior art keywords
- polyester
- component
- acid
- group
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920000728 polyester Polymers 0.000 title claims description 90
- 239000000203 mixture Substances 0.000 title claims description 35
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 60
- -1 phosphorus compound Chemical class 0.000 claims description 43
- 125000004432 carbon atom Chemical group C* 0.000 claims description 27
- 125000003118 aryl group Chemical group 0.000 claims description 23
- 229920000642 polymer Polymers 0.000 claims description 23
- 238000006116 polymerization reaction Methods 0.000 claims description 22
- 239000007795 chemical reaction product Substances 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims description 17
- 239000011574 phosphorus Substances 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000004593 Epoxy Substances 0.000 claims description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 10
- 125000000524 functional group Chemical group 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 4
- 230000001588 bifunctional effect Effects 0.000 claims 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 26
- 239000011734 sodium Substances 0.000 description 23
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 20
- 238000000034 method Methods 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 238000009987 spinning Methods 0.000 description 15
- 239000000975 dye Substances 0.000 description 13
- 238000006068 polycondensation reaction Methods 0.000 description 13
- 125000002091 cationic group Chemical group 0.000 description 12
- 239000010408 film Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 230000007062 hydrolysis Effects 0.000 description 11
- 238000006460 hydrolysis reaction Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229910001873 dinitrogen Inorganic materials 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 238000005809 transesterification reaction Methods 0.000 description 10
- YZTJKOLMWJNVFH-UHFFFAOYSA-N 2-sulfobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1S(O)(=O)=O YZTJKOLMWJNVFH-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000835 fiber Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 9
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000007334 copolymerization reaction Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 238000002074 melt spinning Methods 0.000 description 5
- 125000002877 alkyl aryl group Chemical group 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- SYSFRXFRWRDPIJ-UHFFFAOYSA-N 2-hexylbenzenesulfonic acid Chemical compound CCCCCCC1=CC=CC=C1S(O)(=O)=O SYSFRXFRWRDPIJ-UHFFFAOYSA-N 0.000 description 3
- QQBZFCFCMKHPPC-UHFFFAOYSA-N 2-pentadecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O QQBZFCFCMKHPPC-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 3
- 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 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- VPGSXIKVUASQIY-UHFFFAOYSA-N 1,2-dibutylnaphthalene Chemical compound C1=CC=CC2=C(CCCC)C(CCCC)=CC=C21 VPGSXIKVUASQIY-UHFFFAOYSA-N 0.000 description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-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
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 229940077388 benzenesulfonate Drugs 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000008569 process Effects 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
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- NMUWSGQKPAEPBA-UHFFFAOYSA-N 1,2-dibutylbenzene Chemical compound CCCCC1=CC=CC=C1CCCC NMUWSGQKPAEPBA-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
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- QTVONDYLMOEYFA-UHFFFAOYSA-N 2,6-bis(2-hydroxyethoxycarbonyl)benzenesulfonic acid Chemical compound OCCOC(=O)C1=CC=CC(C(=O)OCCO)=C1S(O)(=O)=O QTVONDYLMOEYFA-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
- QFNSAOSWJSCHID-UHFFFAOYSA-N 2-butylbenzenesulfonic acid Chemical compound CCCCC1=CC=CC=C1S(O)(=O)=O QFNSAOSWJSCHID-UHFFFAOYSA-N 0.000 description 1
- WHNBDXQTMPYBAT-UHFFFAOYSA-N 2-butyloxirane Chemical compound CCCCC1CO1 WHNBDXQTMPYBAT-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- NJWSNNWLBMSXQR-UHFFFAOYSA-N 2-hexyloxirane Chemical compound CCCCCCC1CO1 NJWSNNWLBMSXQR-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-M 2-methylbenzenesulfonate Chemical compound CC1=CC=CC=C1S([O-])(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-M 0.000 description 1
- AAMHBRRZYSORSH-UHFFFAOYSA-N 2-octyloxirane Chemical compound CCCCCCCCC1CO1 AAMHBRRZYSORSH-UHFFFAOYSA-N 0.000 description 1
- SYURNNNQIFDVCA-UHFFFAOYSA-N 2-propyloxirane Chemical compound CCCC1CO1 SYURNNNQIFDVCA-UHFFFAOYSA-N 0.000 description 1
- YMTCDSQBRGXFML-UHFFFAOYSA-N 2-tert-butylbenzenesulfonic acid Chemical compound CC(C)(C)C1=CC=CC=C1S(O)(=O)=O YMTCDSQBRGXFML-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
- 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
- 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 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
- DSESLCMEGOXDGW-UHFFFAOYSA-M 3,5-bis(methoxycarbonyl)benzenesulfonate;tributyl(ethyl)phosphanium Chemical compound CCCC[P+](CC)(CCCC)CCCC.COC(=O)C1=CC(C(=O)OC)=CC(S([O-])(=O)=O)=C1 DSESLCMEGOXDGW-UHFFFAOYSA-M 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
- 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
- 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
- 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
- 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 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
- DTCICGXXTMQWMA-UHFFFAOYSA-M C(CCC)[P+](CCCC)(CCCC)CCCC.COC1=C(C=CC=C1)S(=O)(=O)[O-] Chemical compound C(CCC)[P+](CCCC)(CCCC)CCCC.COC1=C(C=CC=C1)S(=O)(=O)[O-] DTCICGXXTMQWMA-UHFFFAOYSA-M 0.000 description 1
- NDFAPYQDFURLEB-UHFFFAOYSA-L C1(=CC=CC=C1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1.C(=O)([O-])C=1C=C(C=CC1)S(=O)(=O)[O-].C1(=CC=CC=C1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1.C(=O)([O-])C=1C=C(C=CC1)S(=O)(=O)[O-].C1(=CC=CC=C1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 NDFAPYQDFURLEB-UHFFFAOYSA-L 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- ZZXDRXVIRVJQBT-UHFFFAOYSA-M Xylenesulfonate Chemical compound CC1=CC=CC(S([O-])(=O)=O)=C1C ZZXDRXVIRVJQBT-UHFFFAOYSA-M 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- HHFLORIUWMQJMT-UHFFFAOYSA-N [PH4+].[PH4+].[O-]P([O-])=O Chemical compound [PH4+].[PH4+].[O-]P([O-])=O HHFLORIUWMQJMT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000007860 aryl ester derivatives Chemical class 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- IKNWWJMESJSJDP-UHFFFAOYSA-N benzyl(tributyl)phosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CC1=CC=CC=C1 IKNWWJMESJSJDP-UHFFFAOYSA-N 0.000 description 1
- YSABSOUZBCDJCR-UHFFFAOYSA-M benzyl(tributyl)phosphanium;3,5-bis(methoxycarbonyl)benzenesulfonate Chemical compound COC(=O)C1=CC(C(=O)OC)=CC(S([O-])(=O)=O)=C1.CCCC[P+](CCCC)(CCCC)CC1=CC=CC=C1 YSABSOUZBCDJCR-UHFFFAOYSA-M 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
- XDTWVRJRJYVXTB-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;3,5-bis(methoxycarbonyl)benzenesulfonate 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)(C=1C=CC=CC=1)CC1=CC=CC=C1 XDTWVRJRJYVXTB-UHFFFAOYSA-M 0.000 description 1
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical compound CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 description 1
- BNMJSBUIDQYHIN-UHFFFAOYSA-N butyl dihydrogen phosphate Chemical compound CCCCOP(O)(O)=O BNMJSBUIDQYHIN-UHFFFAOYSA-N 0.000 description 1
- BEVHTMLFDWFAQF-UHFFFAOYSA-N butyl(triphenyl)phosphanium Chemical class C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 BEVHTMLFDWFAQF-UHFFFAOYSA-N 0.000 description 1
- JHPRWPIHJBDGSI-UHFFFAOYSA-K butyl(triphenyl)phosphanium 5-sulfonatobenzene-1,3-dicarboxylate Chemical compound [O-]C(=O)c1cc(cc(c1)S([O-])(=O)=O)C([O-])=O.CCCC[P+](c1ccccc1)(c1ccccc1)c1ccccc1.CCCC[P+](c1ccccc1)(c1ccccc1)c1ccccc1.CCCC[P+](c1ccccc1)(c1ccccc1)c1ccccc1 JHPRWPIHJBDGSI-UHFFFAOYSA-K 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- XDRMBCMMABGNMM-UHFFFAOYSA-N ethyl benzenesulfonate Chemical compound CCOS(=O)(=O)C1=CC=CC=C1 XDRMBCMMABGNMM-UHFFFAOYSA-N 0.000 description 1
- ZJXZSIYSNXKHEA-UHFFFAOYSA-L ethyl phosphate(2-) Chemical compound CCOP([O-])([O-])=O ZJXZSIYSNXKHEA-UHFFFAOYSA-L 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 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
- CACRRXGTWZXOAU-UHFFFAOYSA-N octadecane-1-sulfonic acid Chemical compound CCCCCCCCCCCCCCCCCCS(O)(=O)=O CACRRXGTWZXOAU-UHFFFAOYSA-N 0.000 description 1
- WLGDAKIJYPIYLR-UHFFFAOYSA-N octane-1-sulfonic acid Chemical compound CCCCCCCCS(O)(=O)=O WLGDAKIJYPIYLR-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 description 1
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229940071104 xylenesulfonate Drugs 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ポリエステル組成物お
よびその製造方法に関する。さらに詳しくは、耐加水分
解性、溶融時または乾燥時の耐熱性および色相に優れ、
異物が少なく、成形性および品質に優れたポリエステル
組成物およびその製造方法に関する。さらに、本発明は
カチオン可染ポリエステルにおいて溶融時または乾燥時
の耐熱性および色相に優れた改質ポリエステル組成物お
よびその製造方法に関する。FIELD OF THE INVENTION The present invention relates to a polyester composition and a method for producing the same. More specifically, it has excellent hydrolysis resistance, heat resistance during melting or drying, and hue,
The present invention relates to a polyester composition having less foreign matter and excellent in moldability and quality, and a method for producing the same. Furthermore, the present invention relates to a modified polyester composition having excellent heat resistance and hue when melted or dried in a cationic dyeable polyester, and a method for producing the same.
【０００２】[0002]
【従来の技術】ポリエステル、特にポリエチレンテレフ
タレートは多くの優れた特性を有しているため、種々の
用途、特に繊維、フィルムに広く利用されている。かか
るポリエステルは、通常テレフタル酸とエチレングリコ
ールとをエステル化反応せしめるか、テレフタル酸ジア
ルキルとエチレングリコールとをエステル交換反応せし
めるか、またはテレフタル酸とエチレンオキサイドとを
反応せしめるかして、テレフタル酸のエチレングリコー
ルエステル及び／又はその低重合体を生成せしめ、次い
でこの生成物を減圧下加熱して所定の重合度になるまで
重縮合反応せしめることによって製造されている。BACKGROUND OF THE INVENTION Polyesters, especially polyethylene terephthalate, have many excellent properties and are therefore widely used in various applications, especially in fibers and films. Such polyesters are usually prepared by esterifying terephthalic acid with ethylene glycol, transesterifying dialkyl terephthalate with ethylene glycol, or reacting terephthalic acid with ethylene oxide to give ethylene of terephthalic acid. It is produced by forming a glycol ester and / or a low polymer thereof, and then heating the product under reduced pressure to cause a polycondensation reaction until a predetermined degree of polymerization is reached.
【０００３】このようにして得られたポリエステルは、
溶融状態で微細な孔（紡糸孔）またはスリットから繊維
状またはフィルム状に押出し、次いで延伸して実用化さ
れる。ポリエステルはその製造工程時に重縮合反応時及
び形成工程において、高温下溶融状態で長時間保持され
ることが多く、その間の熱分解を防止し、品質特に色調
の良好なポリエステル成形物を得るため種々の燐化合
物、例えば燐酸、亜燐酸、これらの低級アルキルエステ
ル、アリールエステル等が一般に使用されている。The polyester thus obtained is
It is put into practical use by extruding it in a molten state from fine holes (spinning holes) or slits into a fibrous or film shape, and then stretching. Polyester is often kept in a molten state at a high temperature for a long time during the polycondensation reaction during the production process and during the formation process, and in order to prevent thermal decomposition during that period and to obtain a polyester molded product with good quality, especially a good color tone. Phosphorus compounds such as phosphoric acid, phosphorous acid, lower alkyl esters and aryl esters thereof are generally used.
【０００４】しかしながら、耐熱性および色調に関し
て、未だ充分に満足しうるポリエステルは得られておら
ず、なお一層の改良が要望されている。一方ポリエステ
ル成形物は、湿熱条件下で使用されることも多く、この
場合加水分解による強度の低下、色相の劣化などが問題
となっている。この問題を解決するため、従来ポリエス
テルの末端ＣＯＯＨ基を減少させる方法（特公昭４４−
２７９１１号公報、特開昭５４−６０５１号公報参
照）、ポリエステル中にカルボジイミド化合物を添加す
る方法（特公昭３８−１５２２０号公報、特公昭４６−
５３８９号公報参照）などが提案されているが、これら
の方法はいずれも湿熱条件によって未だ満足すべきもの
とは云えなかった。However, polyesters which are sufficiently satisfactory in heat resistance and color tone have not yet been obtained, and further improvement is demanded. On the other hand, polyester molded products are often used under wet heat conditions, and in this case, there are problems such as reduction in strength due to hydrolysis and deterioration in hue. In order to solve this problem, the conventional method of reducing the terminal COOH groups of polyester (Japanese Patent Publication No.
No. 27911, JP-A No. 54-6051), a method of adding a carbodiimide compound to polyester (Japanese Patent Publication No. 38-15220, Japanese Patent Publication No. 46-46).
(See Japanese Patent No. 5389), but none of these methods can be said to be satisfactory depending on the wet heat conditions.
【０００５】さらにポリエステル中には、微細な不溶性
異物が存在するが、これらを分析するとその多くは使用
したエステル交換触媒、重合触媒、安定剤からなる粒子
であることが判った。これらの不溶性異物は、ポリエス
テルの成形工程、特に繊維状またはフィルム状に押し出
す際および延伸する際に種々のトラブルを引きおこす。
特に、最近、ポリエステルよりなる繊維、フィルムには
ファインデニール化、薄物化、高級化等の要求が多く、
また生産性向上のため紡糸、成形等の速度を高速化する
ことが試みられているが、上記不溶性異物の生成はいず
れの場合にも重大な障害になる。Further, fine insoluble foreign matters are present in the polyester, and it was found that most of them were particles composed of the used transesterification catalyst, polymerization catalyst and stabilizer. These insoluble foreign matters cause various troubles during the molding process of polyester, particularly when extruding into a fiber or film and stretching.
In particular, recently, there have been many demands for fine denier, thinning, and higher quality of polyester fibers and films.
Further, in order to improve productivity, attempts have been made to increase the speed of spinning, molding, etc., but the formation of the insoluble foreign matter is a serious obstacle in any case.
【０００６】一方、ポリエステルは多くの優れた特性を
有しているため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
困難であり、その改善が求められていた。染色性を改良
する方法としては、例えばポリエステル主鎖中に、５−
Ｎａスルホイソフタル酸の如きスルホン酸金属塩基を有
するイソフタル酸成分を共重合することによってカチオ
ン染料で染色可能とする方法が古くから知られている
（特公昭３４−１０４９７号公報参照）。しかしなが
ら、この方法ではカチオン染料で染色した際の濃色性や
鮮明発色性が不充分であるのみならず、該成分の共重合
によってポリマーの溶融粘度が著しく増大し、重合度を
充分に上げることが困難になると同時に紡糸等の成形が
困難となるため低強度の成形物しか得られない欠点があ
った。On the other hand, polyester is widely used as a fiber or a film because it has many excellent properties, but it has a low dyeing property, and it is difficult to dye especially dyes other than disperse dyes, and its improvement is It was wanted. As a method for improving the dyeability, for example, in the polyester main chain, 5-
A method for dyeing with a cationic dye by copolymerizing an isophthalic acid component having a sulfonic acid metal base such as Na sulfoisophthalic acid has long been known (see Japanese Patent Publication No. 34-10497). However, with this method, the dark color when dyed with a cationic dye and
Not only the vivid color development is insufficient, but also the melt viscosity of the polymer is remarkably increased by the copolymerization of the components, making it difficult to sufficiently raise the degree of polymerization, and at the same time, it is difficult to form such as spinning, resulting in low strength. There was a drawback that only the molded product of
【０００７】かかるカチオン染料可染性ポリエステルの
欠点を解消するため、特定の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を共重合した改質ポリエス
テルの製造法および改質ポリエステル繊維が開示されて
いる（特公平３−６１７６６号公報参照）。この方法に
よれば、ポリマーの増粘作用が抑制されるため、高重合
度でかつ低溶融粘度のポリエステルが容易に得られ、高
強度の成形物が製造できるようになるだけでなく、カチ
オン染料で染色した際の濃色性や鮮明発色性が改良され
る。しかしながら、耐熱性および色相の面で未だ充分に
満足しうるカチオン可染化ポリエステルは得られておら
ず、なお一層の改良が望まれている。In order to solve the drawbacks of such a polyester dyeable with a cationic dye, a method for producing a modified polyester obtained by copolymerizing an isophthalic acid component having a specific phosphonium sulfonate group, and a modified polyester fiber are disclosed. (See Japanese Patent Publication No. 3-61766). According to this method, since the thickening action of the polymer is suppressed, a polyester having a high polymerization degree and a low melt viscosity can be easily obtained, and not only a high-strength molded article can be produced, but also a cationic dye. The deep color and vivid color development when dyed with are improved. However, a cationic dyeable polyester which is sufficiently satisfactory in terms of heat resistance and hue has not been obtained yet, and further improvement is desired.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、前記ポリエ
ステル成形物およびその製造工程に基づく問題点を解消
すべくなされたものであり、その第１の目的は、耐加水
分解性、溶融並びに乾燥時に耐熱性および色相に優れ、
且つポリマー中の不溶性異物の量が少なく、成形性並び
に品質が改良されたポリエステル組成物およびその製造
方法を提供することにある。SUMMARY OF THE INVENTION The present invention has been made to solve the problems associated with the above-mentioned polyester molded product and the manufacturing process thereof, and the first object thereof is hydrolysis resistance, melting and drying. Sometimes excellent in heat resistance and hue,
Another object of the present invention is to provide a polyester composition having a small amount of insoluble foreign matter in the polymer, improved moldability and quality, and a method for producing the same.
【０００９】さらに本発明の第２の目的は、前記したカ
チオン染料により濃色かつ鮮明に染色可能であると共
に、耐熱性および色相の面でも良好であり、通常の未改
質ポリエステル繊維と同等の強度を有するカチオン染料
可染性ポリエステル繊維を製造することができる改質ポ
リエステル組成物およびその製造方法を提供することに
ある。A second object of the present invention is that it can be dyed deeply and vividly with the above-mentioned cationic dye, and that it is also excellent in heat resistance and hue, and is equivalent to ordinary unmodified polyester fibers. It is an object of the present invention to provide a modified polyester composition capable of producing a cationic dye-dyeable polyester fiber having strength and a method for producing the same.
【００１０】[0010]
【課題を解決するための手段】本発明者は、前記本発明
の目的を達成するため研究を重ねた結果、安定剤として
使用するリン化合物の種類がポリエステルの耐加水分解
性、耐熱性、色相およ不溶性異物の量に大きく影響し、
或る特定のリン化合物を使用することにより、これら特
性を大幅に向上させることができることを見出し、本発
明に到達した。すなわち、本発明によれば（Ａ）芳香族
ポリエステル（Ａ成分）に（Ｂ）下記一般式［Ｉ］で表
わされるリン化合物と下記一般式［ＩＩ］で表わされる
エポキシ化合物との反応生成物（Ｂ成分）を配合させて
なる芳香族ポリエステル組成物が提供される。Means for Solving the Problems As a result of repeated studies for achieving the above-mentioned object of the present invention, the present inventors have found that the type of phosphorus compound used as a stabilizer is hydrolysis resistance, heat resistance and hue of polyester. And greatly affect the amount of insoluble foreign matter,
The present inventors have found that the use of a specific phosphorus compound can significantly improve these properties, and have arrived at the present invention. That is, according to the present invention, a reaction product of (A) an aromatic polyester (A component) with (B) a phosphorus compound represented by the following general formula [I] and an epoxy compound represented by the following general formula [II] ( Provided is an aromatic polyester composition containing B component).
【００１１】[0011]
【化４】 [Chemical 4]
【００１２】［式中、Ｒ1、Ｒ2およびＲ3は、それぞれ
同一または異なり、水素原子、炭素原子数１〜４のアル
キル基または炭素原子数６〜１２のアリール基を示
す。］[Wherein R 1 , R 2 and R 3 are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms]. ]
【００１３】[0013]
【化５】 [Chemical 5]
【００１４】［式中、ｌ1、ｌ2およびｌ3は、それぞれ
同一または異なり、水素原子または炭素原子数１〜４の
アルキル基を示し、ｌ4は炭素原子数１〜１５のアルキ
ル基または炭素原子数６〜１２のアリール基を示す。］[Wherein l 1 , l 2 and l 3 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and l 4 is an alkyl group having 1 to 15 carbon atoms or An aryl group having 6 to 12 carbon atoms is shown. ]
【００１５】さらに本発明によれば、二官能性芳香族カ
ルボン酸及び／又はそのエステル形成性誘導体と、アル
キレングリコール及び／又はそのエスルテ形成性誘導体
とを反応せしめて二官能性芳香族カルボン酸のグリコー
ルエステル及び／又はその低重合体を生成させ、次いで
重合反応せしめてポリエステルを製造するに際し、前記
Ｂ成分を、ポリエステルの重合が終了するまでの任意の
時期に添加することを特徴とする芳香族ポリエステル組
成物の製造方法が提供される。Further, according to the present invention, a difunctional aromatic carboxylic acid and / or an ester-forming derivative thereof is reacted with an alkylene glycol and / or an ester forming derivative thereof to form a difunctional aromatic carboxylic acid. An aromatic compound characterized in that, when a polyester is produced by producing a glycol ester and / or a low polymer thereof and then subjecting it to a polymerization reaction, the component B is added at an arbitrary time until the polymerization of the polyester is completed. A method of making a polyester composition is provided.
【００１６】以下、本発明についてさらに詳細に説明す
る。本発明においてポリエステル（Ａ成分）としては、
二官能性芳香族カルボン酸を主たる酸成分とし、アルキ
レングリコールを主たるジオール成分とするポリエステ
ルを主たる対象とする。好ましく用いられる二官能性芳
香族カルボン酸としては、例えばテレフタル酸、イソフ
タル酸、ナフタレンジカルボン酸、ジフェニルカルボン
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−オキシ安息香酸等をあげること
ができ、また、アルキレングコリールとしては、例えば
エチレングリコール、トリメチレングリコール、テトラ
メチレングリコール等を挙げることができる。なかで
も、主たる酸成分がテレフタル酸であり、主たるグリコ
ール成分がエチレングリコールであるポリエチレンテレ
フタレート系ポリエステルが好ましい。The present invention will be described in more detail below. In the present invention, as the polyester (component A),
The main target is a polyester containing a difunctional aromatic carboxylic acid as a main acid component and an alkylene glycol as a main diol component. Examples of the difunctional aromatic carboxylic acid preferably used include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenylcarboxylic acid, diphenoxyethanedicarboxylic acid, β-hydroxyethoxybenzoic acid, p-oxybenzoic acid and the like. Further, examples of the alkylene gukoril include ethylene glycol, trimethylene glycol, tetramethylene glycol and the like. Among them, a polyethylene terephthalate polyester whose main acid component is terephthalic acid and whose main glycol component is ethylene glycol is preferable.
【００１７】また、上述の「主たる」とは、二官能性芳
香族カルボン酸以外の二官能性カルボン酸成分及び／又
はアルキレングリコール以外のジオール成分を、全酸成
分に対して１５モル％以下、好ましくは１０モル％以
下、特に好ましくは５モル％以下共重合してもよいこと
を意味する。The above-mentioned "main" means that the content of the difunctional carboxylic acid component other than the difunctional aromatic carboxylic acid and / or the diol component other than the alkylene glycol is 15 mol% or less with respect to the total acid component, It means that the copolymerization may preferably be 10 mol% or less, particularly preferably 5 mol% or less.
【００１８】ここで使用される二官能性カルボン酸とし
ては、例えばアジピン酸、セバシン酸、１,４−シクロ
ヘキサンジカルボン酸の如き脂肪族、脂環族の二官能性
カルボン酸を挙げることができ、また、アルキレングリ
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Ａ、ビスフェノールＳの如き脂環
族、芳香族のジオール化合物及びポリオキシアルキレン
グリコールを挙げることができる。Examples of the difunctional carboxylic acid used here include aliphatic and alicyclic difunctional carboxylic acids such as adipic acid, sebacic acid, and 1,4-cyclohexanedicarboxylic acid. Examples of the diol compound other than the alkylene glycol include cyclohexane-1,4-dimethanol, neopentyl glycol, alicyclic and aromatic diol compounds such as bisphenol A and bisphenol S, and polyoxyalkylene glycol. it can.
【００１９】さらに、本発明の効果が実質的に損なわれ
ない範囲内で、５−ナトリウムスルホイソフタル酸の如
きスルホン酸塩基を有するイソフタル酸、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
如きポリオールを共重合成分として用いてもよい。Further, polyphthalic acid such as isophthalic acid having a sulfonate group such as 5-sodiumsulfoisophthalic acid, trimellitic acid and pyromellitic acid, and glycerin within a range in which the effects of the present invention are not substantially impaired. A polyol such as trimethylolpropane or pentaerythritol may be used as a copolymerization component.
【００２０】かかるポリエステルは任意の方法によって
合成される。例えばポリエチレンテレフタレートについ
て説明すれば、通常、テレフタル酸とエチレングリコー
ルとを直接エステル化反応させるか、テレフタル酸ジメ
チルの如きテレフタル酸の低級アルキルエステルとエチ
レングリコールとをエステル交換反応させるか又はテレ
フタル酸とエチレンオキサイドとを反応させるかしてテ
レフタル酸のグリコールエステル及び／又はその低重合
体を生成させる第一段階の反応と、第一段階の反応生成
物を重合触媒の存在下で減圧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。The polyester can be synthesized by any method. For example, polyethylene terephthalate will be described. Usually, terephthalic acid and ethylene glycol are directly esterified, or a lower alkyl ester of terephthalic acid such as dimethyl terephthalate is transesterified with ethylene glycol, or terephthalic acid and ethylene glycol are used. The reaction in the first step of reacting with oxide to produce a glycol ester of terephthalic acid and / or its low polymer and heating the reaction product in the first step under reduced pressure in the presence of a polymerization catalyst It is produced by a second stage reaction in which a polycondensation reaction is carried out until the degree of polymerization is reached.
【００２１】本発明において前記芳香族ポリエステル
（Ａ成分）に配合されるのは、前記一般式［Ｉ］で表わ
されるリン化合物（Ｂ−１成分）と前記一般式［ＩＩ］
で表わされるエポキシ化合物（Ｂ−２成分）との反応生
成物（Ｂ成分）である。このＢ成分の合成に使用される
一般式［Ｉ］のリン化合物の具体例としては、正リン
酸、リン酸モノメチル、リン酸モノエチル、リン酸モノ
ブチル、リン酸トリメチル、リン酸トリエチル、リン酸
トリブチル、リン酸モノフェニルおよびリン酸トリフェ
ニル等が挙げられ、これらは２種以上の混合物であって
もよい。In the present invention, the aromatic compound (component A) is blended with the phosphorus compound (component B-1) represented by the general formula [I] and the general formula [II].
It is a reaction product (component B) with the epoxy compound (component B-2) represented by. Specific examples of the phosphorus compound of the general formula [I] used for the synthesis of the component B include orthophosphoric acid, monomethyl phosphate, monoethyl phosphate, monobutyl phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate. , Monophenyl phosphate, triphenyl phosphate and the like, and these may be a mixture of two or more kinds.
【００２２】また一般式［ＩＩ］のエポキシ化合物（Ｂ
−２成分）としては、ｌ1、ｌ2およびｌ3はそれぞれ同
一もしくは異なり、水素原子または炭素原子数１〜４の
アルキル基であり、好ましくは水素原子である。またｌ
4は炭素原子数１〜１５、好ましくは１〜１０のアルキ
ル基または炭素原子数６〜１２のアリール基好ましくは
フェニル基である。これらは基の間にエーテル結合を有
していてもよい。かかるエポキシ化合物の具体例として
は、例えば１,２−エポキシプロパン、１,２−エポキシ
ブタン、１,２−エポキシペンタン、１,２−エポキシヘ
キサン、１,２−エポキシオクタン、１,２−エポキシノ
ナンおよび１,２−エポキシデカンが挙げられるがこれ
らは２種以上の混合物であってもよい。The epoxy compound (B) of the general formula [II]
-2 component), l 1 , l 2 and l 3 are the same or different and each is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom. Also l
4 is an alkyl group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, preferably a phenyl group. These may have an ether bond between groups. Specific examples of such an epoxy compound include, for example, 1,2-epoxypropane, 1,2-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyoctane, 1,2-epoxy. Nonane and 1,2-epoxydecane are mentioned, but these may be a mixture of two or more kinds.
【００２３】前記リン化合物（Ｂ−１成分）とエポキシ
化合物（Ｂ−２成分）との反応生成物を得る反応条件
は、リン化合物（Ｂ−１成分）を７０〜１３０℃、好ま
しくは８０〜１２０℃の温度に加熱し、そこにエポキシ
化合物（Ｂ−２成分）を、滴下終了後、反応混合物を１
〜７時間、好ましくは２〜６時間加温を続行するのが望
ましい。反応温度が７０℃より低いと、反応が充分に進
行せず、一方１３０℃を超えると反応が急激になり危険
であるばかりでなく、反応生成物が着色するので好まし
くない。加熱反応時間が１時間未満の場合反応が充分に
進まず、一方、７時間を超えると、反応生成物が着色す
る傾向かある。Ｂ−１成分とＢ−２成分の反応割合はモ
ル比で１：１〜１：５、好ましくは１：２〜１：４の範
囲が有利である。The reaction conditions for obtaining the reaction product of the phosphorus compound (B-1 component) and the epoxy compound (B-2 component) are 70 to 130 ° C., preferably 80 to 130 ° C. for the phosphorus compound (B-1 component). After heating to a temperature of 120 ° C. and adding an epoxy compound (B-2 component) thereto, the reaction mixture was mixed with 1
It is desirable to continue heating for ~ 7 hours, preferably 2-6 hours. If the reaction temperature is lower than 70 ° C., the reaction does not proceed sufficiently, while if it exceeds 130 ° C., the reaction becomes abrupt and dangerous, and the reaction product is colored, which is not preferable. If the heating reaction time is less than 1 hour, the reaction does not proceed sufficiently, while if it exceeds 7 hours, the reaction product tends to be colored. The reaction ratio of the component B-1 and the component B-2 is in a molar ratio range of 1: 1 to 1: 5, preferably 1: 2 to 1: 4.
【００２４】かくして得られたＢ−１成分とＢ−２成分
の反応生成物（Ｂ成分）は、ポリエステル（Ａ成分）に
配合されるが、好ましい方法はポリエステル製造が終了
する任意の段階にＢ成分をその製造工程に添加すること
である。好ましい添加時期はエステル化或いはエステル
交換反応によって低重合体を生成した後、すなわち重縮
合反応の前、或いは中に添加するのが有利である。Ｂ成
分の配合割合は触媒金属配合割合にもよるが、リン含量
としてポリエステル１００重量部当り、０.０００５〜
０.２重量部、好ましくは０.００２〜０.１５重量部の
範囲が適当である。Ｂ成分の配合割合が、ポリエステル
１００重量部当り０.０００５重量部より少ないと、添
加効果がなく、一方０.２重量部を超えると、それ以上
添加しても添加効果が増大するわけではなく、むしろ不
経済となる。The reaction product of the B-1 component and the B-2 component (component B) thus obtained is blended with the polyester (component A), but the preferred method is B at any stage where the polyester production is completed. Adding ingredients to the manufacturing process. It is advantageous to add it after the low polymer is produced by the esterification or transesterification reaction, that is, before or during the polycondensation reaction. The blending ratio of the component B depends on the blending ratio of the catalyst metal, but is 0.0005 to 100 parts by weight of polyester as the phosphorus content.
A range of 0.2 parts by weight, preferably 0.002 to 0.15 parts by weight is suitable. If the blending ratio of the component B is less than 0.0005 parts by weight per 100 parts by weight of polyester, the addition effect is not obtained, while if it exceeds 0.2 parts by weight, the addition effect does not increase even if it is added more. , Rather uneconomical.
【００２５】さらに本発明者らの研究によれば、前記し
た本発明のポリエステル組成物およびその製造方法は、
通常のポリエステルにおいて前記目的および効果が達成
されるが、或る特定のスルホン酸ホスホニウム塩を共重
合して得られた改質ポリエステルにおいても優れた効
果、すなわちカチオン染料可染性を有している共に、耐
熱性および色相が良好であるという効果が達成できるこ
とが見出された。Further, according to the study by the present inventors, the above-mentioned polyester composition of the present invention and a method for producing the same are
Although the above-mentioned objects and effects are achieved in a normal polyester, the modified polyester obtained by copolymerizing a specific phosphonium sulfonate has an excellent effect, that is, a cationic dye dyeability. Both have been found to be able to achieve the effects of good heat resistance and good hue.
【００２６】すなわち、本発明によれば、前記芳香族ポ
リエステル（Ａ成分）として、下記一般式［ＩＩＩ］That is, according to the present invention, as the aromatic polyester (component A), the following general formula [III]
【００２７】[0027]
【化６】 [Chemical 6]
【００２８】［式中、Ａは芳香族基または脂肪族基であ
り、Ｘ1はエステル形成性官能基であり、Ｘ2はＸ1と同
一若しくは異なるエステル形成性官能基または水素原子
であり、Ｑ1、Ｑ2、Ｑ3およびＱ4のそれぞれは、アルキ
ル基およびアリール基よりなる群から選ばれる同一また
は異なる基であり、そして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、ポリエステルを
形成する二官能性芳香族カルボン酸成分に対して０.１
〜１０モル％共重合した改質芳香族ポリエステルを使用
した改質ポリエステル組成物も提供される。[In the formula, A is an aromatic group or an aliphatic group, X 1 is an ester-forming functional group, X 2 is the same or different from X 1 , an ester-forming functional group or a hydrogen atom, Each of Q 1 , Q 2 , Q 3 and Q 4 is the same or different group selected from the group consisting of an alkyl group and an aryl group, and n represents a positive integer. ] The sulfonic acid phosphonium salt represented by the above formula is added to the difunctional aromatic carboxylic acid component forming the polyester in an amount of 0.1.
Modified polyester compositions using modified aromatic polyesters copolymerized at -10 mol% are also provided.
【００２９】かかる改質ポリエステル組成物は、前記し
たポリエステルの合成が完了する以前の任意の段階で、
好ましくは第二段階の反応の初期以前の任意の段階で添
加すればよい。一般式［ＩＩＩ］の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は、ポリエス
テルを構成する酸成分（スルホン酸ホスホニウム塩を除
く）に対して０.１〜１０モル％の範囲であり、０.５〜
５モル％の範囲が好ましい。共重合割合が０.１モル％
より少ないと、得られる改質ポリエステル組成物をカチ
オン染料で染色した際の濃色性や鮮明発色性が不充分に
なり、１０モル％より多くなると濃色性や鮮明発色性は
最早著しい向上を示さず、かえって改質ポリエステル組
成物の物性が低下する。Such a modified polyester composition may be prepared at any stage before the completion of the above polyester synthesis,
Preferably, it may be added at any stage before the beginning of the second stage reaction. The proportion of the sulfonic acid phosphonium salt of the general formula [III] to be copolymerized with the polyester is in the range of 0.1 to 10 mol% with respect to the acid component (excluding the phosphonic acid phosphonium salt) constituting the polyester, and is 0.1. 5-
A range of 5 mol% is preferred. Copolymerization ratio is 0.1 mol%
When the amount is less, the darkness and vivid coloration when the obtained modified polyester composition is dyed with a cationic dye is insufficient, and when it is more than 10 mol%, the darkness and vivid coloration are improved remarkably. Not shown, and the physical properties of the modified polyester composition are rather deteriorated.
【００３０】前記一般式［ＩＩＩ］において、Ａは芳香
族基または脂肪族基を示し、なかでも芳香族基（好まし
くは炭素原子数６〜１５）が好ましい。Ｘ1はエステル
形成性官能基を示し、具体例としてIn the above general formula [III], A represents an aromatic group or an aliphatic group, and among them, an aromatic group (preferably having 6 to 15 carbon atoms) is preferable. X 1 represents an ester-forming functional group, and as a specific example,
【００３１】[0031]
【化７】 [Chemical 7]
【００３２】（但し、Ｒ'は低級アルキル基またはフェ
ニル基を示し、ａおよびｄは１以上の整数、ｂは２以上
の整数である）等を挙げることができる。Ｘ2はＸ1と同
一もしくは異なるエステル形成性官能基または水素原子
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。(However, R'represents a lower alkyl group or a phenyl group, a and d are integers of 1 or more, and b is an integer of 2 or more) and the like. X 2 represents an ester-forming functional group which is the same as or different from X 1 , or a hydrogen atom, and is preferably an ester-forming functional group.
【００３３】Ｑ1、Ｑ2、Ｑ3およびＱ4はアルキル基（好
ましくは炭素原子数１〜６）およびアリール基（好まし
くは炭素原子数６〜１５）よりなる群から選ばれた同一
または異なる基を示す。ｎは正の整数（好ましくは１〜
３）である。Q 1 , Q 2 , Q 3 and Q 4 are the same or different selected from the group consisting of an alkyl group (preferably having 1 to 6 carbon atoms) and an aryl group (preferably having 6 to 15 carbon atoms). Indicates a group. n is a positive integer (preferably 1 to
3).
【００３４】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、または
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 a phosphonium sulfonate salt can generally be easily synthesized by reacting a corresponding sulfonic acid with a phosphine, or by reacting a corresponding metal sulfonate with a phosphonium halide.
【００３５】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
シベンセ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−ヒドロキシエトキシ
ベンゼンスルホン酸テトラブチルホスホニウム塩、２,
６−ジカルボキシナフタレン−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
ルホコハク酸等を挙げることができる。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 above-mentioned phosphonium sulfonate include 3,5-dicarboxybenzenesulfonic acid tetrabutylphosphonium salt, 3,5-dicarboxybenzene sulfonic acid ethyltributylphosphonium salt and 3,5-dicarboxybenzene. Benzyl tributylphosphonium sulfonate, 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-dicarbocarbonate Methoxybenzenesulfonic acid tetrabutylphosphonium salt, 3,5-dicarbomethoxybenzenesulfonic acid ethyltributylphosphonium salt, 3,5-dicarbomethoxybenzenesulfonic acid benzyltributylphosphonium salt, 3,5-dicarbomethoxybenzenesulfonic acid phenyl Tributylphosphonium salt, 3,5-dicarbomethoxybenzenesulfonic acid tetraphenylphosphonium salt, 3,5-dicarbomethoxybenzenesulfonic acid ethyl triphenylphosphonium salt, 3,5-dicarbomethoxy Cybenzenesulfonic 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,
Examples thereof include 6-dicarboxynaphthalene-4-sulfonic acid tetrabutylphosphonium salt and α-tetrabutylphosphonium sulfosuccinic acid. The above phosphonium sulfonate salts may be used alone or in combination of two or more.
【００３６】さらに本発明の前記した改質ポリエステル
組成物は、下記一般式［ＩＶ］で表わされる有機スルホ
ン酸金属塩を配合していてもよく、また下記一般式
［Ｖ］で表わされるスルホイソフタル酸金属塩を共重合
していていもよい。
ＹＳＯ3Ｍ ・・・・［ＩＶ］
［式中、Ｙは炭素原子数３〜３０のアルキル基あるいは
炭素原子数６〜４０のアリール基またはアルキルアリー
ル基であり、Ｍはアルカリ金属を示す。］Further, the modified polyester composition of the present invention may contain an organic sulfonic acid metal salt represented by the following general formula [IV], and sulfoisophthale represented by the following general formula [V]. The acid metal salt may be copolymerized. YSO 3 M ... [IV] [In the formula, Y represents an alkyl group having 3 to 30 carbon atoms or an aryl group or alkylaryl group having 6 to 40 carbon atoms, and M represents an alkali metal. ]
【００３７】[0037]
【化８】 [Chemical 8]
【００３８】［式中、Ｚ1およびＺ2は同一または異な
り、水素原子、−（ＣＨ2）n−Ｈまたは−（ＣＨ2）n−
ＯＨ（ここでｎは１〜６の整数を示す）を示し、Ｍはア
ルカリ金属を示す。］[Wherein Z 1 and Z 2 are the same or different and each represents a hydrogen atom,-(CH 2 ) n --H or-(CH 2 ) n-
OH (where n is an integer of 1 to 6), and M is an alkali metal. ]
【００３９】前記一般式［ＩＶ］の有機スルホン酸金属
塩において、Ｙは炭素原子数３〜３０のアルキル基ある
いは炭素原子数６〜４０のアリール基またはアルキルア
リール基であり、Ｍはアルカリ金属を示す。Ｙがアルキ
ル基のときはＹは直鎖状であってもまたは分岐した側鎖
を有していてもよい。Ｙとしては、なかでも炭素原子数
６〜４０のアリール基またはアルキルアリール基がより
大きな効果が奏されるのがより好ましい。Ｙがアルキル
アリール基の場合のアルキルは直鎖状であってもまたは
分岐した側鎖を有していてもよい。ＭはＮａ、Ｋ、Ｌｉ
等のアルカリ金属であり、なかでもＬｉ、ＮａまたはＫ
が好ましい。In the organic sulfonic acid metal salt of the general formula [IV], Y is an alkyl group having 3 to 30 carbon atoms or an aryl group or alkylaryl group having 6 to 40 carbon atoms, and M is an alkali metal. Show. When Y is an alkyl group, Y may be linear or may have a branched side chain. As Y, it is more preferable that an aryl group having 6 to 40 carbon atoms or an alkylaryl group be more effective. When Y is an alkylaryl group, the alkyl may be linear or may have a branched side chain. M is Na, K, Li
Alkali metals such as Li, Na or K
Is preferred.
【００４０】上記式［ＩＶ］で表わされる化合物の好ま
しい具体例としては、ドデシルベンゼンスルホン酸Ｎａ
（ハード型、ソフト型）、ドデシルベンゼンスルホン酸
Ｌｉ（ハード型、ソフト型）、ドデシルベンゼンスルホ
ン酸Ｋ（ハード型、ソフト型）、ペンタデシルベンゼン
スルホン酸Ｎａ、ペンタデシルベンゼンスルホン酸Ｌ
ｉ、ペンタデシルベンゼンスルホン酸Ｋ、ヘキシルベン
ゼンスルホン酸Ｎａ、ヘキシルベンゼンスルホン酸Ｌ
ｉ、ヘキシルベンゼンスルホン酸Ｋ、ｎ−ブチルベンゼ
ンスルホン酸Ｎａ、ｔ−ブチルベンゼンスルホン酸Ｎ
ａ、ジブチルベンゼンスルホン酸Ｎａ、エチルベンゼン
スルホン酸Ｎａ、キシレンスルホン酸Ｎａ、トルエンス
ルホン酸Ｎａ、ベンゼンスルホン酸Ｎａ、ジブチルナフ
タレンスルホン酸Ｎａ、ジブチルナフタレンスルホン酸
Ｌｉ、炭素原子数の平均が１４であるアルキルスルホン
酸Ｎａ混合物、炭素原子数の平均が１５であるアルキル
スルホン酸Ｎａ混合物、炭素原子数の平均が２２である
アルキルスルホン酸Ｎａ混合物、炭素原子数の平均が１
１であるアルキルスルホン酸Ｎａ、炭素原子数の平均が
１２であるアルキルスルホン酸Ｎａ、オクチルスルホン
酸Ｎａ、ブチルスルホン酸Ｎａ、プロピルスルホン酸Ｎ
ａ、ステアリルスルホン酸Ｎａ等を挙げることができ
る。Specific preferred examples of the compound represented by the above formula [IV] include sodium dodecylbenzene sulfonate.
(Hard type, soft type), dodecylbenzene sulfonic acid Li (hard type, soft type), dodecyl benzene sulfonic acid K (hard type, soft type), pentadecyl benzene sulfonic acid Na, pentadecyl benzene sulfonic acid L
i, pentadecylbenzenesulfonic acid K, hexylbenzenesulfonic acid Na, hexylbenzenesulfonic acid L
i, hexylbenzenesulfonic acid K, n-butylbenzenesulfonic acid Na, t-butylbenzenesulfonic acid N
a, Na dibutyl benzene sulfonate, Na ethyl benzene sulfonate, Na xylene sulfonate, Na toluene sulfonate, Na benzene sulfonate, Na dibutyl naphthalene sulfonate, Li dibutyl naphthalene sulfonate, Alkyl having an average number of carbon atoms of 14 Na sulphonate mixture, Na alkyl sulphonate mixture with an average number of carbon atoms of 15, Alkyl sulphonate Na mixture with an average number of carbon atoms of 22, Average number of carbon atoms is 1
1 alkyl sulfonate Na, alkyl sulfonate Na having an average number of carbon atoms of 12, octyl sulfonate Na, butyl sulfonate Na, propyl sulfonate N
a, Na stearyl sulfonate, etc. can be mentioned.
【００４１】一方、一般式［Ｖ］で表わされるスルホイ
ソフタル酸金属塩において、Ｚ1およびＺ2は同一または
異なり、水素原子、−（ＣＨ2）n−Ｈまたは−（Ｃ
Ｈ2）n−ＯＨである。ｎは１〜６の整数であり、好まし
くは１〜４の整数であり、なかでも１または２であるの
が特に好ましい。Ｍはアルカリ金属であり、なかでもＮ
ａ、ＬｉまたはＫが好ましい。On the other hand, in the metal salt of sulfoisophthalic acid represented by the general formula [V], Z 1 and Z 2 are the same or different and each is a hydrogen atom,-(CH 2 ) n --H or-(C
It is a H 2) n -OH. n is an integer of 1 to 6, preferably an integer of 1 to 4, particularly preferably 1 or 2. M is an alkali metal, especially N
Preferred is a, Li or K.
【００４２】上記一般式［Ｖ］で示されるスルホイソフ
タル酸金属塩の好ましい具体例としては、Ｎａスルホイ
ソフタル酸ジメチル、Ｎａスルホイソフタル酸、Ｎａス
ルホイソフタル酸（β−ヒドロキシエチル）、Ｌｉスル
ホイソフタル酸ジメチル、Ｌｉスルホイソフタル酸、Ｌ
ｉスルホイソフタル酸ビス（β−ヒドロキシエチル）、
Ｋスルホイソフタル酸ジメチル、Ｋスルホイソフタル
酸、Ｋスルホイソフタル酸ビス（β−ヒドロキシエチ
ル）、Ｎａスルホイソフタル酸ビス（δ−ヒドロキシブ
チル）等を挙げることができる。Preferred specific examples of the metal salt of sulfoisophthalic acid represented by the above general formula [V] include dimethyl Na sulfoisophthalate, Na sulfoisophthalic acid, Na sulfoisophthalic acid (β-hydroxyethyl) and Li sulfoisophthalic acid. Dimethyl, Li Sulfoisophthalic acid, L
i bis (β-hydroxyethyl) sulfoisophthalate,
Examples include dimethyl Ksulfoisophthalate, Ksulfoisophthalic acid, bis (β-hydroxyethyl) Ksulfoisophthalate, and bis (δ-hydroxybutyl) Nasulfoisophthalate.
【００４３】前記一般式［ＩＶ］及び／又は［Ｖ］で表
わされる化合物は、それぞれ１種のみでもよく、或いは
２種以上を用いてもよい。一般式［ＩＶ］及び／又は
［Ｖ］の化合物の配合量または共重合割合は、一般式
［ＩＩＩ］のスルホン酸ホスホニウム塩に対して１.０
〜１００モル％の範囲が適当であり、なかでも５〜８０
モル％の範囲が好ましい。The compounds represented by the above general formulas [IV] and / or [V] may be used alone or in combination of two or more. The compounding amount or the copolymerization ratio of the compound of the general formula [IV] and / or [V] is 1.0 with respect to the phosphonium sulfonate salt of the general formula [III].
The range of 100 to 100 mol% is suitable, and the range of 5 to 80 is especially preferable.
A range of mol% is preferred.
【００４４】前記一般式［ＩＶ］及び／又は［Ｖ］の化
合物を添加した改質ポリエステルを製造する場合、式
［ＩＶ］の有機スルホン酸金属塩の添加については、改
質ポリエステルの成形が終了するまでの任意の段階、例
えば改質ポリエステルの重縮合反応開始前、重縮合反応
途中、重縮合反応終了時であってまだ溶融状態にある時
点、紛粒状態、成形段階等において、上記有機スルホン
酸金属塩を添加混合することが推奨される。添加に際し
ては１回の操作で添加しても、または２回以上に分割添
加してもよい。また、有機スルホン酸金属塩［ＩＶ］を
予め通常の未改質ポリエステルに配合し、その後成形前
等において、この配合物を改質ポリエステルに混合する
こともできる。さらに、重縮合反応終了前に添加すると
きは、有機スルホン酸金属塩［ＩＶ］をグリコール等の
溶媒に溶解または分散させて添加することもできる。In the case of producing a modified polyester to which the compound of the general formula [IV] and / or [V] is added, regarding the addition of the organic sulfonic acid metal salt of the formula [IV], the molding of the modified polyester is completed. At any stage up to, for example, before starting the polycondensation reaction of the modified polyester, during the polycondensation reaction, at the end of the polycondensation reaction and at the time when it is still in the molten state, powder state, molding step, etc. It is recommended to add and mix the acid metal salt. Upon addition, it may be added in one operation, or may be added in two or more portions. Alternatively, the organic sulfonic acid metal salt [IV] may be mixed in advance with a normal unmodified polyester, and then this mixture may be mixed with the modified polyester before molding or the like. Furthermore, when it is added before the completion of the polycondensation reaction, the organic sulfonic acid metal salt [IV] can be added after being dissolved or dispersed in a solvent such as glycol.
【００４５】また、一般式［Ｖ］で表わされるスルホイ
ソフタル酸金属塩については、重合反応が完了する以前
の任意の段階で、好ましくは第二段階の反応の初期以前
の任意の段階で添加すればよい。The sulfoisophthalic acid metal salt represented by the general formula [V] may be added at any stage before the completion of the polymerization reaction, preferably at any stage before the beginning of the second stage reaction. Good.
【００４６】これら一般式［ＩＶ］および［Ｖ］で表わ
される化合物を添加すると多量のエーテル結合が副生す
ることがあるが、この難点は特開昭４８−６６６５０号
公報、特公昭５３−２８９５５号公報等に開示されたア
ルカリ金属化合物の添加によって回避することができ
る。このようなアルカリ金属化合物の具体例としては、
例えば酢酸ナトリウム、炭酸ナトリウム、ナトリウムメ
トキシド、安息香酸ナトリウム、酢酸リチウム、炭酸リ
チウム、酢酸カリウムおよび炭酸カリウム等を挙げるこ
とができる。When the compounds represented by the general formulas [IV] and [V] are added, a large amount of ether bond may be produced as a by-product, but this difficulty is caused by the problems of JP-A-48-66650 and JP-B-53-28955. This can be avoided by adding the alkali metal compound disclosed in Japanese Patent Publication No. Specific examples of such an alkali metal compound include:
Examples thereof include sodium acetate, sodium carbonate, sodium methoxide, sodium benzoate, lithium acetate, lithium carbonate, potassium acetate and potassium carbonate.
【００４７】なお、本発明の改質ポリエステル組成物に
は、必要に応じて酸化防止剤、紫外線吸収剤、難燃剤、
蛍光増白剤、艶消剤、着色剤、消艶剤、その他の添加剤
等を配合してもよい。In the modified polyester composition of the present invention, if necessary, an antioxidant, an ultraviolet absorber, a flame retardant,
You may mix | blend a fluorescent whitening agent, a matting agent, a coloring agent, a matting agent, and other additives.
【００４８】本発明の改質ポリエステル組成物から繊維
を製造する場合には、任意の製糸条件を何等の支障なく
採用することができる。例えば５００〜２,５００ｍ／
分の速度で溶融紡糸し、延伸・熱処理する方法、１,５
００〜５,０００ｍ／分の速度で溶融紡糸し、延伸と仮
燃加工とを同時にまたは続いて行う方法、５,０００ｍ
／分以上の高速で溶融紡糸し、用途によっては延伸を省
略する方法等の任意の製糸条件を採用することができ
る。When fibers are produced from the modified polyester composition of the present invention, any yarn-making conditions can be adopted without any trouble. For example, 500 to 2,500m /
Method of melt-spinning at the speed of minute, drawing and heat treatment 1,5
Method in which melt spinning is carried out at a speed of from 0 to 5,000 m / min, and drawing and pre-combustion processing are carried out simultaneously or subsequently, 5,000 m
It is possible to employ any spinning conditions such as a method of performing melt spinning at a high speed of not less than 1 minute / minute and omitting stretching depending on the application.
【００４９】また、本発明の改質ポリエステル組成物を
用いて引取速度２,０００ｍ／分以上、特に４,０００ｍ
／分以上の高速で、溶融紡糸を行った場合、不溶性異物
の量が少ないため、紡糸時の糸切れの大幅な減少が認め
られる。ここで、紡糸条件としてはポリエステルの溶融
紡糸条件を任意に採用することができる。異物減少の理
由はいまだに解明されていないが、以下のごとく推定さ
れる。すなわち、ポリエステル製造時に添加したエステ
ル交換触媒及び／又は重縮合触媒は、通常リン化合物と
反応して粒子となるが、本発明のリン化合物はエポキシ
化合物との反応生成物であり、このためポリエステルと
の相溶性が増し、ポリエステル中において不溶性異物粒
子を析出しにくくするものと考えられる。Further, using the modified polyester composition of the present invention, a take-up speed of 2,000 m / min or more, particularly 4,000 m
When melt spinning is carried out at a high speed of not less than 1 minute / minute, the amount of insoluble foreign matter is small, and thus the yarn breakage during spinning is significantly reduced. Here, melt spinning conditions of polyester can be arbitrarily adopted as the spinning conditions. The reason for the decrease in foreign matter has not been clarified yet, but it is estimated as follows. That is, the transesterification catalyst and / or polycondensation catalyst added at the time of polyester production usually reacts with a phosphorus compound to form particles, but the phosphorus compound of the present invention is a reaction product with an epoxy compound, and therefore, the polyester and It is considered that the compatibility of the above is increased and it becomes difficult to precipitate insoluble foreign particles in the polyester.
【００５０】また、本発明の改質ポリエステル組成物
は、フィルムやシートの製造にも使用することができ、
この際任意の成形条件を何らの支障なく採用することが
できる。例えば製膜後一方向のみに張力を作用させて異
方性膜を製造する方法、同時にまたは任意の順序で膜を
二方向に延伸する方法、および膜を二段以上に多段延伸
する方法等を任意の条件で採用することができる。The modified polyester composition of the present invention can also be used for producing films and sheets,
At this time, arbitrary molding conditions can be adopted without any trouble. For example, a method of producing an anisotropic film by applying tension only in one direction after film formation, a method of stretching the film in two directions simultaneously or in any order, a method of stretching the film in two or more stages, and the like. It can be adopted under any conditions.
【００５１】[0051]
【発明の効果】以上に詳述した本発明によれば、耐加水
分解性、熱安定性、色調に優れポリエステル中不溶性異
物の少ないポリエステルが提供される。その理由は未だ
解明されていないが、以下の如く推定される。すなわ
ち、ポリエステル製造時に添加したエステル交換反応触
媒及び／又は重縮合触媒は通常リン化合物と反応して粒
子となるが、本発明のリン化合物はエポキシ化合物との
反応生成物であり、その反応を適度に抑制して不溶性異
物粒子として析出することが少くなる。また本発明のＢ
成分の場合は酸触媒としての活性が適度に抑制されてい
るため、ポリエステルの耐加水分解性、耐熱性が向上
し、色調も良好となると推定される。According to the present invention described in detail above, a polyester having excellent hydrolysis resistance, heat stability, and color tone and containing little insoluble foreign matter in the polyester is provided. The reason has not been clarified yet, but it is estimated as follows. That is, the transesterification catalyst and / or polycondensation catalyst added at the time of polyester production usually reacts with a phosphorus compound to form particles, but the phosphorus compound of the present invention is a reaction product with an epoxy compound, and the reaction is appropriately performed. To lessen the precipitation of insoluble foreign particles. In addition, B of the present invention
Since the activity as an acid catalyst is appropriately suppressed in the case of the component, it is presumed that the hydrolysis resistance and heat resistance of the polyester are improved and the color tone is also improved.
【００５２】その上、本発明の改質ポリエステル組成物
によれば、カチオン染料で染色した際に改善された濃色
性や鮮明発色性が得られると共に耐熱性および色相の面
でも良好という従来見ない効果が奏される。従って、本
発明の改質ポリエステル組成物は特に繊維に有用であ
る。さらに、本発明の改質ポリエステル組成物から得ら
れるフィルムやシートは、強度に優れると共に優れた制
電性、吸水性、印刷性、接着性等を有するので有用であ
る。Moreover, according to the modified polyester composition of the present invention, improved darkness and vivid color development when dyed with a cationic dye are obtained, and heat resistance and hue are also good. There is no effect. Therefore, the modified polyester composition of the present invention is particularly useful for fibers. Further, the film or sheet obtained from the modified polyester composition of the present invention is useful because it is excellent in strength and has excellent antistatic property, water absorption property, printability, adhesive property and the like.
【００５３】[0053]
【実施例】以下に実施例を挙げてさらに詳細に説明す
る。なお、実施例中の部および％は重量部および重量％
を表わし、また各測定値は下記の方法に従った。（１）固有粘度
：
ポリマーの固有粘度［ＩＶ］は、３５℃のオルソクロロ
フェノール溶液で測定した値から求めた。EXAMPLES The present invention will be described in more detail below with reference to examples. All parts and percentages in the examples are parts by weight and% by weight
And each measured value was in accordance with the following method. (1) Intrinsic viscosity : The intrinsic viscosity [IV] of the polymer was determined from the value measured with an orthochlorophenol solution at 35 ° C.
【００５４】（２）色調：重合体の色調を表わすＬ値及
びｂ値はハンター型色差計を用いて測定した値であり、
Ｌ値が大きい程白度が向上していることを示し、ｂ値が
大きい程黄色味の強いことを示している。すなわちＬ値
が大きく、ｂ値が小さいほど色調が良好であることを示
す。また、染色布の視感染色性は染色布のＬ*値、ａ
*値、ｂ*値をミノルタ色彩色差計ＣＲ−２００（ミノル
タカメラ販売（株））を用いて測定し、深色度（Ｌ*）
および彩度｛（ａ*2＋ｂ*2）1/2｝により深色性と鮮明
発色性を求めた。深色度が小さいほど深色性が大きく、
また彩度が大きいほど鮮明発色性が大きいことを示す。 (2) Color tone : L value and b value representing the color tone of the polymer are values measured using a Hunter color difference meter,
The larger the L value, the higher the whiteness, and the larger the b value, the stronger the yellowness. That is, the larger the L value and the smaller the b value, the better the color tone. Further, the visual infection color of the dyed cloth is L * value of the dyed cloth, a
The * and b * values were measured using a Minolta color difference meter CR-200 (Minolta Camera Sales Co., Ltd.), and the bathochromaticity (L * ) was measured.
And the saturation {(a * 2 + b * 2 ) 1/2 } were used to determine the bathochromatism and the vivid color development. The smaller the bathochromicity, the greater the bathochromicity,
Also, the greater the saturation, the greater the vivid color development.
【００５５】（３）耐加水分解性および耐熱性：耐加水
分解性および耐熱性は以下のとおり評価した。直径０.
３ｍｍの紡糸孔３０個を有する紡糸口金を使用して吐出
量８０ｇ／ｍｉｎ、捲取速度１,２００ｍ／ｍｉｎで紡
糸して得られた未延伸を、延伸温度８５℃、延伸倍率
３.５倍、延伸速度１１００ｍ／ｍｉｎで延伸して、１
５０デニール／３０フィラメント２５ｋｇ巻とした。紡
糸前後の固有粘度［ＩＶ］の変化から耐熱性を判断し
た。一方得られた糸サンプルを１３５℃、６０時間湿熱
下に保持し、その時の糸強度を測定し、未処理糸対比の
強度保持率で耐加水分解性を示した。すなわち、強度保
持率が高いほど、耐加水分解性が良好といえる。 (3) Hydrolysis resistance and heat resistance : The hydrolysis resistance and heat resistance were evaluated as follows. Diameter 0.
An unstretched film obtained by spinning at a discharge rate of 80 g / min and a winding speed of 1,200 m / min using a spinneret having 30 3-mm spinning holes was drawn at a drawing temperature of 85 ° C and a draw ratio of 3.5 times. , 1 at a drawing speed of 1100 m / min
A 50 kg / 30 filament 25 kg roll was prepared. The heat resistance was judged from the change in intrinsic viscosity [IV] before and after spinning. On the other hand, the obtained yarn sample was kept under humid heat at 135 ° C. for 60 hours, the yarn strength at that time was measured, and hydrolysis resistance was shown by the strength retention ratio relative to the untreated yarn. That is, it can be said that the higher the strength retention rate, the better the hydrolysis resistance.
【００５６】（４）不溶性異物の量：不溶性異物の量は
以下のとおり測定し評価した。ポリマーを１０ミクロン
の厚さの薄膜フィルムにした後、光学顕微鏡で異物径お
よび異物数を測定し、少ないサンプルを○、やや少ない
サンプルを△、多いサンプルを×とする三段階で評価し
た。（５）紡糸時の断糸度数
：引取速度３,０００ｍ／分、
５,０００ｍ／分で紡糸を行い、そのときのポリマー１
トン当りの断糸数を調べた。 (4) Amount of insoluble foreign matter: The amount of insoluble foreign matter was measured and evaluated as follows. After the polymer was formed into a thin film having a thickness of 10 μm, the particle diameter and the number of particles were measured with an optical microscope, and evaluated in three stages, with a small sample as ◯, a slightly small sample as Δ, and a large sample as x. (5) Breakage frequency during spinning : take-off speed 3,000 m / min,
Spinning at 5,000 m / min, polymer 1 at that time
The number of yarn breakages per ton was examined.
【００５７】［反応生成物（Ｂ成分）の合成］表１に示
すリン化合物（Ｂ−１成分）の２５部に窒素ガスを流し
ながら９５℃に加熱還流しているところに、表１に示す
種類、量のエポキシ化合物（Ｂ−２成分）を約３０分か
けて少量ずつ滴下した。滴下終了後も加熱還流しなが
ら、５時間反応を続けて、反応生成物（Ｂ成分）を得
た。[Synthesis of Reaction Product (Component B)] Table 1 shows that 25 parts of the phosphorus compound (Component B-1) shown in Table 1 was heated and refluxed at 95 ° C. while flowing nitrogen gas. The epoxy compound (B-2 component) of the kind and amount was dropped little by little over about 30 minutes. After completion of the dropping, the reaction was continued for 5 hours while heating under reflux to obtain a reaction product (component B).
【００５８】実施例１〜８および比較例１〜３
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０.０３１部（テレフタル酸
ジメチルに対して０.０２５モル％）をエステル交換缶
に仕込み、窒素ガス雰囲気下３時間かけて、１４０℃か
ら２２０℃まで昇温して生成するメタノールを系外に留
出しながらエステル交換反応させた。次いで、合成した
反応生成物（Ｂ成分）を表２記載の種類および量を添加
した後、過剰のエチレングリコールの昇温追出しを開始
した。１０分後に重縮合反応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０.０２７モ
ル％）を添加した。内温が２４０℃に到達した時点で、
エチレングリコールの追出しを終了し、反応生成物を重
合缶に移し、次いで昇温しながら３０分間常圧反応させ
た後、１時間かけて７６０ｍｍＨｇから１ｍｍＨｇまで
減圧し、同時に１時間３０分かけて内温を２９０℃まで
昇温した。１ｍｍＨｇ以下の減圧下、重合温度２９０℃
でさらに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２９０℃でポリ
マーの吐出を行った。得られたポリマーの品質および耐
熱性、耐加水分解後の評価結果は表２に示したとおりで
あった。Examples 1-8 and Comparative Examples 1-3 100 parts dimethyl terephthalate, ethylene glycol 6
0 part and 0.031 part of manganese acetate tetrahydrate (0.025 mol% relative to dimethyl terephthalate) were charged into a transesterification can, and the temperature was raised from 140 ° C to 220 ° C over 3 hours under a nitrogen gas atmosphere. The transesterification reaction was carried out while distilling off the produced methanol out of the system. Then, the synthesized reaction product (component B) was added in the types and amounts shown in Table 2, and then the temperature rising / expulsion of excess ethylene glycol was started. After 10 minutes, 0.04 part of antimony trioxide (0.027 mol% based on dimethyl terephthalate) was added as a polycondensation reaction catalyst. When the internal temperature reaches 240 ° C,
After expulsion of ethylene glycol was completed, the reaction product was transferred to a polymerization vessel and then subjected to a normal pressure reaction for 30 minutes while raising the temperature. Then, the pressure was reduced from 760 mmHg to 1 mmHg over 1 hour, and at the same time, over 1 hour 30 minutes. The temperature was raised to 290 ° C. Polymerization temperature 290 ° C under reduced pressure of 1 mmHg or less
When the polymerization was continued for 2 hours, the vacuum was broken with nitrogen gas to terminate the polymerization reaction, and the polymer was discharged at 290 ° C. under the pressure of nitrogen gas. The quality, heat resistance, and evaluation results after hydrolysis resistance of the obtained polymer are shown in Table 2.
【００５９】[0059]
【表１】 [Table 1]
【００６０】[0060]
【表２】 [Table 2]
【００６１】実施例９
テレフタル酸ジメチル １００部、エチレングリコール
６０部、酢酸マンガン４水塩 ０.０３部（テレフタル酸
ジチメルに対して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％）、カチオン染料可染化剤と
してテレフタル酸ジメチルに対して１.５モル％となる
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および安定剤としてテレ
フタル酸ジメチルに対して０.０５０モル％のテトラエ
チルアンモニウムハイドロオキサイドをエステル交換缶
に仕込み、窒素ガス雰囲気下３時間かけて１４０℃から
２２０℃まで昇温して生成するメタノールを系外に留去
しながらエステル交換反応させた。続いて得られた生成
物にエステル交換触媒失活剤として前記Ｂ成分の合成で
得られた反応生成物（Ｂ）を０.１２部添加し、同時に
過剰のエチレングコリールの昇温追出しを開始した。１
０分後に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、反応生成物を重合缶に移し
た。Example 9 100 parts of dimethyl terephthalate, ethylene glycol
60 parts, manganese acetate tetrahydrate 0.03 parts (0.024 mol% with respect to dithymel terephthalate), cobalt acetate tetrahydrate as a color matching agent 0.009 parts (dimethyl terephthalate 0.007 mol) %), An amount of 1.5 mol% of 3,5-dicarbomethoxybenzenesulfonic acid tetra-n-butylphosphonium salt based on dimethyl terephthalate as a cationic dye dyeing agent, and dimethyl terephthalate as a stabilizer. On the other hand, 0.050 mol% of tetraethylammonium hydroxide was charged into a transesterification can, and the temperature was raised from 140 ° C. to 220 ° C. in a nitrogen gas atmosphere for 3 hours to distill off methanol produced to transesterify. It was made to react. Subsequently, 0.12 parts of the reaction product (B) obtained by the synthesis of the above-mentioned component B was added to the obtained product as a transesterification catalyst deactivator, and at the same time, the excess temperature of the ethylene-gucoril was removed. Started. 1
After 0 minutes, 0.04 part of antimony trioxide (0.027 mol% based on dimethyl terephthalate) was added as a polycondensation catalyst. When the internal temperature reached 240 ° C., the expulsion of ethylene glycol was terminated, and the reaction product was transferred to the polymerization vessel.
【００６２】昇温して内温が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１ｍ
ｍＨｇまで減圧し、同時に１時間３０分かけて内温を２
８０℃まで昇温した。１ｍｍＨｇ以下の減圧下、重合温
度２８０℃でさらに２時間重合した時点で窒素ガスで真
空を破って重合反応を終了し、窒素ガス加圧下でポリマ
ーを吐出し、冷却してチップ化した。得られたポリマー
の固有粘度［η］は表３に記載のとおりであった。ま
た、チップの色相を示すＬ値も表３に示した。また、ポ
リマーの熱安定性の指標となるポリマーの固有粘度と延
伸糸の固有粘度の差を表３に示した。After the temperature was raised and the reaction was carried out at normal pressure until the internal temperature reached 260 ° C., it was changed from 760 mmHg to 1 m over 1 hour.
The pressure was reduced to mHg and the internal temperature was increased to 2 at the same time over 1 hour 30 minutes.
The temperature was raised to 80 ° C. When the polymerization was further performed at a polymerization temperature of 280 ° C. under a reduced pressure of 1 mmHg or less for 2 hours, the vacuum was broken with nitrogen gas to terminate the polymerization reaction, and the polymer was discharged under pressure of nitrogen gas and cooled to form chips. The intrinsic viscosity [η] of the obtained polymer was as shown in Table 3. In addition, Table 3 also shows the L value indicating the hue of the chip. Further, Table 3 shows the difference between the intrinsic viscosity of the polymer and the intrinsic viscosity of the drawn yarn, which is an index of the thermal stability of the polymer.
【００６３】このポリマーチップを常法により乾燥した
後、２８５℃で溶融し、スリット幅０.１５ｍｍのＹ字
型孔を２４個穿設した紡糸口金を使用して紡糸速度１,
１００ｍ／分にて紡出し、次いで、得られる延伸糸の伸
度が３５％になるような延伸倍率で、延伸速度１,２０
０ｍ／分にて、８４℃の加熱ローラーと１８０℃のプレ
ートヒーターを使って延伸・熱処理を行い、５０デニー
ル／２４フィラメントの三葉型断面の延伸糸を得た。得
られた延伸糸の固有粘度を表３に示した。This polymer chip was dried by a conventional method, then melted at 285 ° C., and a spinning nozzle with 24 Y-shaped holes having a slit width of 0.15 mm was used for spinning speed 1,
It is spun at 100 m / min and then drawn at a draw ratio of 1,20 at a draw ratio such that the elongation of the resulting drawn yarn is 35%.
At 0 m / min, drawing and heat treatment were performed using a heating roller at 84 ° C. and a plate heater at 180 ° C., and a drawn yarn having a trilobal cross section of 50 denier / 24 filament was obtained. The intrinsic viscosity of the obtained drawn yarn is shown in Table 3.
【００６４】得られた延伸糸を常法に従ってメリヤス編
地に製編後、常法により精練、プリセットした後 Cathi
lon Blue ＣＤ−ＦＲＬＨ／Cathilon Blue ＣＤ−ＦＢ
ＬＨ＝１／１［保土谷化学（株）製］２％ｏｗｆで芒硝
３ｇ／Ｌ、酢酸０.３ｇ／Ｌを含む染浴中にて１３０℃
で６０分間染色し、その後常法に従ってソーピングして
青色布を得た。表３に染色布の深色度および彩度を示し
た。The drawn yarn obtained was knitted into a knitted fabric by a conventional method, scoured and preset by a conventional method, and then Cathi
lon Blue CD-FRLH / Cathilon Blue CD-FB
LH = 1/1 [Hodogaya Chemical Co., Ltd.] 2% owf at 130 ° C. in a dye bath containing Glauber's salt 3 g / L and acetic acid 0.3 g / L.
It was dyed for 60 minutes, and then soaped according to a conventional method to obtain a blue cloth. Table 3 shows the bathochromaticity and saturation of the dyed fabric.
【００６５】実施例１０
実施例９において使用したＢ成分を（Ｂ）に変えて
（Ａ）を０.０８８部使用する以外は実施例９と同様に
行った。結果を表３に示した。Example 10 Example 9 was repeated except that the component (B) used in Example 9 was changed to (B) and 0.088 part of (A) was used. The results are shown in Table 3.
【００６６】実施例１１
実施例９において使用したスルホン酸ホスホニウム塩の
共重合量を変更しさらにスルホン酸金属塩化合物を共重
合および重合反応よりブレンドした場合の結果を表３に
示した。Example 11 Table 3 shows the results obtained by changing the copolymerization amount of the phosphonium sulfonate salt used in Example 9 and further blending the sulfonate metal salt compound by copolymerization and polymerization reaction.
【００６７】実施例１２
実施例１１においてスルホン酸金属塩化合物の添加量を
変更し、Ｂ成分を（Ｂ）から（Ｅ）に変えた場合の結果
を表３に示した。Example 12 Table 3 shows the results when the addition amount of the sulfonic acid metal salt compound was changed in Example 11 and the B component was changed from (B) to (E).
【００６８】比較例４〜６
実施例９、１１および１２において使用したＢ成分に変
えて正リン酸の５６％水溶液を０.０３部（テレフタル
酸ジメチルに対して０.０３３モル％）を添加した場合
の結果を表３に示した。Comparative Examples 4 to 6 In place of the component B used in Examples 9, 11 and 12, 0.03 part of a 56% aqueous solution of orthophosphoric acid (0.033 mol% based on dimethyl terephthalate) was added. Table 3 shows the results of the cases.
【００６９】[0069]
【表３】 [Table 3]
【００７０】実施例１３〜２１および比較例７〜９
テレフタル酸ジメチル １００部、エチレングリコール
６０部、酢酸マンガン４水塩 ０.０３１部（テレフタル
酸ジメチルに対して０.０２５モル％）をエステル交換
缶に仕込み、窒素ガス雰囲気下３時間かけて１４０℃か
ら２２０℃まで昇温して生成するメタノールを系外に流
出しながらエステル交換反応させた。次いで、合成した
反応生成物（Ｂ成分）を表４記載の種類および量を添加
した後、過剰のエチレングリコールの追出しを開始し
た。１０分後に重縮合反応触媒として三酸化アンチモン
０.０４部（テレフタル酸に対して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
コリールの追出しを終了し、反応生成物を重合缶に移
し、次いで昇温しながら３０分間常圧反応させた後、１
時間かけて７６０ｍｍＨｇから１ｍｍＨｇまで減圧し、
同時に１時間３０分かけて内温を２９０℃まで昇温し
た。１ｍｍＨｇ以下の減圧下、重合温度２９０℃でさら
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２９０℃でポリマーの
吐出を行った。得られたポリマーの品質は表４に示した
とおりであった。[0070] Examples 13-21 and Comparative Examples 7-9 100 parts of dimethyl terephthalate, ethylene glycol
60 parts and 0.031 parts of manganese acetate tetrahydrate (0.025 mol% with respect to dimethyl terephthalate) were charged into a transesterification can and heated from 140 ° C to 220 ° C over 3 hours under a nitrogen gas atmosphere. The produced methanol was allowed to flow out of the system for transesterification. Next, the synthesized reaction product (component B) was added in the types and amounts shown in Table 4, and then excess ethylene glycol was expelled. After 10 minutes, 0.04 part of antimony trioxide (0.027 mol% based on terephthalic acid) was added as a polycondensation reaction catalyst. When the internal temperature reached 240 ° C., the expulsion of ethylene glycol was completed, the reaction product was transferred to a polymerization vessel, and the reaction was continued for 30 minutes at normal pressure while raising the temperature.
Reduce pressure from 760 mmHg to 1 mmHg over time,
At the same time, the internal temperature was raised to 290 ° C. over 1 hour and 30 minutes. When the polymerization was further continued for 2 hours at a polymerization temperature of 290 ° C. under a reduced pressure of 1 mmHg or less, the vacuum was broken with nitrogen gas to terminate the polymerization reaction, and the polymer was discharged at 290 ° C. under the pressure of nitrogen gas. The quality of the obtained polymer was as shown in Table 4.
【００７１】かくして得られたポリマーを、紡糸温度２
９０℃、冷却風線速度１５ｍ／分（２６℃、相対湿度７
０％）、引取速度３,０００ｍ／分もしくは５,０００ｍ
／分で７５デニール、３６フィラメントの糸を紡糸し
た。糸の不溶性異物数、紡糸時の断糸数については表４
に示した。なお、表４の中で、実施例１４が最も優れた
ものである。The polymer thus obtained was subjected to a spinning temperature of 2
90 ° C, cooling air linear velocity 15 m / min (26 ° C, relative humidity 7
0%), take-off speed 3,000m / min or 5,000m
A yarn of 75 denier, 36 filaments per minute was spun. Table 4 shows the number of insoluble foreign matters in the yarn and the number of yarn breakage during spinning.
It was shown to. In addition, in Table 4, Example 14 is the most excellent.
【００７２】なお、表４中、１）〜３）はそれぞれ下記
の意味を有する。
１）添加量はテレフタル酸ジメチル１００重量部に対す
るＢ成分の重量部として示した。
２）ポリマー中のリン含量は、ポリエステル１００重量
部に対するリンの重量部として示した。
３）○：１ケ／ｃｍ2以下；△：１〜５ケ／ｃｍ2；×：
５ケ／ｃｍ2以上In Table 4, 1) to 3) have the following meanings. 1) The addition amount is shown as parts by weight of the component B with respect to 100 parts by weight of dimethyl terephthalate. 2) The phosphorus content in the polymer is shown as parts by weight of phosphorus based on 100 parts by weight of polyester. 3) ○: 1 piece / cm 2 or less; △: 1 to 5 pieces / cm 2 ; ×:
5 pieces / cm 2 or more
【００７３】[0073]
【表４】 [Table 4]
【００７４】[0074]
───────────────────────────────────────────────────── フロントページの続き (72)発明者 山本 智義 愛媛県松山市北吉田町77番地 帝人株式 会社 松山事業所内 (72)発明者 三田 利弘 愛媛県松山市北吉田町77番地 帝人株式 会社 松山事業所内 (56)参考文献 特開 平４−149269（ＪＰ，Ａ) 特開 昭54−152057（ＪＰ，Ａ) 特開 昭50−105792（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08G 63/00 - 63/91 C08L 67/00 - 67/02 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tomoyoshi Yamamoto 77 Kitayoshida-cho, Matsuyama-shi, Ehime Teijin Limited Matsuyama Business Office (72) Inventor Toshihiro Mita 77 Kitayoshida-cho, Matsuyama-shi Ehime Teijin Limited Matsuyama Business In-house (56) Reference JP-A-4-149269 (JP, A) JP-A-5415-2057 (JP, A) JP-A-50-105792 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) C08G 63/00-63/91 C08L 67/00-67/02
Claims (6)
一般式［ＩＩ］で表わされるエポキシ化合物との反応生
成物（Ｂ成分）を配合させてなる芳香族ポリエステル組
成物。 【化１】 ［式中、Ｒ1、Ｒ2およびＲ3は、それぞれ同一または異
なり、水素原子、炭素原子数１〜４のアルキル基または
炭素原子数６〜１２のアリール基を示す。］ 【化２】 ［式中、ｌ1、ｌ2およびｌ3は、それぞれ同一または異
なり、水素原子または炭素原子数１〜４のアルキル基を
示し、ｌ4は炭素原子数１〜１５のアルキル基または炭
素原子数６〜１２のアリール基を示す。］1. A reaction product (component B) of (A) an aromatic polyester (component A) with (B) a phosphorus compound represented by the following general formula [I] and an epoxy compound represented by the following general formula [II]. An aromatic polyester composition obtained by blending [Chemical 1] [In the formula, R 1 , R 2 and R 3 are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms. ] [Chemical 2] [Wherein, l 1 , l 2 and l 3 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and l 4 is an alkyl group having 1 to 15 carbon atoms or the number of carbon atoms 6 to 12 aryl groups are shown. ]
物と該エポキシ化合物とを、モル比で１：１〜１：５の
割合でかつ７０〜１３０℃の温度で反応させた生成物で
ある請求項１記載のポリエステル組成物。2. The reaction product (component B) is produced by reacting the phosphorus compound and the epoxy compound at a molar ratio of 1: 1 to 1: 5 and at a temperature of 70 to 130 ° C. The polyester composition according to claim 1, which is a product.
合がリン含量として０.０００５〜０.２重量部である請
求項１記載のポリエステル組成物。3. The polyester composition according to claim 1, wherein the ratio of the component B is 0.0005 to 0.2 part by weight based on 100 parts by weight of the component A.
記一般式［ＩＩＩ］ 【化３】 ［式中、Ａは芳香族基または脂肪族基であり、Ｘ1はエ
ステル形成性官能基であり、Ｘ2はＸ1と同一若しくは異
なるエステル形成性官能基または水素原子であり、
Ｑ1、Ｑ2、Ｑ3およびＱ4のそれぞれは、アルキル基およ
びアリール基よりなる群から選ばれる同一または異なる
基であり、そして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、ポリエステルを形成する
二官能性芳香族カルボン酸成分に対して０.１〜１０モ
ル％共重合した改質芳香族ポリエステルである請求項１
記載のポリエステル組成物。4. The aromatic polyester (component A) has the following general formula [III]: [Wherein A is an aromatic group or an aliphatic group, X 1 is an ester-forming functional group, X 2 is the same or different from X 1 , an ester-forming functional group or a hydrogen atom,
Each of Q 1 , Q 2 , Q 3 and Q 4 is the same or different group selected from the group consisting of an alkyl group and an aryl group, and n represents a positive integer. ] The modified aromatic polyester obtained by copolymerizing the phosphonium sulfonate represented by the formula (1) to 0.1 to 10 mol% with respect to the difunctional aromatic carboxylic acid component forming the polyester.
The polyester composition described.
のエステル形成性誘導体と、アルキレングリコール及び
／又はそのエステル形成性誘導体とを反応せしめて二官
能性芳香族カルボン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、次いで重合反応せしめてポリ
エステルを製造するに際し、前記請求項１記載のＢ成分
を、ポリエステルの重合が終了するまでの任意の時期に
添加することを特徴とする芳香族ポリエステル組成物の
製造方法。5. A bifunctional aromatic carboxylic acid and / or an ester-forming derivative thereof is reacted with an alkylene glycol and / or an ester-forming derivative thereof to form a glycol ester of a bifunctional aromatic carboxylic acid and / or When the low polymer is produced and then subjected to a polymerization reaction to produce a polyester, the component B according to claim 1 is added at an arbitrary time until the polymerization of the polyester is completed. Method for producing polyester composition.
前記請求項４記載の一般式［ＩＩＩ］で表わされるスル
ホン酸ホスホニウム塩を、二官能性芳香族カルボン酸及
び／又はそのエステル形成性誘導体に対して０.１〜１
０モル％添加する請求項５記載の製造方法。6. When producing a polyester, the phosphonium sulfonate represented by the general formula [III] according to claim 4 is further added to the difunctional aromatic carboxylic acid and / or its ester- forming derivative. 0.1-1
The manufacturing method according to claim 5, wherein 0 mol% is added.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27756295A JP3530900B2 (en) | 1994-10-26 | 1995-10-25 | Polyester composition and method for producing the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6-262649 | 1994-10-26 | ||
| JP26264994 | 1994-10-26 | ||
| JP27756295A JP3530900B2 (en) | 1994-10-26 | 1995-10-25 | Polyester composition and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08208965A JPH08208965A (en) | 1996-08-13 |
| JP3530900B2 true JP3530900B2 (en) | 2004-05-24 |
Family
ID=26545634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27756295A Expired - Fee Related JP3530900B2 (en) | 1994-10-26 | 1995-10-25 | Polyester composition and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3530900B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6818293B1 (en) | 2003-04-24 | 2004-11-16 | Eastman Chemical Company | Stabilized polyester fibers and films |
| JP5373357B2 (en) * | 2008-10-16 | 2013-12-18 | 帝人株式会社 | Normal pressure cationic dyeable copolyester and fiber |
-
1995
- 1995-10-25 JP JP27756295A patent/JP3530900B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08208965A (en) | 1996-08-13 |
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