JPH01192821A - Production of formed article of copolymerized polyester - Google Patents
Production of formed article of copolymerized polyesterInfo
- Publication number
- JPH01192821A JPH01192821A JP1320988A JP1320988A JPH01192821A JP H01192821 A JPH01192821 A JP H01192821A JP 1320988 A JP1320988 A JP 1320988A JP 1320988 A JP1320988 A JP 1320988A JP H01192821 A JPH01192821 A JP H01192821A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- ester
- salt
- fine particles
- polyester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- -1 alkylene glycols Chemical class 0.000 claims abstract description 29
- 239000010419 fine particle Substances 0.000 claims abstract description 24
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011164 primary particle Substances 0.000 claims abstract description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 8
- 125000000524 functional group Chemical group 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 37
- 238000000465 moulding Methods 0.000 claims description 10
- 229920001634 Copolyester Polymers 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 13
- 125000002091 cationic group Chemical group 0.000 abstract description 9
- 239000002245 particle Substances 0.000 abstract description 6
- 239000010409 thin film Substances 0.000 abstract description 5
- 230000001588 bifunctional effect Effects 0.000 abstract description 2
- 229920001577 copolymer Polymers 0.000 abstract 3
- 238000002074 melt spinning Methods 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 13
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 12
- 239000000975 dye Substances 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000004744 fabric Substances 0.000 description 9
- 238000009987 spinning Methods 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000004043 dyeing Methods 0.000 description 5
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical class CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 5
- 238000005809 transesterification reaction Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- 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 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- XQKKWWCELHKGKB-UHFFFAOYSA-L calcium acetate monohydrate Chemical compound O.[Ca+2].CC([O-])=O.CC([O-])=O XQKKWWCELHKGKB-UHFFFAOYSA-L 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-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
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-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
- 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
- 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
- 238000009835 boiling Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229940067460 calcium acetate monohydrate Drugs 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- GELSOTNVVKOYAW-UHFFFAOYSA-N ethyl(triphenyl)phosphanium Chemical class C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 GELSOTNVVKOYAW-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 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
- 238000003786 synthesis reaction Methods 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- GFZMLBWMGBLIDI-UHFFFAOYSA-M tetrabutylphosphanium;acetate Chemical compound CC([O-])=O.CCCC[P+](CCCC)(CCCC)CCCC GFZMLBWMGBLIDI-UHFFFAOYSA-M 0.000 description 2
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 2
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical class C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 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
- QLAJNZSPVITUCQ-UHFFFAOYSA-N 1,3,2-dioxathietane 2,2-dioxide Chemical compound O=S1(=O)OCO1 QLAJNZSPVITUCQ-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
- ZRPKEUVFESZUKX-UHFFFAOYSA-N 2-(2-hydroxyethoxy)benzoic acid Chemical compound OCCOC1=CC=CC=C1C(O)=O ZRPKEUVFESZUKX-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
- YZTJKOLMWJNVFH-UHFFFAOYSA-N 2-sulfobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1S(O)(=O)=O YZTJKOLMWJNVFH-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-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
- HYGCHOFPZRYRNH-UHFFFAOYSA-N CCCCP.CCCCP.CCCCP.OP(O)O Chemical compound CCCCP.CCCCP.CCCCP.OP(O)O HYGCHOFPZRYRNH-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 102100027373 Melanin-concentrating hormone receptor 2 Human genes 0.000 description 1
- 101710089759 Melanin-concentrating hormone receptor 2 Proteins 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical class [Na] KEAYESYHFKHZAL-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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- QEZIKGQWAWNWIR-UHFFFAOYSA-N antimony(3+) antimony(5+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Sb+3].[Sb+5] QEZIKGQWAWNWIR-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- GGYWALSYXQTHCR-UHFFFAOYSA-M benzyl-dodecyl-dimethylphosphanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[P+](C)(C)CC1=CC=CC=C1 GGYWALSYXQTHCR-UHFFFAOYSA-M 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000006664 bond formation reaction Methods 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
- MFIUDWFSVDFDDY-UHFFFAOYSA-M butyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 MFIUDWFSVDFDDY-UHFFFAOYSA-M 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- USJRLGNYCQWLPF-UHFFFAOYSA-N chlorophosphane Chemical compound ClP USJRLGNYCQWLPF-UHFFFAOYSA-N 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical group OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 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
- MIQYOHNNWUEBSP-UHFFFAOYSA-N dodecyl(trimethyl)phosphanium Chemical compound CCCCCCCCCCCC[P+](C)(C)C MIQYOHNNWUEBSP-UHFFFAOYSA-N 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- NCXJEOYEONUMAC-UHFFFAOYSA-M ethyl(trihexyl)phosphanium;chloride Chemical compound [Cl-].CCCCCC[P+](CC)(CCCCCC)CCCCCC NCXJEOYEONUMAC-UHFFFAOYSA-M 0.000 description 1
- PPMPHRIJIMNDPU-UHFFFAOYSA-M ethyl(trioctyl)phosphanium;chloride Chemical compound [Cl-].CCCCCCCC[P+](CC)(CCCCCCCC)CCCCCCCC PPMPHRIJIMNDPU-UHFFFAOYSA-M 0.000 description 1
- 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 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
- NCCOOTMRZHTROF-UHFFFAOYSA-N ethylphosphanium;bromide Chemical compound [Br-].CC[PH3+] NCCOOTMRZHTROF-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000003993 interaction Effects 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
- 239000006224 matting agent Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- QHVUZLUPVYICJZ-UHFFFAOYSA-M octadecanoate;tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC.CCCCCCCCCCCCCCCCCC([O-])=O QHVUZLUPVYICJZ-UHFFFAOYSA-M 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 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
- 230000003595 spectral effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000003746 surface roughness Effects 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
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 description 1
- DFQPZDGUFQJANM-UHFFFAOYSA-M tetrabutylphosphanium;hydroxide Chemical compound [OH-].CCCC[P+](CCCC)(CCCC)CCCC DFQPZDGUFQJANM-UHFFFAOYSA-M 0.000 description 1
- CCIYPTIBRAUPLQ-UHFFFAOYSA-M tetrabutylphosphanium;iodide Chemical compound [I-].CCCC[P+](CCCC)(CCCC)CCCC CCIYPTIBRAUPLQ-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
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-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
- FBOJNMRAZJRCNS-UHFFFAOYSA-M tetraethylphosphanium;chloride Chemical compound [Cl-].CC[P+](CC)(CC)CC FBOJNMRAZJRCNS-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
- ZTXFOCMYRCGSMU-UHFFFAOYSA-M tetramethylphosphanium;bromide Chemical compound [Br-].C[P+](C)(C)C ZTXFOCMYRCGSMU-UHFFFAOYSA-M 0.000 description 1
- NJFUXFRJVIXVSG-UHFFFAOYSA-M tetramethylphosphanium;chloride Chemical compound [Cl-].C[P+](C)(C)C NJFUXFRJVIXVSG-UHFFFAOYSA-M 0.000 description 1
- CRUVUWATNULHFA-UHFFFAOYSA-M tetramethylphosphanium;hydroxide Chemical compound [OH-].C[P+](C)(C)C CRUVUWATNULHFA-UHFFFAOYSA-M 0.000 description 1
- TVVPMLFGPYQGTG-UHFFFAOYSA-M tetramethylphosphanium;iodide Chemical compound [I-].C[P+](C)(C)C TVVPMLFGPYQGTG-UHFFFAOYSA-M 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
- 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 1
- WAGFXJQAIZNSEQ-UHFFFAOYSA-M tetraphenylphosphonium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WAGFXJQAIZNSEQ-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
- QBAUHKSMFOSSGE-UHFFFAOYSA-M tetrapropylphosphanium;chloride Chemical compound [Cl-].CCC[P+](CCC)(CCC)CCC QBAUHKSMFOSSGE-UHFFFAOYSA-M 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VTYPOYRICJLXSB-UHFFFAOYSA-M tributyl(cyclohexyl)phosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)C1CCCCC1 VTYPOYRICJLXSB-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
- NNENFOSYDBTCBO-UHFFFAOYSA-M tributyl(hexadecyl)phosphanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[P+](CCCC)(CCCC)CCCC NNENFOSYDBTCBO-UHFFFAOYSA-M 0.000 description 1
- JWZDVHOYCNIXDA-UHFFFAOYSA-N tributyl(phenyl)phosphanium Chemical class CCCC[P+](CCCC)(CCCC)C1=CC=CC=C1 JWZDVHOYCNIXDA-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- CVFVQXOZIJNRLO-UHFFFAOYSA-M trimethyl(octadecyl)phosphanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[P+](C)(C)C CVFVQXOZIJNRLO-UHFFFAOYSA-M 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Artificial Filaments (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、カチオン染料可染型の共重合ポリエステル成
形物の製造法に関し、更に詳しくは、カチオン染料可染
型の共重合ポリエステルに微粒子を添加して、成形性を
改良すると共に深色性に優れた共重合ポリエステル成形
物を製造する方法に関する。Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a method for producing a cationic dye-dyeable copolyester molded product, and more specifically, a method for producing a cationic dye-dyeable copolyester molded product. It also relates to a method for producing a copolyester molded product which has improved moldability and excellent bathochromic properties by adding it.
（従来の技術）
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、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４７−２２３３４号公報
、米国特許第３．７３２．１８３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、溶融粘度が通常溶融成
形できる範囲におさえられる。(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 known method is to copolymerize a sulfonic acid phosphonium salt with a polyester to make it dyeable with a cationic dye (Japanese Patent Publication No. 47-22334, U.S. 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 molding.
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
が得られるようになる。This makes it possible to obtain high-strength cationic dye-dyeable polyester fibers.
（発明が解決しようとする課題）
しかしながら、この方法では、成形性が悪く、紡出糸条
、成形フィルムの破断が生し、更には延伸工程でのロー
ラ巻付きなどが発生して、安定した状態で成形するのが
困難であり、特に細繊度糸条、厚さの薄いフィルムの成
形は不可能であった。(Problems to be Solved by the Invention) However, with this method, the formability is poor, the spun yarn and formed film break, and furthermore, roller wrapping occurs during the stretching process, resulting in a stable It is difficult to mold the film in such a state, and in particular, it is impossible to mold a film with a fine yarn or a thin thickness.
本発明の目的は、かかる従来技術の問題点を解消し、安
定な成形性のもとて成形物、特に繊度の細い糸条あるい
は厚さの薄いフィルムを製造することのできる方法を提
供することにある。あわせて、ポリエステル繊維特有の
染色時の色の深みや鮮明性に劣るという問題を解消し、
染色時の深色性、鮮明性に優れた成形物の製造方法を提
供するものである。An object of the present invention is to provide a method that can solve the problems of the prior art and produce molded products, particularly fine yarns or thin films, with stable moldability. It is in. At the same time, we have solved the problem of poor color depth and clarity during dyeing, which is unique to polyester fibers.
The object of the present invention is to provide a method for producing a molded article with excellent deep color properties and sharpness during dyeing.
（課題を解決するための手段）
本発明者らは、上記目的を達成すべく鋭意検討を重ねた
結果、平均一次粒子径が１００ｍμ以下の微粒子を添加
することによって、成形性が著しく改善されると共に、
染色時の深色性、鮮明性の良好な成形物が得られること
を見出し、本発明に到達した。即ち、本発明は、テレフ
タル酸を主と゛する二官能性カルボン酸又はそのエステ
ル形成性誘導体、少なくとも一種のアルキレングリコー
ル又はそのそのエステル形成性誘導体及び該二官能性カ
ルボン酸成分に対して０．５〜１０．０モル％の下記式
で表わされるスルホン酸ホスボニウム塩からなる共重合
ポリエステルを溶融成形するに際し、溶融成形以前の任
意の段階で、平均一次粒子径が１００ｍμ以下の微粒子
を該共重合ポリエステルに対して０．１〜５重量％添加
することを特徴とする共重合ポリエステル成形物の製造
法である。(Means for Solving the Problems) As a result of intensive studies to achieve the above object, the present inventors have found that moldability is significantly improved by adding fine particles with an average primary particle diameter of 100 mμ or less. With,
It was discovered that molded products with good bathochromic properties and sharpness during dyeing can be obtained, and the present invention was achieved. That is, the present invention provides a difunctional carboxylic acid mainly consisting of terephthalic acid or its ester-forming derivative, at least one alkylene glycol or its ester-forming derivative, and 0.5% of the difunctional carboxylic acid component. When melt-molding a copolymerized polyester consisting of ~10.0 mol% of a sulfonic acid phosbonium salt represented by the following formula, fine particles with an average primary particle diameter of 100 mμ or less are added to the copolymerized polyester at any stage before melt-molding. This is a method for producing a copolyester molded product characterized by adding 0.1 to 5% by weight.
Ｘ、 −Ａ−Ｘ２
（ＳＯ３Ｃ）Ｐ○Ｒ＋ Ｒ２Ｒ３Ｒａ ）ｎ本発明
で用いるポリエステルは、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た少なくとも１種のフルキレン
グリコールを主たる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。X, -A-X2 (SO3C)P○R+ R2R3Ra)nThe polyester used in the present invention has terephthalic acid as the main acid component and is selected from at least one type of glycol, preferably ethylene glycol, trimethylene glycol, and tetramethylene glycol. The main target is polyester whose main glycol component is at least one type of fullkylene glycol.
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」二記グリコ
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 a part of the glycol component is replaced with a diglycol 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臭香酸、ρ−オ
キシ安臭香酸、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
明の効果が実質的に奏せられる範囲で５−すトリウムス
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, and ρ-oxybenzoic acid. Examples include aromatic, aliphatic, and alicyclic difunctional carboxylic acids such as adipic acid, sebacic acid, and 1,4-cyclohexanedicarboxylic acid. Furthermore, isophthalic acid having a sulfonic acid metal base such as 5-storium sulfoisophthalic acid may be used as a copolymerization component as long as the effects of the present invention can be substantially achieved.
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−ジメタツール、ネオペ
ンチルグリコール、ビスフェノールＡ、ビスフェノール
Ｓの如き脂肪族、脂環族、芳香族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-dimetatool, neopentyl glycol, bisphenol A, 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
リント酸、ピロメリット酸の如きポリカルボン酸、クリ
セリン、トリメチロールプロパン。Additionally, polycarboxylic acids such as trimellitic acid, pyromellitic acid, chrycerin, trimethylolpropane to the extent that the polyester is substantially linear.
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
かできる。Polyols such as pentaerythritol can be used.
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、テレフク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
チレンオキザ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ゼ
る第１段階の反応と、第１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２段
階の反応によって製造される。For example, in the case of polyethylene terephthalate, it is usually a direct esterification reaction between terephthalic acid and ethylene glycol, a transesterification reaction between a lower alkyl ester of terephthalic acid such as dimethyl terephthalate and ethylene glycol, or a transesterification reaction between terephthalic acid and ethylene glycol. The first step is to react with oxide to produce a glycol ester of terephthalic acid and/or its low polymer, and the reaction product of the first step is heated under reduced pressure to achieve the desired degree of polymerization. It is produced by a second step of polycondensation reaction until it becomes .
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で表わされる。The sulfonic acid phosphonium salt used as a copolymerization component in the method of the present invention is represented by the following general formula.
Ｘ、−Ａ−Ｘ２
□
（Ｓ ０３０ＰＱＲ＋ Ｒ２Ｒ３Ｒａ ） ｎ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。Ｘ、はエステル形成性官能基を示し、具体
例として
−０−Ｃ−Ｒ’、−Ｃ−〇Ｈ，−Ｃ−ＯＲ’。In the formula: X represents an ester-forming functional group, and specific examples include -0-C-R', -C-〇H, and -C-OR'.
ＩＩ ＩＩ ＩＩｏ ０
０
一４ＮＣＨｚｈ−〇Ｈ。II II IIo 0
0-4NCHzh-〇H.
−（ＭＣＨ２斤→Ｏ（ＣＨｚ）ｂテｒＯＨ。-(MCH2 catty→O(CHz)bterOH.
−ＣＡ Ｏ（ＣＨ２） ｖすＴＯ）Ｉ
Ｉ１
等をあげることができる。Ｘ２はＸｌ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。ＲＩ、
Ｒ２、Ｒａ及びＲ４はアルキル基及びアリール基よりな
る群から選ばれた同−又は異なる基を示す。ｎは正の整
数である。-CA O(CH2) vSUTO)I I1 etc. can be mentioned. X2 represents an ester-forming functional group or a hydrogen atom that is the same as or different from Xl, and is preferably an ester-forming functional group. RI,
R2, Ra 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
ルボン酸とボスフィン類との反応又は対応するスルボン
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 bosphines 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−ジカルボキシヘ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ボニウム塩、３．５−ジ
カルボキシヘンゼンスルホン酸ヘンジルトリブチルホス
ポニウム塩、’３．５−ジカルボキシベンゼンスルボン
酸フェニルトリブチルホスボニウム塩、３，５−ジカル
ボキシヘンゼンスルホン酸テトラフェニルホスホニウム
塩、３゜５−ジカルボキシヘ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−ジカルボキシへン
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
ェニルボスホニウム塩、３，５−ジカルボン１〜キシヘ
ンゼンスルホン酸テトラブチルホスホニウム塩、３．５
−ジカルポメトキシヘ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−ジカルポキシヘンゼンスル
ホン酸ヘンシ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−ジカルボメトキシヘンゼンスルホ
ン酸テトラフェニルボスホニウム塩、３，５−ジカルボ
メトキシヘ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−ジカルポメトキシヘンゼンスルホン
酸プチルトリフェニルホスボニウム塩、３，５−ジカル
ポメトキシヘンゼンスルホン酸ヘンシルトリフェニルホ
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
キシヘンゼンスルホン酸テトラブチルホスホニウム塩。Preferred specific examples of the sulfonic acid phosphonium salts include 3,5-dicarboxybenzenesulfonic acid tetrabutylphosphonium salt, 3,5-dicarboxybenzenesulfonic acid ethyltributylphosphonium salt, and 3,5-dicarboxyhenzenesulfonic acid tetrabutylphosphonium salt. Zensulfonic acid henzyltributylphosponium salt, '3,5-dicarboxybenzenesulfonic acid phenyltributylphosponium salt, 3,5-dicarboxybenzenesulfonic acid tetraphenylphosphonium salt, 3゜5-dicarboxy Henzenesulfonic acid ethyltriphenylphosphonium salt, 3,5-dicarboxyhenzenesulfonic acid butyltriphenylphosphonium salt, 3
, 5-dicarboxybenzenesulfonic acid benzyltriphenylbosphonium salt, 3,5-dicarboxybenzenesulfonic acid tetrabutylphosphonium salt, 3.5
-Dicarpomethoxyhenzenesulfonic acid ethyltributylphosphonium salt, 3゜5-dicarpoxyhenzenesulfonic acid henzyltributylphosphonium salt 3.5-dicarboxybenzenesulfonic acid phenyltributylphosphonium salt, 3.5-dicarbomethoxyhene Zenesulfonic acid tetraphenylbosphonium salt, 3,5-dicarbomethoxyhenzenesulfonic acid ethyltriphenylphosphonium salt, 3,5-dicarbomethoxyhenzenesulfonic acid butyltriphenylphosphonium salt, 3,5- Dicarpomethoxyhenzenesulfonic acid hensyltriphenylphosphonium salt, 3-carboxybenzenesulfonic acid tetrabutylphosphonium salt, 3-carboxybenzenesulfonic acid tetraphenylphosphonium salt, 3-carbomethoxyhenzenesulfonic acid tetrabutylphosphonium salt.
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）ヘ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）ヘ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）ヘンゼン
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）ヘンゼンスルホン酸テト
ラフェニルホスホニウム塩、４−ヒドロキシェトキシヘ
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。3-Carbomethoxybenzenesulfonic acid tetraphenylphosphonium salt, 3,5-di(β-hydroxyethoxycarbonyl)henzenesulfonic acid tetrabutylphosphonium salt, 3,5-di(β-hydroxyethoxycarbonyl)henzenesulfonic acid tetra Phenylphosphonium salt, 3-(β-hydroxyethoxycarbonyl)henzenesulfonic acid tetrabutylphosphonium salt, 3-(β-hydroxyethoxycarbonyl)henzenesulfonic acid tetraphenylphosphonium salt, 4-hydroxyethoxyhenzenesulfonic acid tetra Butylphosphonium salt, 2,6
Examples include -dicarpoxynaphthalene-4-sulfonic acid tetrabutylphosphonium salt, α-tetrabutylphosphonium sulfosuccinic acid, and the like. The above-mentioned 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１段の反応が終了する以
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０．５〜１０モル％の範囲が適当であ
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 first stage reaction is completed. The proportion of the sulfonic acid phosphonium salt copolymerized with the polyester is suitably in the range of 0.5 to 10 mol % based on the bifunctional carboxylic acid component (excluding the sulfonate) constituting the polyester.
共重合割合が０．５モル％より少ないと、得られる共重
合ポリエステルのカチオン染料に対する染色性が不充分
になり、１０モル％より多くなるとポリエステルの物性
が低下する。If the copolymerization ratio is less than 0.5 mol %, the resulting copolymerized polyester will have insufficient dyeability with cationic dyes, and if it exceeds 10 mol %, the physical properties of the polyester will deteriorate.
本発明において使用する微粒子は、平均の一次粒子が１
００ｍμ以下であれば特に限定する必要はなく、例えば
シリカゲル（いわゆるコロイダルシリカ）、乾式法シリ
カ、酸化アルミニウムを含有する乾式法シリカ、粒子表
面にアルキル基を有し、且つ粒子表面のシラノール基を
封鎖した乾式法シリカ、アルミナゾル（いわゆるコロイ
ダルアルミナ）、微粒子アルミナ、極微粒子酸化チタン
、炭酸カルシウムゾル（いわゆるコロイダル炭酸カルシ
ウム）、微粒子状炭酸カルシウム等の不活性無機微粒子
やリン化合物と金属化合物とをポリエステル反応系内部
で反応させて析出せしめた内部析出系微粒子等を好まし
く例示できる。内部析出系微粒子の好ましい具体例とし
ては、例えば下記一般式
％式％
（式中、Ｒ１は及びＲ２は１価の有機基、Ｘは１価の有
機基又は金属、ｎは１又はＯを示す）で表わされるリン
化合物とアルカリ土類金属化合物との反応により析出せ
しめた内部析出系微粒子等をあげることができる。The fine particles used in the present invention have an average primary particle of 1
There is no need to specifically limit as long as it is 00 mμ or less, such as silica gel (so-called colloidal silica), dry process silica, dry process silica containing aluminum oxide, having an alkyl group on the particle surface and blocking the silanol group on the particle surface. Inert inorganic fine particles such as dry process silica, alumina sol (so-called colloidal alumina), fine alumina, ultrafine titanium oxide, calcium carbonate sol (so-called colloidal calcium carbonate), finely divided calcium carbonate, phosphorus compounds, and metal compounds are reacted with polyester. Preferred examples include internally precipitated fine particles that are precipitated by reaction within the system. Preferred specific examples of internally precipitated fine particles include, for example, the following general formula % (wherein R1 and R2 are monovalent organic groups, X is a monovalent organic group or metal, and n is 1 or O). ) Internally precipitated fine particles precipitated by the reaction between a phosphorus compound and an alkaline earth metal compound can be mentioned.
上記微粒子の平均の一次粒子径は系１００ｍμ以・
下である必要があり、好ましくは５０ｍμ以下、更に好
ましくは３０ｍμ以下である。平均の一次粒子径が１０
０ｍμを超えると、成形性の向上が顕著でなくなり、更
に最終的に充分な色の深みと鮮明性が得られない。なお
、ここでいう一次粒子径とは該一次粒子と同し容積を有
する想像上の球の直径を意味する。The average primary particle diameter of the above fine particles is 100 mμ or more.
It is preferably 50 mμ or less, more preferably 30 mμ or less. Average primary particle size is 10
If it exceeds 0 mμ, the improvement in moldability will not be significant, and furthermore, sufficient color depth and clarity will not be obtained. In addition, the primary particle diameter here means the diameter of an imaginary sphere having the same volume as the primary particle.
かかる微粒子の含有量は、あまりに少ないときには、成
形性向上の効果が少なく、また、最終的に得られるポリ
エステル繊維の表面凹凸形成が不充分となり色の深みや
鮮明性を改善する効果が認められ難い。この量を多くす
るに従って、成形性が向上し、色の深みや鮮明性は増加
するが、あまりムこ多くなると、成形が極めて困難にな
り、そのうえ最早色の深みや鮮明性は著しい向上を示さ
ず、かえって耐摩擦性が悪化するようになる。このため
、微粒子の含有量は０．１〜５重量％の範囲内であるこ
とが必要で、なかでも０．１〜３重量％の範囲が好まし
い。If the content of such fine particles is too small, the effect of improving moldability will be small, and the surface roughness formation of the final polyester fiber will be insufficient, making it difficult to recognize the effect of improving color depth and clarity. . As this amount increases, moldability improves and color depth and clarity increase; however, if it becomes too bulky, molding becomes extremely difficult, and furthermore, color depth and clarity no longer show significant improvement. On the contrary, the abrasion resistance deteriorates. For this reason, the content of fine particles needs to be in the range of 0.1 to 5% by weight, and preferably in the range of 0.1 to 3% by weight.
上記微粒子の添加時期は、溶融成形以前の任意の段階で
よく、特に、ポリエステル合成反応の第１段階の反応が
完了する以前に添加するのが好ましい。また、前記スル
ホン酸ホスホニウム塩と同時に添加しても、別々に任意
の順序で添加してもよい。The fine particles may be added at any stage before melt molding, and it is particularly preferable to add them before the first stage of the polyester synthesis reaction is completed. Further, the phosphonium sulfonate salts may be added simultaneously or separately in any order.
なお、本発明において使用するスルホン酸ホスホニウム
塩を共重合させたポリエステルは、該共重合成分の耐熱
性が劣るために共重合ポリエステルの重合反応過程や溶
融成形過程の高熱条件下で自ら分解したり、又はポリマ
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
に着色せしめ、且つポリエステルの重合度を低下せしめ
、更にこの着色が染色した際に色調を悪化させる。その
ため、この共重合ポリエステルの耐熱性を向上させるこ
とを目的として、テトラメチルホスホニウムクロライド
、テトラメチルホスホニウムブロマイド、テトラメチル
ホスホニウムアイオダイド、テトラメチルホスホニウム
ハイドロオキサイド、テトラエチルホスホニウムクロラ
イド、テトラプロピルホスホニウムクロライド、テトラ
イソプロピルホスホニウムクロライド、テトラブチルホ
スホニウムクロライド、テトラブチルホスホニウムブロ
マイド、テトラブチルホスホニウムアイオダイド、テト
ラブチルホスホニウムハイドロオキサイド、ブチルトリ
フェニルホスホニウムクロライド。In addition, the polyester copolymerized with the sulfonic acid phosphonium salt used in the present invention has poor heat resistance, so it may decompose by itself under high heat conditions during the polymerization reaction process or melt molding process of the copolymerized polyester. Or, it accelerates the decomposition of the polymer, colors the produced polyester or molded article yellowish brown, and lowers the degree of polymerization of the polyester, and furthermore, this coloring worsens the color tone when dyed. Therefore, in order to improve the heat resistance of this copolymerized polyester, tetramethylphosphonium chloride, tetramethylphosphonium bromide, tetramethylphosphonium iodide, tetramethylphosphonium hydroxide, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetraisopropyl Phosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide, tetrabutylphosphonium hydroxide, butyltriphenylphosphonium chloride.
エチルトリオクチルホスホニウムクロライド、ヘキザデ
シルトリブチルホスホニウムクロライド。Ethyltrioctylphosphonium chloride, hexadecyltributylphosphonium chloride.
エチルトリヘキシルホスホニウムクロライド、シクロへ
キシルトリブチルホス示ニウムクロライド。Ethyltrihexylphosphonium chloride, cyclohexyltributylphosphonium chloride.
ヘンシルトリブチルホスホニウムクロライド、テトラフ
ェニルホスホニウムクロライド、テトラフェニルホスホ
ニウムハイドロオキサイド、オクチルトリメチルホスホ
ニウムクロライド、オクチルジメチルへンジルホスホニ
ウムクロライド、ラウリルジメチルベンジルホスホニウ
ムクロライド。Hensyltributylphosphonium chloride, tetraphenylphosphonium chloride, tetraphenylphosphonium hydroxide, octyltrimethylphosphonium chloride, octyldimethylhendylphosphonium chloride, lauryldimethylbenzylphosphonium chloride.
ラウリルジメチルヘンシルホスホニウムハイドロオキサ
イド、ステアリルトリメチルホスホニウムクロライド、
ラウリルトリメチルホスホニウムエトサルフェート、ラ
ウリルヘンゼントリメチルボスホニウムメトサルフェー
ト、ラウリルジメチル−０−クロルベンジルホスホニウ
ムクロライド。lauryldimethylhensylphosphonium hydroxide, stearyltrimethylphosphonium chloride,
Lauryltrimethylphosphonium ethosulfate, laurylhenzentrimethylbosphonium methosulfate, lauryldimethyl-0-chlorobenzylphosphonium chloride.
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
ムアセテート。Stearylethyldihydroxyethylphosphonium ethosulfate, tetrabutylphosphonium acetate,
Tetrabutylphosphonium dodecylbenzenesulfonate, tetrabutylphosphonium tosylate, tetrabutylphosphonium stearate, tetrabutylphosphonium acetate.
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、エチルしりフェニルホス
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、ヘンシルトリフェニル
ホスホニウムクロライド、トリブチル了りルホスホニウ
ムブ０マイト、エチレンビストリス（２−シアノエチル
）ホスホニウムブロマイド、トリス−２−シアノエチル
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）ホスホニラムク１：Ｉライド等の第４
級ホスホニウム化合物、あるい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。Tetrabutylphosphonium phosphate, tetra, butylphosphonium phosphite, ethylphosphonium bromide, tetrabutylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium bromide, hensyltriphenylphosphonium chloride, tributylphosphonium bromide phosphonium bromide, ethylenebistris(2-cyanoethyl)phosphonium bromide, tris-2-cyanoethylallylphosphonium chloride, tetrakis(hydroxymethyl)phosphonium sulfate, tetrakis(hydroxymethyl)phosphonylamuc 1:I ride, etc.
grade phosphonium compounds, or tetramethylammonium hydroxide, tetramethylammonium chloride, tetraethylammonium hydroxide, tetraethylammonium chloride.
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、塩化
テトラフェニルアンモニウム等の第４級アンモニウム塩
などを添加するのが好ましい。Tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium hydroxide, tetrapropylammonium chloride, tetraisopropylammonium hydroxide, tetraisopropylammonium chloride,
It is preferable to add quaternary ammonium salts such as tetrabutylammonium hydroxide, tetrabutylammonium chloride, tetraphenylammonium hydroxide, and tetraphenylammonium chloride.
また、本発明で用いる共重合ポリエステルには、立体障
害フェノール系化合物、１−リアゾール系化金物の如き
耐酸化剤を配合するのが好ましく、更に、エーテル結合
生成抑制剤、例えば酢酸ナトリウムの如き有機ナトリウ
ム金属塩を添加するのも望ましい。その他必要に応じて
任意の添加剤、例えば触媒１着色防止剤、耐熱剤、難燃
剤、酸化防止剤、艶消剤９着色剤、無機微粒子等が含ま
れていてもよい。In addition, the copolymerized polyester used in the present invention preferably contains an oxidation-resistant agent such as a sterically hindered phenol compound or a 1-riazole metal compound, and further contains an ether bond formation inhibitor such as an organic compound such as sodium acetate. It is also desirable to add sodium metal salts. Other arbitrary additives such as catalyst 1 coloring inhibitor, heat resistant agent, flame retardant, antioxidant, matting agent 9 coloring agent, inorganic fine particles, etc. may be included as necessary.
上述の共重合ポリエステルを成形するには、任意の成形
条件を採用することができる。例えば、製糸に際しては
、５００〜２５００ｍ／分の速度で紡糸し、延伸、熱処
理する方法、１５００〜５０００ｍ／分の速度で紡糸し
、延伸、仮撚加工を同時に又は続いて行う方法、５００
０ ｍ７分以上の高速で紡糸し、用途によっては延伸工
程を省略する方法等任意の製糸条件が採用される。この
場合、単繊維繊度が１．０デニール以下の細繊度糸条の
製造が可能となる。また、フィルムやシートの用途に使
用する際にも、任意の成形条件を採用することができる
。Any molding conditions can be employed to mold the above-mentioned copolymerized polyester. For example, when spinning yarn, a method of spinning at a speed of 500 to 2,500 m/min, drawing and heat treatment, a method of spinning at a speed of 1,500 to 5,000 m/min, drawing and false twisting simultaneously or sequentially,
Any spinning conditions may be adopted, such as spinning at a high speed of 0 m7 minutes or more and omitting the stretching step depending on the application. In this case, it becomes possible to produce fine yarn having a single fiber fineness of 1.0 denier or less. Moreover, when used for film or sheet applications, arbitrary molding conditions can be adopted.
例えば製膜後一方向のみに張力をかけて異方性を持たせ
る方法、同時に又は任意の順序で二方向に延伸する方法
、２段階以上の多段延伸する方法等任意の条件が採用さ
れる。この場合にも、フィルムの厚さが１０μｍ以下の
薄いフィルムの製造が可能となる。For example, any conditions may be employed, such as a method of applying tension in only one direction after film formation to provide anisotropy, a method of stretching in two directions simultaneously or in an arbitrary order, a method of multi-stage stretching of two or more stages, etc. In this case as well, it is possible to manufacture a thin film with a thickness of 10 μm or less.
更に、上記微粒子含有共重合ポリエステル成形物をアル
カＩＪ ｉｌ重量処理ると、微粒子の一部が除去されて
成形物表面に黴細な凹凸が多数形成され、染色時の深色
性、鮮明性が改良される。かかる微粒子の除去は、成形
後必要に応じて延伸熱処理し、また糸条の場合は仮撚加
工等を施した後、又は更に布帛にした後、アルカリ化合
物の水溶液で処理することにより容易に行うことができ
る。Furthermore, when the fine particle-containing copolyester molded product is subjected to alkaline IJ il weight treatment, some of the fine particles are removed and many moldy irregularities are formed on the surface of the molded product, resulting in poor deep color and vividness during dyeing. Improved. Such fine particles can be easily removed by subjecting the fabric to a stretching heat treatment if necessary after forming, or in the case of yarn, by subjecting it to false twisting, etc., or by further treating it with an aqueous solution of an alkaline compound after it is made into a fabric. be able to.
ここで使用するアルカリ化合物としては水酸化ナトリウ
ム、水酸化カリウム、テトラメチルアンモニウムハイド
ロオキサイド、炭酸ナトリウム。The alkaline compounds used here include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, and sodium carbonate.
炭酸カリウム等をあげることができる。なかでも水酸化
ナトリウム、水酸化カリウムが特に好ましい。Examples include potassium carbonate. Among these, sodium hydroxide and potassium hydroxide are particularly preferred.
かかるアルカリ化合物の水溶液の濃度は、アルカリ化合
物の種類、処理条件等によって異なるが、通常０．０１
〜４０重量％の範囲が好ましく、特に０．１〜３０重量
％の範囲が好ましい。処理温度は常温〜１００℃の範囲
が好ましく、処理時間は１分〜４時間の範囲で通常行わ
れる。また、このアルカリ化合物の水溶液の処理によっ
て溶出除去する量は、成形物の重量に対して２重量％以
上にすべきである。このようにアルカリ化合物の水溶液
で処理することによって、可視光線の波長域又はそれ以
下の大きさの凹凸を成形物表面の全面に多数有するポリ
エステル成形物が得られ、染色した際に、深色性、鮮明
性が良好となる。The concentration of such an aqueous solution of an alkali compound varies depending on the type of alkali compound, processing conditions, etc., but is usually 0.01.
A range of 40% by weight is preferred, and a range of 0.1 to 30% by weight is particularly preferred. The treatment temperature is preferably in the range of room temperature to 100°C, and the treatment time is usually in the range of 1 minute to 4 hours. Further, the amount of the alkaline compound eluted and removed by treatment with the aqueous solution should be 2% by weight or more based on the weight of the molded article. By treating with an aqueous solution of an alkaline compound in this way, a polyester molded product having many irregularities in the visible light wavelength range or smaller on the entire surface of the molded product can be obtained, and when dyed, it has a deep color property. , the clarity is good.
（作用）
本発明によれば、スルホン酸ホスホニウム塩共重合ポリ
エステルの成形性が向上し、繊維の細い糸条、厚さの薄
いフィルムを容易に成形することが可能となるが、その
理由は未だ明確ではない。(Function) According to the present invention, the moldability of the sulfonic acid phosphonium salt copolymerized polyester is improved, and it becomes possible to easily mold thin fiber threads and thin films, but the reason for this is still unknown. It's not clear.
従来から、ポリエステル繊維に平均の一次粒径が１００
ｍμ以下の微粒子を添加して、アルカＩＪ 重量処理す
ることにより繊維表面に微細な凹凸を多数形成せしめ、
ポリエステル繊維を染色した際の深色性、鮮明性を改良
することが、例えば、特開昭５５−１０７５１２号公報
、特開昭５７〜１３９１１８号公報などで知られている
。しかしながら、従来公知の通常のポリエステル繊維に
、平均一次粒子径が１００ｍμ以下の微粒子を添加して
も、成形性はほとんど改善されないのである。Traditionally, polyester fibers have an average primary particle size of 100
By adding fine particles of less than mμ and subjecting the fiber to alkali IJ weight treatment, many fine irregularities are formed on the fiber surface.
It is known, for example, in JP-A-55-107512 and JP-A-57-139118 to improve the deep color and sharpness when dyeing polyester fibers. However, even if fine particles having an average primary particle diameter of 100 mμ or less are added to conventionally known ordinary polyester fibers, the moldability is hardly improved.
おそらく、スルホン酸ホスホニウム塩共重合ポリエステ
ルと微粒子との相互作用によって、成形性が大幅に向上
するものと考えられる。It is thought that the moldability is greatly improved probably due to the interaction between the sulfonic acid phosphonium salt copolymerized polyester and the fine particles.
（実施例）
次に実施例をあげて本発明を更に詳述する。実施例中の
部及び％はそれぞれ重量部および重量％を示し、ポリマ
ーの極限粘度〔η〕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ものである。製糸性は紡糸
時の断糸回数（回／１０６ｍ）及び延伸時のランプ率（
２，５ｋｇ巻ボビン１００本を延伸する際の単糸切れに
よるローラ巻付回数）で示した。(Example) Next, the present invention will be explained in further detail by giving examples. Parts and % in the examples indicate parts by weight and % by weight, respectively, and the intrinsic viscosity [η] of the polymer was determined from the value measured in an orthochlorophenol solution at 35°C. The spinning property is determined by the number of yarn breaks during spinning (times/106m) and the ramp rate during drawing (
It is expressed as the number of roller windings due to single yarn breakage when drawing 100 2.5 kg bobbins.
また、深色性を示す尺度としては、深色度（Ｋ／Ｓ）を
用いた。この値はサンプル布の分光反射率（Ｒ）を島津
ＲＣ−３３０型分光度計にて測定し、次に示すクベルカ
ームンク（Ｋｕｂｅｌｋａ−Ｍｕｎｋ）の式から求めた
。この値が大きいほど深色効果が大きいことを示す。Furthermore, as a measure of bathochromicity, bathochromicity (K/S) was used. This value was determined by measuring the spectral reflectance (R) of the sample cloth using a Shimadzu RC-330 spectrometer and using the Kubelka-Munk equation shown below. The larger this value is, the greater the deep color effect is.
なお、Ｋは吸収係数、Ｓは散乱係数を示す。Note that K represents an absorption coefficient and S represents a scattering coefficient.
実施例１〜７、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０．０３部（テレフタル酸ジ
メチルに対して０．０２４モル％）及び整色剤として酢
酸コバルト４水塩０．００９部（テレフタル酸ジメチル
に対して０．００７モル％）をエステル交換缶に仕込み
、窒素ガス雰囲気下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。Examples 1-7, Comparative Examples 1-3 100 parts of dimethyl terephthalate, 6 ethylene glycol
0 parts, 0.03 parts of manganese acetate tetrahydrate (0.024 mol % based on dimethyl terephthalate) and 0.009 parts of cobalt acetate tetrahydrate (0.007 mol based on dimethyl terephthalate) as a coloring agent. %) in a transesterification tank and heated from 140℃ to 220℃ for 3 hours under nitrogen gas atmosphere.
The transesterification reaction was carried out while the methanol produced by raising the temperature to 100°C was distilled out of the system.
続いて得られた生成物に第１表記載量の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
ム塩を２０％加熱エチレングリコール溶液の状態で添加
し、次いで、第１表に示す微粒子を生成ポリエステルに
対して３重量％となるように添加し、その後２２０°Ｃ
で２０分間攪拌した後、安定剤として正リン酸の５６％
水溶液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、同時に過剰エチレングリコー
ルの昇温追出しを開始した。１０分後重縮合触媒として
二酸化アンチモン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。内温か２４０°
Ｃ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た。次いで昇温しなから
内温か２６０℃に到達するまで常圧反応させた後、１時
間かけて７６０ ｍ ｍ ｌ ｇから１ｍｍｔ１ｇまで
減圧し、同時に１時間３０分かげて内温を２８０℃まで
昇温した。Subsequently, 3,5-dicarboxybenzenesulfonic acid tetra-n-butylphosphonium salt in the amount listed in Table 1 was added to the obtained product in the form of a 20% heated ethylene glycol solution, and then the fine particles shown in Table 1 were added. was added to the resulting polyester at a concentration of 3% by weight, and then heated at 220°C.
After stirring for 20 minutes at 56% of orthophosphoric acid as a stabilizer.
0.03 parts of aqueous solution (0.03 parts per dimethyl terephthalate)
033 mol %) was added, and at the same time, expulsion of excess ethylene glycol was started at elevated temperature. After 10 minutes, 0.04 part of antimony dioxide (0.027 mol % based on dimethyl terephthalate) was added as a polycondensation catalyst. Internal temperature 240°
When reaching C, the expulsion of ethylene glycol was completed, and the reaction product was transferred to a polymerization vessel. Next, the reaction was carried out under normal pressure until the internal temperature reached 260°C without increasing the temperature, and then the pressure was reduced from 760 mml g to 1 mmt1g over 1 hour, and at the same time the internal temperature was raised to 280°C over 1 hour and 30 minutes. It was warm.
１ｍ＊ＩＩｇ以下の減圧下、重合温度２８０℃で極限粘
度〔η〕が略０．６４になるまで反応を続けた。なお、
第１表に示す微粒子のうち、リン酸Ｃａ系内部粒子は、
リン酸トリメチルと酢酸カルシウム１水塩とをエチレン
グリコール中で反応せしめて調整したリン酸エステルカ
ルシウム塩溶液に酢酸カルシウム１水塩を溶解せしめて
得たリン酸ジエステルカルシウム塩と酢酸カルシウムと
の混合溶液をポリエステル反応系に添加して析出させた
ものである。The reaction was continued under reduced pressure of 1 m*IIg or less at a polymerization temperature of 280° C. until the intrinsic viscosity [η] reached approximately 0.64. In addition,
Among the fine particles shown in Table 1, the Ca phosphate internal particles are:
A mixed solution of diester calcium phosphate and calcium acetate obtained by dissolving calcium acetate monohydrate in a calcium phosphate salt solution prepared by reacting trimethyl phosphate and calcium acetate monohydrate in ethylene glycol. is added to a polyester reaction system and precipitated.
このポリマーを常法に従ってチップ化し、乾燥して、孔
径０．３龍の円形紡糸孔を２４個穿設した紡糸口金を使
用して２８５℃で熔融紡糸した。次いで得られた未延伸
糸を、最終的に得られる延伸糸の伸度が３０％になる延
伸倍率で、８４℃の供給ローラと１８０°Ｃのプレート
ヒーターを使って延伸、熱処理して５０デニール／４８
フイラメントの延伸糸を得た。この延伸糸に、Ｓ 撚２
５００ Ｔ ／ ｍ及びＺ撚２５００Ｔ／Ｍの強撚を施
し、続いて該強撚糸を８０℃で３０分間蒸熱処理して燃
上めを行った。該燃上め強撚糸を緯密度４７本／ ｃｍ
、緯密度３２本／ ｃｍでｓ、ｚ撚を２本交互に配して
梨地ジョーゼット織物を製織した。This polymer was chipped according to a conventional method, dried, and melt-spun at 285° C. using a spinneret having 24 circular spinning holes with a hole diameter of 0.3 mm. Next, the obtained undrawn yarn was drawn and heat-treated at a draw ratio such that the elongation of the finally obtained drawn yarn was 30% using a supply roller at 84°C and a plate heater at 180°C, and was heat-treated to give a 50 denier. /48
A drawn filament yarn was obtained. This drawn yarn has S twist 2
A strong twist of 500 T/m and a Z twist of 2500 T/M was applied, and then the highly twisted yarn was steamed at 80° C. for 30 minutes to heat it up. The weft density of the hard-twisted yarn is 47 threads/cm.
A satin georgette fabric was woven by alternately arranging two s and z twists at a weft density of 32 threads/cm.
得られた生機をロータリーワッシャーにて沸騰温度で２
０分間リラックス処理を施し、シボ立てを行い、常法に
よりプリセント後、３．５％の水酸化ナトリウム水溶液
で沸騰温度にて処理し、減量率が２０重量％の布帛を得
た。これらのアルカリ処理後の布帛をカチオン染料Ｃａ
ｔｈｉｌｏｎ ＣＤ−ＰＲＬＨ／Ｃａｔｈｉ１ｏｎ Ｂ
ｌｕｅ ＣＤ−ＦＢＬＨ＝ １ ： １ （保土谷化
学（株）製）を２％ｏｗｆ含む染浴（助剤として芒硝３
ｇ／ρ、酢酸０．３ ｇ ／ ｊ２を含む）で１２０°
Ｃ６０分間染色した。このときの製糸性及び染色布帛の
深色度は第２表に示す通りであった。The obtained gray fabric is heated to boiling temperature in a rotary washer for 2 hours.
The fabric was subjected to a relaxing treatment for 0 minutes, embossed, prescented using a conventional method, and then treated with a 3.5% aqueous sodium hydroxide solution at boiling temperature to obtain a fabric with a weight loss rate of 20%. These alkali-treated fabrics are treated with cationic dye Ca.
thilon CD-PRLH/Cathi1on B
dye bath containing 2% owf of lue CD-FBLH = 1:1 (manufactured by Hodogaya Chemical Co., Ltd.) (with 3 ml of Glauber's salt as an auxiliary agent).
g/ρ, including 0.3 g/j2 of acetic acid) at 120°
C. Stained for 60 minutes. The spinning properties and the bathochromic degree of the dyed fabric at this time were as shown in Table 2.
実施例８
実施例２において、カチオン染料可染化剤として使用し
た３、５−ジカルボキシヘンゼンスルホン酸テトラ−ｎ
−ブチルホスホニウム塩に代えて、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
塩を使用する以外は実施例２と同様に行った。結果を第
２表に示す。Example 8 Tetra-n 3,5-dicarboxyhenzenesulfonic acid used as a cationic dye dyeing agent in Example 2
The same procedure as in Example 2 was carried out except that 3,5-dicarboxybenzenesulfonic acid butyltriphenylphosphonium salt was used in place of the -butylphosphonium salt. The results are shown in Table 2.
実施例９
実施例２においてカチオン染料可染化剤として使用した
３、５−ジカルボキシヘンゼンスルホン酸テトラｎ−ブ
チルホスホニウム塩に代えて３．５＝ジカルボメトキシ
ヘンゼンスルホン酸テトラｎ −ブチルホスホニウム塩
を使用すると共にその添加時期をエステル交換反応開始
前に変更する以外は実施例２と同様に行った。結果は第
２表に示す通りであった。Example 9 Tetra n-butyl 3,5-dicarboxyhenzenesulfonate used as a cationic dye dyeing agent in Example 2 was replaced with tetra n-butyl 3,5-dicarboxyhenzenesulfonate. Example 2 was carried out in the same manner as in Example 2, except that a phosphonium salt was used and the timing of its addition was changed to before the start of the transesterification reaction. The results were as shown in Table 2.
（本頁、以下余白）
第 １ 表
第２表
実施例１０〜１３、比較例４．５
実施例２において、リン酸Ｃａ系内部粒子の添別置を第
３表に示すように種々変更し、それ以外は実施例２と同
様にして実験を行った。結果を第３表に示す。(This page, blank space below) Table 1 Table 2 Examples 10 to 13, Comparative Example 4.5 In Example 2, the placement of the Ca phosphate internal particles was variously changed as shown in Table 3. The experiment was conducted in the same manner as in Example 2 except for the above. The results are shown in Table 3.
第 ３ 表
実施例１４〜１６ 比較例６
実施例４において、コロイダルシリカの平均一次粒子径
を第４表に示すように種々変更し、それ以外は実施例４
と同様にして実験を行った。結果を第４表に示す。Table 3 Examples 14 to 16 Comparative Example 6 In Example 4, the average primary particle diameter of colloidal silica was variously changed as shown in Table 4, and the rest was as in Example 4.
An experiment was conducted in the same manner. The results are shown in Table 4.
（木頁、以下余白）
第 ４ 表
（発明の効果）
本発明方法によれば、スルホン酸ホスボニウム塩共重合
ポリエステルを安定した状態で成形することができ、特
に繊度の小さい糸条、厚さの薄いフィルムの成形が可能
となる。更に、成形物を染色した際の深色性、鮮明性が
アクリル、アセテート成形物並に向上し、スポーツ衣料
、スポーツ用具などに特に好適に用いることができる。(Wood pages, blank space below) Table 4 (Effects of the Invention) According to the method of the present invention, sulfonic acid phosbonium salt copolymerized polyester can be molded in a stable state, and especially yarns with small fineness and thickness can be molded. It becomes possible to form thin films. Furthermore, when the molded product is dyed, the deep color and clarity are improved to the same level as those of acrylic and acetate molded products, making it particularly suitable for use in sports clothing, sports equipment, and the like.
Claims (1)
のエステル形成性誘導体、少なくとも一種のアルキレン
グリコール又はそのそのエステル形成性誘導体及び該二
官能性カルボン酸成分に対して０．５〜１０．０モル％
の下記一般式で表わされるスルホン酸ホスホニウム塩か
らなる共重合ポリエステルを溶融成形するに際し、溶融
成形以前の任意の段階で、平均一次粒子径が１００ｍμ
以下の微粒子を該共重合ポリエステルに対して０．１〜
５重量％添加することを特徴とする共重合ポリエステル
成形物の製造方法。 ▲数式、化学式、表等があります▼ 〔式中、Ａは芳香族基又は脂肪族基、Ｘ＿１はエステル
形成性官能基、Ｘ＿２はＸ＿１と同一又は異なるエステ
ル形成性官能基又は、水素原子、Ｒ＿１、Ｒ＿２、Ｒ＿
３及びＲ＿４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。〕[Scope of Claims] 1. 0 for difunctional carboxylic acid mainly consisting of terephthalic acid or its ester-forming derivative, at least one alkylene glycol or its ester-forming derivative, and the difunctional carboxylic acid component. .5-10.0 mol%
When melt-molding a copolymerized polyester consisting of a sulfonic acid phosphonium salt represented by the following general formula, the average primary particle diameter is 100 mμ at any stage before melt-molding.
The following fine particles are added to the copolyester from 0.1 to
A method for producing a copolyester molded article, characterized in that 5% by weight is added. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, A is an aromatic group or an aliphatic group, X_1 is an ester-forming functional group, X_2 is an ester-forming functional group that is the same as or different from X_1, or a hydrogen atom, R_1 , R_2, R_
3 and R_4 are the same or different groups selected from alkyl groups and aryl groups, and n represents a positive integer. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1320988A JPH01192821A (en) | 1988-01-22 | 1988-01-22 | Production of formed article of copolymerized polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1320988A JPH01192821A (en) | 1988-01-22 | 1988-01-22 | Production of formed article of copolymerized polyester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01192821A true JPH01192821A (en) | 1989-08-02 |
Family
ID=11826761
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1320988A Pending JPH01192821A (en) | 1988-01-22 | 1988-01-22 | Production of formed article of copolymerized polyester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01192821A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04228615A (en) * | 1990-12-27 | 1992-08-18 | Teijin Ltd | Production of hygroscopic polyester fiber |
| JPH0625397A (en) * | 1992-07-07 | 1994-02-01 | Polyplastics Co | Production of polyester resin or of its composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6081314A (en) * | 1983-10-13 | 1985-05-09 | Teijin Ltd | Preparation of polyester yarn |
| JPS6091314A (en) * | 1983-10-26 | 1985-05-22 | Matsushita Electric Ind Co Ltd | Automatic focus adjusting device of camera |
| JPS61275422A (en) * | 1985-05-24 | 1986-12-05 | Teijin Ltd | Polyester fiber |
-
1988
- 1988-01-22 JP JP1320988A patent/JPH01192821A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6081314A (en) * | 1983-10-13 | 1985-05-09 | Teijin Ltd | Preparation of polyester yarn |
| JPS6091314A (en) * | 1983-10-26 | 1985-05-22 | Matsushita Electric Ind Co Ltd | Automatic focus adjusting device of camera |
| JPS61275422A (en) * | 1985-05-24 | 1986-12-05 | Teijin Ltd | Polyester fiber |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04228615A (en) * | 1990-12-27 | 1992-08-18 | Teijin Ltd | Production of hygroscopic polyester fiber |
| JPH0625397A (en) * | 1992-07-07 | 1994-02-01 | Polyplastics Co | Production of polyester resin or of its composition |
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