JP2009161693A - Atmospheric pressure cation-dyeable polyester composition and polyester fiber composed of it - Google Patents
Atmospheric pressure cation-dyeable polyester composition and polyester fiber composed of it Download PDFInfo
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- JP2009161693A JP2009161693A JP2008002397A JP2008002397A JP2009161693A JP 2009161693 A JP2009161693 A JP 2009161693A JP 2008002397 A JP2008002397 A JP 2008002397A JP 2008002397 A JP2008002397 A JP 2008002397A JP 2009161693 A JP2009161693 A JP 2009161693A
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- JP
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- Prior art keywords
- atmospheric pressure
- polyester
- dyeable polyester
- polyester composition
- cationic dyeable
- 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.)
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- 229920000728 polyester Polymers 0.000 title claims abstract description 113
- 239000000835 fiber Substances 0.000 title claims abstract description 49
- 239000000203 mixture Substances 0.000 title claims abstract description 40
- 239000002245 particle Substances 0.000 claims abstract description 56
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- 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 claims abstract description 28
- 150000003839 salts Chemical class 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 14
- 230000009477 glass transition Effects 0.000 claims abstract description 12
- 238000009826 distribution Methods 0.000 claims abstract description 7
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001768 cations Chemical class 0.000 claims abstract description 4
- 125000002091 cationic group Chemical group 0.000 claims description 54
- 229920001634 Copolyester Polymers 0.000 claims description 32
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 29
- -1 phosphonium ion Chemical class 0.000 claims description 22
- 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 claims description 14
- 238000007334 copolymerization reaction Methods 0.000 claims description 14
- 238000002074 melt spinning Methods 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 8
- 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 claims description 8
- 208000016261 weight loss Diseases 0.000 claims description 8
- 239000001506 calcium phosphate Substances 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 5
- 235000011010 calcium phosphates Nutrition 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000013585 weight reducing agent Substances 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 235000019731 tricalcium phosphate Nutrition 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000378 calcium silicate Substances 0.000 claims description 2
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052622 kaolinite Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 2
- 229940078499 tricalcium phosphate Drugs 0.000 claims description 2
- 238000004043 dyeing Methods 0.000 abstract description 18
- 229920001577 copolymer Polymers 0.000 abstract description 11
- 150000004714 phosphonium salts Chemical class 0.000 abstract description 6
- 230000014509 gene expression Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 14
- 238000006068 polycondensation reaction Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000975 dye Substances 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 10
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- 239000004744 fabric Substances 0.000 description 7
- 238000009987 spinning Methods 0.000 description 7
- 208000012886 Vertigo Diseases 0.000 description 6
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- 238000005809 transesterification reaction Methods 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- CBFCDTFDPHXCNY-UHFFFAOYSA-N octyldodecane Natural products CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 150000003609 titanium compounds Chemical class 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 2
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical group O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 239000000986 disperse dye Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 150000002531 isophthalic acids Chemical class 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 150000003503 terephthalic acid derivatives Chemical class 0.000 description 2
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 229920006307 urethane fiber Polymers 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 description 1
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- KPOUTQVXTNYPMU-UHFFFAOYSA-K 5-sulfonatobenzene-1,3-dicarboxylate tetrabutylazanium Chemical compound [O-]C(=O)c1cc(cc(c1)S([O-])(=O)=O)C([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC KPOUTQVXTNYPMU-UHFFFAOYSA-K 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
- OYVSCOIPUCWFLU-UHFFFAOYSA-K 5-sulfonatobenzene-1,3-dicarboxylate tetraethylazanium Chemical compound CC[N+](CC)(CC)CC.CC[N+](CC)(CC)CC.CC[N+](CC)(CC)CC.[O-]C(=O)c1cc(cc(c1)S([O-])(=O)=O)C([O-])=O OYVSCOIPUCWFLU-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
- OWTRJRFDEXASRF-UHFFFAOYSA-K CC(CCC)([P+](CCCC)(CCCC)CCCC)C.S(=O)(=O)([O-])C=1C=C(C=C(C(=O)[O-])C1)C(=O)[O-].CC(CCC)(C)[P+](CCCC)(CCCC)CCCC.CC(CCC)(C)[P+](CCCC)(CCCC)CCCC Chemical compound CC(CCC)([P+](CCCC)(CCCC)CCCC)C.S(=O)(=O)([O-])C=1C=C(C=C(C(=O)[O-])C1)C(=O)[O-].CC(CCC)(C)[P+](CCCC)(CCCC)CCCC.CC(CCC)(C)[P+](CCCC)(CCCC)CCCC OWTRJRFDEXASRF-UHFFFAOYSA-K 0.000 description 1
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- BMHLGLFBHFUNDQ-UHFFFAOYSA-K [O-]C(=O)c1cc(cc(c1)S([O-])(=O)=O)C([O-])=O.c1ccc(cc1)[N+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[N+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[N+](c1ccccc1)(c1ccccc1)c1ccccc1 Chemical compound [O-]C(=O)c1cc(cc(c1)S([O-])(=O)=O)C([O-])=O.c1ccc(cc1)[N+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[N+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[N+](c1ccccc1)(c1ccccc1)c1ccccc1 BMHLGLFBHFUNDQ-UHFFFAOYSA-K 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- MAAPEMRACZBJAD-UHFFFAOYSA-K benzyl(tributyl)phosphanium 5-sulfonatobenzene-1,3-dicarboxylate Chemical compound [O-]C(=O)c1cc(cc(c1)S([O-])(=O)=O)C([O-])=O.CCCC[P+](CCCC)(CCCC)Cc1ccccc1.CCCC[P+](CCCC)(CCCC)Cc1ccccc1.CCCC[P+](CCCC)(CCCC)Cc1ccccc1 MAAPEMRACZBJAD-UHFFFAOYSA-K 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
- QGLYFXPXNKWSHU-UHFFFAOYSA-N benzyl-dimethyl-propan-2-ylazanium Chemical class CC(C)[N+](C)(C)CC1=CC=CC=C1 QGLYFXPXNKWSHU-UHFFFAOYSA-N 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-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
- 229910052792 caesium Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- VKONPUDBRVKQLM-UHFFFAOYSA-N cyclohexane-1,4-diol Chemical compound OC1CCC(O)CC1 VKONPUDBRVKQLM-UHFFFAOYSA-N 0.000 description 1
- VEIOBOXBGYWJIT-UHFFFAOYSA-N cyclohexane;methanol Chemical compound OC.OC.C1CCCCC1 VEIOBOXBGYWJIT-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- SXCBDZAEHILGLM-UHFFFAOYSA-N heptane-1,7-diol Chemical compound OCCCCCCCO SXCBDZAEHILGLM-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Chemical group 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003297 rubidium Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229940087562 sodium acetate trihydrate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- YXTFRJVQOWZDPP-UHFFFAOYSA-M sodium;3,5-dicarboxybenzenesulfonate Chemical compound [Na+].OC(=O)C1=CC(C(O)=O)=CC(S([O-])(=O)=O)=C1 YXTFRJVQOWZDPP-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- OZKLODFEDYOIKC-UHFFFAOYSA-N terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1.OC(=O)C1=CC=C(C(O)=O)C=C1.OC(=O)C1=CC=C(C(O)=O)C=C1 OZKLODFEDYOIKC-UHFFFAOYSA-N 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- KLIUHARZXKNLFV-UHFFFAOYSA-N tert-butyl(triethyl)azanium Chemical class CC[N+](CC)(CC)C(C)(C)C KLIUHARZXKNLFV-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 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
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- IUBRMIZRRQJMGV-UHFFFAOYSA-N tributyl(2-methylpentan-2-yl)azanium Chemical class CCCC[N+](CCCC)(CCCC)C(C)(C)CCC IUBRMIZRRQJMGV-UHFFFAOYSA-N 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
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
- Artificial Filaments (AREA)
Abstract
Description
本発明は、常圧下でカチオン染料に可染性である常圧カチオン可染ポリエステル組成物及びそれよりなるポリエステル繊維に関する。 The present invention relates to a normal pressure cationic dyeable polyester composition that is dyeable to a cationic dye under normal pressure, and a polyester fiber comprising the same.
ポリエチレンテレフタレートを代表とするポリエステル繊維は、その化学的特性から分散染料、アゾイック染料でしか染色できないため、鮮明且つ深みのある色相が得られにくいという欠点があった。かかる欠点を解消する方法として、ポリエステルにスルホイソフタル酸の金属塩を２〜３モル％共重合する方法が提案されている（例えば、特許文献１、特許文献２参照。）。 Polyester fibers typified by polyethylene terephthalate have the disadvantage that, because of their chemical properties, they can be dyed only with disperse dyes and azoic dyes, and thus it is difficult to obtain a clear and deep hue. As a method for eliminating such drawbacks, a method of copolymerizing a metal salt of sulfoisophthalic acid with 2 to 3 mol% of polyester has been proposed (see, for example, Patent Document 1 and Patent Document 2).
しかしながら、かかる方法によって得られるポリエステル繊維は、高温・高圧下でしか染色することができず、天然繊維やウレタン繊維などと交編、交織した後に染色すると、天然繊維、ウレタン繊維が脆化するという問題があった。これを常圧、１００℃付近の温度で十分に染色しようとすれば、スルホイソフタル酸の金属塩を多量にポリエステルに対して共重合されることが必要となるが、この場合スルホネート基による溶融粘度の増粘効果から、ポリエステルの重合度を高くすることができず、溶融紡糸にて得られるポリエステル繊維の強度が著しく低下し、さらに紡糸操業性が著しく悪化するという問題があった。 However, the polyester fiber obtained by such a method can be dyed only under high temperature and high pressure, and if it is dyed after knitting or weaving with natural fiber or urethane fiber, natural fiber and urethane fiber are embrittled. There was a problem. If this is to be sufficiently dyed at normal pressure and at a temperature around 100 ° C., it is necessary to copolymerize a large amount of the metal salt of sulfoisophthalic acid to the polyester. Because of this thickening effect, there is a problem that the degree of polymerization of the polyester cannot be increased, the strength of the polyester fiber obtained by melt spinning is remarkably lowered, and the spinning operability is remarkably deteriorated.
一方、このような問題を解決するため、イオン結合性分子間力の小さいカチオン可染性モノマーを共重合する技術が開示されている（例えば、特許文献３、特許文献４参照。）。イオン結合性分子間力の小さいカチオン可染性モノマーとしては、５−スルホイソフタル酸テトラブチルホスホネートなどが例示されているが、これらのカチオン可染性モノマー共重合ポリエステルは熱安定性が悪く、常圧カチオン可染化させるため、共重合量を増加させようとしても、重合反応途中で熱分解が進行し、高分子量化させることが困難であった。さらに溶融紡糸する際の熱履歴による分解が大きく、結果として得られる糸の強度が弱くなるという欠点を有していた。また、使用する５−スルホイソフタル酸テトラブチルホスホネートは非常に高価であり、結果として得られるカチオン可染性ポリエステルのコストが大幅に増大するという問題があった。 On the other hand, in order to solve such a problem, a technique for copolymerizing a cationic dyeable monomer having a small ion binding intermolecular force has been disclosed (for example, see Patent Document 3 and Patent Document 4). Examples of cationic dyeable monomers having a small ion-binding intermolecular force include 5-sulfoisophthalic acid tetrabutylphosphonate. These cationic dyeable monomer copolyesters have poor thermal stability and are usually Even if an attempt was made to increase the amount of copolymerization for pressure cationic dyeing, thermal decomposition progressed during the polymerization reaction, making it difficult to increase the molecular weight. Furthermore, there is a drawback that the decomposition due to the thermal history during melt spinning is large, and the strength of the resulting yarn is weakened. Further, the 5-sulfoisophthalic acid tetrabutylphosphonate used is very expensive, and the cost of the resulting cationic dyeable polyester is greatly increased.
かかる問題を解決する方法として、スルホイソフタル酸の金属塩に加え、分子量が２０００以上のポリエチレングリコールを共重合する方法、アジピン酸、セバシン酸などの直鎖炭化水素のジカルボン酸を共重合する方法、あるいはジエチレングリコール、ネオペンチルグリコール、シクロヘキサンジメタノールのようなグリコール成分を共重合する方法が提案されている（例えば、特許文献５、特許文献６参照。）。 As a method for solving such a problem, in addition to a metal salt of sulfoisophthalic acid, a method of copolymerizing polyethylene glycol having a molecular weight of 2000 or more, a method of copolymerizing a dicarboxylic acid of a linear hydrocarbon such as adipic acid or sebacic acid, Or the method of copolymerizing glycol components, such as diethylene glycol, neopentyl glycol, and cyclohexane dimethanol, is proposed (for example, refer patent document 5 and patent document 6).
一方、耐光性の低下が少なく、且つ常圧可染性を出す方法としてアジピン酸、セバシン酸のような直鎖炭化水素のジカルボン酸、あるいはジエチレングリコール、ネオペンチルグリコール、シクロヘキサンジメタノールのようなグリコール成分、また、平均分子量が４００〜１０００のポリアルキレングリコールをスルホイソフタル酸の金属塩と共重合する方法が提案されている（例えば、特許文献７参照。）。 On the other hand, as a method for producing a low pressure resistance decrease and normal pressure dyeability, linear hydrocarbon dicarboxylic acids such as adipic acid and sebacic acid, or glycol components such as diethylene glycol, neopentyl glycol, and cyclohexanedimethanol In addition, a method of copolymerizing a polyalkylene glycol having an average molecular weight of 400 to 1000 with a metal salt of sulfoisophthalic acid has been proposed (for example, see Patent Document 7).
しかしながら、これらいずれの方法でも得られたポリエステルを溶融紡糸して得られる常圧カチオン可染性ポリエステル繊維の強度が低くなり、強いては得られる布帛の引き裂き強度が低下する、更には染色堅牢度が低いなどの問題があった。 However, the strength of the atmospheric pressure cationic dyeable polyester fiber obtained by melt spinning the polyester obtained by any of these methods is lowered, and thus the tear strength of the resulting fabric is lowered, and further the dyeing fastness is increased. There was a problem such as low.
また、５−ナトリウムスルホイソフタル酸を共重合したポリエステルを鞘部に、９５モル％以上がエチレンテレフタレートの繰返し単位からなるポリエステルを芯部に配した複合繊維が提案されている（例えば、特許文献８参照。）。しかしながら、鞘部を構成する共重合ポリエステル中のスルホイソフタル酸成分の共重合量には、前述と同様の理由で限界があり、十分な染着性を得ることが困難であること、並びに複合繊維とすることで紡糸工程での加工コストが増加、又は繊維断面形状などに制約が生じるなどの課題があった。 Further, there has been proposed a composite fiber in which a polyester copolymerized with 5-sodium sulfoisophthalic acid is disposed in a sheath portion and a polyester having 95 mol% or more of ethylene terephthalate repeating units disposed in a core portion (for example, Patent Document 8). reference.). However, the copolymerization amount of the sulfoisophthalic acid component in the copolyester constituting the sheath part is limited for the same reason as described above, and it is difficult to obtain sufficient dyeing properties. As a result, there are problems such as an increase in processing cost in the spinning process or a restriction on the fiber cross-sectional shape.
本発明は上記の課題を解決するものであり、常圧下でのカチオン染色が可能で、且つ鮮明性、染色時に深色染色性が発現され、高強度の繊維が得られるほど高固有粘度を有する常圧カチオン可染性ポリエステル繊維を得ることができる常圧カチオン可染性ポリエステル組成物及びそれよりなる繊維を提供するものである。 The present invention solves the above-mentioned problems, and can be cationically dyed under normal pressure, and has a high intrinsic viscosity as a high-strength fiber is obtained. The present invention provides an atmospheric pressure cationic dyeable polyester composition capable of obtaining an atmospheric pressure cationic dyeable polyester fiber and a fiber comprising the same.
上記の課題に鑑み本発明者らは鋭意検討を行った結果、本発明を完成するに至った。すなわち本発明は、常圧カチオン可染性ポリエステルと不活性粒子からなるポリエステル組成物であって、該常圧カチオン可染性ポリエステルが主たる繰返し単位がエチレンテレフタレートより構成される共重合ポリエステルであって、該共重合ポリエステルを構成する酸成分中にスルホイソフタル酸の金属塩（Ａ）及び下記式（Ｉ）で表される化合物（Ｂ）を下記数式（１）及び（２）を同時に満足する状態で含有する共重合ポリエステルであって、該共重合ポリエステルのガラス転移温度が７０〜８５℃の範囲にあり、且つ得られる共重合ポリエステルの固有粘度が０．５５〜１．００ｄＬ／ｇの範囲にある常圧カチオン可染性ポリエステルであり、
３．０≦Ａ＋Ｂ≦５．０ （１）
０．２≦Ｂ／（Ａ＋Ｂ）≦０．７ （２）
［上記数式中、Ａは共重合ポリエステルを構成する全酸成分を基準とするスルホイソフタル酸の金属塩（Ａ）の共重合量（モル％）、Ｂは共重合ポリエステルを構成する全酸成分を基準とする上記式（Ｉ）で表される化合物（Ｂ）の共重合量（モル％）を表す。］
且つ平均粒子径が０．０１〜０．５μｍの範囲であって粒子径が０．５μｍを越える粒子の頻度分布率が不活性粒子全重量を基準として２０重量％以下である不活性粒子を常圧カチオン可染性ポリエステル組成物の重量を基準にして０．１〜５．０重量％含有する常圧カチオン可染性ポリエステル組成物、及び該ポリエステル組成物を溶融紡糸して得られる常圧カチオン可染性ポリエステル繊維である。該常圧カチオン可染性ポリエステル繊維は更にアルカリ減量加工することにより繊維表面に微細な凹凸構造を呈する常圧カチオン可染性ポリエステルとすることもでき、これにより上記の課題が解決できる。
In view of the above problems, the present inventors have intensively studied, and as a result, have completed the present invention. That is, the present invention is a polyester composition comprising a normal pressure cationic dyeable polyester and inert particles, wherein the normal pressure cationic dyeable polyester is a copolyester composed mainly of ethylene terephthalate. In the acid component constituting the copolyester, the metal salt of sulfoisophthalic acid (A) and the compound (B) represented by the following formula (I) satisfy the following formulas (1) and (2) at the same time: In which the glass transition temperature of the copolyester is in the range of 70 to 85 ° C., and the intrinsic viscosity of the copolyester obtained is in the range of 0.55 to 1.00 dL / g. An atmospheric pressure cationic dyeable polyester,
3.0 ≦ A + B ≦ 5.0 (1)
0.2 ≦ B / (A + B) ≦ 0.7 (2)
[In the above formula, A is the copolymerization amount (mol%) of the metal salt of sulfoisophthalic acid (A) based on the total acid component constituting the copolyester, and B is the total acid component constituting the copolyester. This represents the copolymerization amount (mol%) of the compound (B) represented by the above formula (I) as a reference. ]
Inactive particles having an average particle size in the range of 0.01 to 0.5 μm and a frequency distribution ratio of particles having a particle size exceeding 0.5 μm of 20% by weight or less based on the total weight of the inert particles are usually used. Normal pressure cationic dyeable polyester composition containing 0.1 to 5.0% by weight based on the weight of pressure cationic dyeable polyester composition, and normal pressure cation obtained by melt spinning the polyester composition It is a dyeable polyester fiber. The normal pressure cationic dyeable polyester fiber can be further reduced in alkali to obtain a normal pressure cationic dyeable polyester exhibiting a fine concavo-convex structure on the fiber surface, thereby solving the above-mentioned problems.
本発明によれば、常圧下でのカチオン染色による染着性が良好で、且つ鮮明性、染色時に深色染色性が発現される常圧カチオン可染性ポリエステル組成物及びそれよりなる繊維を提供することができる。また繊維の強度が十分な程度に高固有粘度を有するポリエステル組成物を提供することができる。 According to the present invention, there is provided a normal pressure cationic dyeable polyester composition that exhibits good dyeability by cationic dyeing under normal pressure, and that exhibits vividness and deep color dyeability during dyeing, and fibers comprising the same. can do. Moreover, the polyester composition which has high intrinsic viscosity so that the intensity | strength of a fiber is sufficient can be provided.
以下、本発明について詳細に説明する。
本発明に使用される共重合ポリエステルとは、テレフタル酸又はそのエステル形成性誘導体と、エチレングリコール成分とを重縮合反応せしめて得られるエチレンテレフタレートを主たる繰返し単位とする共重合ポリエステルであり、共重合成分としてスルホイソフタル酸の金属塩（Ａ）及び下記式（Ｉ）で表される化合物（Ｂ）を下記数式（１）及び（２）を同時に満足する状態で含有する共重合ポリエステルであり、該共重合ポリエステルのガラス転移温度が７０〜８５℃の範囲にあり、且つ得られる共重合ポリエステルの固有粘度が０．５５〜１．００ｄＬ／ｇの範囲にあることを特徴とするポリエステルである。
Hereinafter, the present invention will be described in detail.
The copolymerized polyester used in the present invention is a copolymerized polyester having ethylene terephthalate as a main repeating unit obtained by polycondensation reaction of terephthalic acid or an ester-forming derivative thereof and an ethylene glycol component. A copolyester containing a metal salt of sulfoisophthalic acid (A) as a component and a compound (B) represented by the following formula (I) in a state satisfying the following mathematical formulas (1) and (2) simultaneously: The polyester is characterized in that the glass transition temperature of the copolyester is in the range of 70 to 85 ° C., and the intrinsic viscosity of the copolyester obtained is in the range of 0.55 to 1.00 dL / g.
３．０≦Ａ＋Ｂ≦５．０ （１）
０．２≦Ｂ／（Ａ＋Ｂ）≦０．７ （２）
［上記数式中、Ａは共重合ポリエステルを構成する全酸成分を基準とするスルホイソフタル酸の金属塩（Ａ）の共重合量（モル％）、Ｂは共重合ポリエステルを構成する全酸成分を基準とする上記式（Ｉ）で表される化合物（Ｂ）の共重合量（モル％）を表す。］
3.0 ≦ A + B ≦ 5.0 (1)
0.2 ≦ B / (A + B) ≦ 0.7 (2)
[In the above formula, A is the copolymerization amount (mol%) of the metal salt of sulfoisophthalic acid (A) based on the total acid component constituting the copolyester, and B is the total acid component constituting the copolyester. This represents the copolymerization amount (mol%) of the compound (B) represented by the above formula (I) as a reference. ]
ここでテレフタル酸のエステル形成性誘導体とは、テレフタル酸の、ジメチルエステル、ジエチルエステル、ジプロピルエステル、ジブチルエステル、ジヘキシルエステル、ジオクチルエステル、ジデシルエステル、若しくはジフェニルエステル又はテレフタル酸ジクロライド、テレフタル酸ジブロマイドを挙げる事ができるが、これらの中でもテレフタル酸ジメチルエステルが好ましい。 Here, the ester-forming derivative of terephthalic acid is dimethyl ester, diethyl ester, dipropyl ester, dibutyl ester, dihexyl ester, dioctyl ester, didecyl ester, or diphenyl ester or terephthalic acid dichloride, terephthalic acid diterephthalic acid. Among them, dimethyl terephthalate is preferable.
（共重合ポリエステルについて）
本発明における共重合ポリエステルとはエチレンテレフタレートを主たる繰返し単位とするポリエステルであり、主たる繰り返し単位とは共重合ポリエステルを構成する全繰り返し単位あたり８０モル％以上がエチレンテレフタレート単位であることを指している。他の２０モル％以下の範囲内で他の成分が共重合されていても良い。好ましくは９０モル％以上がエチレンテレフタレート単位であることである。その他の共重合成分としては、ジカルボン酸成分としてイソフタル酸、２，６−ナフタレンジカルボン酸、２，７−ナフタレンジカルボン酸、４，４’−ジフェニルジカルボン酸、４，４’−ジフェニルメタンジカルボン酸、ジフェニルケトンジカルボン酸、４，４’−ジフェニルスルホンジカルボン酸、コハク酸、アジピン酸、アゼライン酸を挙げる事ができ、グリコール成分として１，２−プロピレングリコール、トリメチレングリコール、テトラメチレングリコール、ヘプタメチレングリコール、ヘキサメチレングリコール、ジエチレングリコール、ジプロピレングリコール、ビス（トリメチレングリコール）、ビス（テトラメチレングリコール）、トリエチレングリコール、１，４−ジヒドロキシシクロヘキサン、１，４−シクロヘキサンジメタノールが挙げる事ができ、これらの１種以上のジカルボン酸と１種以上のグリコール成分を反応させて得られる成分を繰り返し単位として共重合されていても良い。
(About copolymer polyester)
The copolymer polyester in the present invention is a polyester having ethylene terephthalate as a main repeating unit, and the main repeating unit indicates that 80 mol% or more of all repeating units constituting the copolymer polyester is an ethylene terephthalate unit. . Other components may be copolymerized within the other 20 mol% or less range. Preferably 90 mol% or more is an ethylene terephthalate unit. Other copolymer components include diphthalic acid components such as isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenylmethanedicarboxylic acid, diphenyl Examples thereof include ketone dicarboxylic acid, 4,4′-diphenylsulfone dicarboxylic acid, succinic acid, adipic acid, and azelaic acid, and 1,2-propylene glycol, trimethylene glycol, tetramethylene glycol, heptamethylene glycol, Hexamethylene glycol, diethylene glycol, dipropylene glycol, bis (trimethylene glycol), bis (tetramethylene glycol), triethylene glycol, 1,4-dihydroxycyclohexane, 1,4-cyclohexa Can dimethanol mentioned, it may be copolymerized as a repeating unit derived component by reacting these one or more dicarboxylic acids and one or more glycol components.
（スルホイソフタル酸の金属塩（Ａ）について）
本発明で使用されるスルホイソフタル酸の金属塩（Ａ）としては、５−スルホイソフタル酸のアルカリ金属塩（リチウム塩、ナトリウム塩、カリウム塩、ルビジウム塩、セシウム塩）が例示される。必要に応じてこれら化合物のマグネシウム塩、カルシウム塩等のアルカリ土類塩を併用しても良い。また、これらのエステル形成性誘導体も好ましく例示される。エステル形成性誘導体としてはジメチルエステル、ジエチルエステル、ジプロピルエステル、ジブチルエステル、ジヘキシルエステル、ジオクチルエステル、ジデシルエステル、ジフェニルエステル、５−スルホイソフタル酸金属塩のジハロゲン化物を挙げる事ができるが、これらの中でもジメチルエステルが好ましい。これらの化合物群の中では、熱安定性、コストなどの面から、５−スルホイソフタル酸のアルカリ金属塩が好ましく例示され、特に５−ナトリウムスルホイソフタル酸又はそのジメチルエステルである５−ナトリウムスルホイソフタル酸ジメチルが特に好ましく例示される。これらの条件を満たす化合物である場合に、ポリエステル繊維とした場合の充分なカチオン可染性と充分な繊維強度の両立が可能となる。
(About metal salt of sulfoisophthalic acid (A))
Examples of the metal salt (A) of sulfoisophthalic acid used in the present invention include alkali metal salts (lithium salt, sodium salt, potassium salt, rubidium salt, cesium salt) of 5-sulfoisophthalic acid. If necessary, alkaline earth salts such as magnesium salts and calcium salts of these compounds may be used in combination. These ester-forming derivatives are also preferably exemplified. Examples of the ester-forming derivative include dimethyl ester, diethyl ester, dipropyl ester, dibutyl ester, dihexyl ester, dioctyl ester, didecyl ester, diphenyl ester, and dihalogenated metal salt of 5-sulfoisophthalic acid. Of these, dimethyl ester is preferred. Among these compounds, an alkali metal salt of 5-sulfoisophthalic acid is preferably exemplified from the viewpoint of thermal stability, cost, etc., and in particular, 5-sodium sulfoisophthalic acid which is 5-sodium sulfoisophthalic acid or a dimethyl ester thereof. Particularly preferred is dimethyl acid. In the case of a compound satisfying these conditions, it is possible to achieve both sufficient cationic dyeability and sufficient fiber strength when used as a polyester fiber.
（化合物（Ｂ）について）
また、上記式（Ｉ）で表される化合物（Ｂ）としては、５−スルホイソフタル酸又はその低級アルキルエステルの４級ホスホニウム塩又は４級アンモニウム塩である。４級ホスホニウム塩、４級アンモニウム塩としては、リン原子又は窒素原子にアルキル基、ベンジル基又はフェニル基が結合した４級ホスホニウム塩、４級アンモニウム塩が好ましく、特に４級ホスホニウム塩であることが好ましい。また、４つある置換基は同一であっても異なっていても良い。上記式（Ｉ）で表される化合物の具体例としては、５−スルホイソフタル酸テトラブチルホスホニウム塩、５−スルホイソフタル酸エチルトリブチルホスホニウム塩、５−スルホイソフタル酸ベンジルトリブチルホスホニウム塩、５−スルホイソフタル酸フェニルトリブチルホスホニウム塩、５−スルホイソフタル酸テトラフェニルホスホニウム塩、５−スルホイソフタル酸ブチルトリフェニルホスホニウム塩、５−スルホイソフタル酸ベンジルトリフェニルホスホニウム塩、５−スルホイソフタル酸テトラメチルアンモニウム塩、５−スルホイソフタル酸テトラエチルアンモニウム塩、５−スルホイソフタル酸テトラブチルアンモニウム塩、５−スルホイソフタル酸テトラフェニルアンモニウム塩、５−スルホイソフタル酸ベンジルトリメチルアンモニウム塩、５−スルホイソフタル酸ベンジルトリメチルアンモニウム塩、あるいはこれらイソフタル酸誘導体のジメチルエステル、ジエチルエステル、ジプロプルエステル、ジブチルエステル、ジへキシルエステル、ジオクチルエステル、ジデシルエステルが好ましく例示される。これらのイソフタル酸誘導体の中でも、５−スルホイソフタル酸ジメチルテトラブチルホスホニウム塩、５−スルホイソフタル酸ジメチルベンジルトリブチルホスホニウム塩、５−スルホイソフタル酸ジメチルテトラフェニルホスホニウム塩、５−スルホイソフタル酸ジメチルテトラメチルアンモニウム塩、５−スルホイソフタル酸ジメチルテトラエチルアンモニウム塩、５−スルホイソフタル酸ジメチルテトラブチルアンモニウム塩、５−スルホイソフタル酸ジメチルベンジルトリメチルアンモニウム塩がより好ましく例示される。これらの条件を満たす化合物である場合に、ポリエステル繊維とした場合の充分なカチオン可染性と充分な繊維強度の両立が可能となる。
(Compound (B))
The compound (B) represented by the above formula (I) is quaternary phosphonium salt or quaternary ammonium salt of 5-sulfoisophthalic acid or a lower alkyl ester thereof. As the quaternary phosphonium salt or quaternary ammonium salt, a quaternary phosphonium salt or a quaternary ammonium salt in which an alkyl group, a benzyl group or a phenyl group is bonded to a phosphorus atom or a nitrogen atom is preferable, and a quaternary phosphonium salt is particularly preferable. preferable. The four substituents may be the same or different. Specific examples of the compound represented by the above formula (I) include 5-sulfoisophthalic acid tetrabutylphosphonium salt, 5-sulfoisophthalic acid ethyltributylphosphonium salt, 5-sulfoisophthalic acid benzyltributylphosphonium salt, and 5-sulfoisophthalic acid. Acid phenyltributylphosphonium salt, 5-sulfoisophthalic acid tetraphenylphosphonium salt, 5-sulfoisophthalic acid butyltriphenylphosphonium salt, 5-sulfoisophthalic acid benzyltriphenylphosphonium salt, 5-sulfoisophthalic acid tetramethylammonium salt, 5- Sulfoisophthalic acid tetraethylammonium salt, 5-sulfoisophthalic acid tetrabutylammonium salt, 5-sulfoisophthalic acid tetraphenylammonium salt, 5-sulfoisophthalic acid benzyl trime Le ammonium salt, 5-sulfoisophthalic acid benzyl trimethyl ammonium salt, or dimethyl esters thereof isophthalic acid derivatives, the diethyl ester, dipropionate pull ester, dibutyl ester, hexyl ester to di, dioctyl ester, didecyl ester is preferably exemplified. Among these isophthalic acid derivatives, 5-sulfoisophthalic acid dimethyltetrabutylphosphonium salt, 5-sulfoisophthalic acid dimethylbenzyltributylphosphonium salt, 5-sulfoisophthalic acid dimethyltetraphenylphosphonium salt, 5-sulfoisophthalic acid dimethyltetramethylammonium salt More preferred examples include salts, dimethyltetraethylammonium salt of 5-sulfoisophthalic acid, dimethyltetrabutylammonium salt of 5-sulfoisophthalic acid, and dimethylbenzyltrimethylammonium salt of 5-sulfoisophthalic acid. In the case of a compound satisfying these conditions, it is possible to achieve both sufficient cationic dyeability and sufficient fiber strength when used as a polyester fiber.
（数式（１）について）
本発明において、ポリエステルに共重合させる上記のスルホイソフタル酸の金属塩（Ａ）と上記の化合物（Ｂ）の合計は共重合ポリエステルを構成する全酸成分を基準として、（Ａ）成分と（Ｂ）成分の和Ａ＋Ｂが３．０〜５．０モル％の範囲である必要がある。３．０モル％より少ないと、常圧下でのカチオン染色では十分な染着を得ることができない。一方、５．０モル％より多くなると、得られるポリエステル糸の強度が低下するため実用に適さない。さらに染料を過剰に消費するため、コスト面でも不利である。好ましくは３．２〜４．８モル％であり、より好ましくは３．３〜４．７モル％である。
(About Formula (1))
In the present invention, the total of the above-mentioned sulfoisophthalic acid metal salt (A) to be copolymerized with the polyester and the above-mentioned compound (B) is based on the total acid component constituting the copolymerized polyester, and the (A) component and (B ) The sum A + B of the components needs to be in the range of 3.0 to 5.0 mol%. If it is less than 3.0 mol%, sufficient dyeing cannot be obtained by cationic dyeing under normal pressure. On the other hand, if it exceeds 5.0 mol%, the strength of the resulting polyester yarn is lowered, which is not suitable for practical use. Further, since the dye is consumed excessively, it is disadvantageous in terms of cost. Preferably it is 3.2-4.8 mol%, More preferably, it is 3.3-4.7 mol%.
（数式（２）について）
また、スルホイソフタル酸の金属塩（Ａ）と化合物（Ｂ）の成分比は上記のモル％の値にて、Ｂ／（Ａ＋Ｂ）が０．２〜０．７の範囲にある必要がある。０．２以下、つまり成分Ａの割合が多い状態では、スルホイソフタル酸金属塩による増粘効果により、得られる共重合ポリエステルの重合度を上げることが困難になる。一方、０．７以上、つまり化合物（Ｂ）の割合が多い状態では、重縮合反応が遅くなり、さらに化合物（Ｂ）の比率が多くなると熱分解反応が進むため重合度を上げることが困難となる。さらに、化合物（Ｂ）の比率多くなると共重合ポリエステルの熱安定性が悪化し、溶融紡糸段階で再溶融した際の熱分解反応による分子量の低下が大きくなるため、得られるポリエステル糸の強度が低下するため、好ましくない。好ましくは０．２３〜０．６５であり、より好ましくは０．２５〜０．６０である。
(About Formula (2))
Further, the component ratio of the metal salt (A) of sulfoisophthalic acid and the compound (B) needs to be in the range of 0.2 to 0.7, with B / (A + B) being the value of the above mol%. In the state of 0.2 or less, that is, in a state where the proportion of component A is large, it is difficult to increase the degree of polymerization of the resulting copolyester due to the thickening effect by the metal salt of sulfoisophthalic acid. On the other hand, when the ratio of the compound (B) is 0.7 or more, that is, the polycondensation reaction is slow, and when the ratio of the compound (B) is further increased, it is difficult to increase the degree of polymerization because the thermal decomposition reaction proceeds. Become. Furthermore, when the ratio of the compound (B) increases, the thermal stability of the copolyester deteriorates, and the decrease in the molecular weight due to the thermal decomposition reaction upon remelting at the melt spinning stage increases, so the strength of the resulting polyester yarn decreases. Therefore, it is not preferable. Preferably it is 0.23-0.65, More preferably, it is 0.25-0.60.
スルホイソフタル酸の金属塩（Ａ）をポリエステルに共重合することによりカチオン可染性は付与する事ができるが、スルホン酸金属塩基間のイオン結合に由来すると思われる共重合ポリエステルの溶融粘度の増粘効果のため共重合ポリエステルを高重合度化することが困難であった。そのため十分に高い重合度、高い固有粘度を有する共重合ポリエステルが得られず、その高い固有粘度でない共重合ポリエステルから得られるポリエステル繊維は、繊維強度が著しく低下する問題があった。一方その問題を解消するためにスルホイソフタル酸のテトラアルキルアンモニウム塩又はスルホイソフタル酸のテトラアルキルホスホニウム塩、即ち化合物（Ｂ）をポリエステルに共重合することが開示されているが、当該化合物は重合反応中に熱分解を起こしやすいため、共重合量を上げようとすると熱分解反応が進みやすい問題があり、繊維強度を高い値にすることが依然として困難であった。本発明の共重合ポリエステルにおいては、これらのスルホイソフタル酸の金属塩（Ａ）と化合物（Ｂ）を併用し、双方の化合物の共重合量、共重合比率、共重合ポリエステルのガラス転移温度及び固有粘度を特定の範囲に設定することによって、充分なカチオン染料による染色性と高い繊維強度が得られるほどの高固有粘度物性を両立させ、且つ繊維にし染色した際の鮮明性、深色染色性と言った物性をも同時に有する事を見出し本発明に至ったものである。 Although cationic dyeability can be imparted by copolymerizing a metal salt of sulfoisophthalic acid (A) with polyester, an increase in the melt viscosity of the copolymerized polyester that is thought to be derived from ionic bonds between the metal sulfonate groups. It was difficult to increase the degree of polymerization of the copolyester due to the viscous effect. Therefore, a copolyester having a sufficiently high degree of polymerization and a high intrinsic viscosity cannot be obtained, and the polyester fiber obtained from the copolyester having no high intrinsic viscosity has a problem that the fiber strength is remarkably lowered. On the other hand, in order to solve the problem, it is disclosed that a tetraalkylammonium salt of sulfoisophthalic acid or a tetraalkylphosphonium salt of sulfoisophthalic acid, that is, a compound (B) is copolymerized with a polyester. Since thermal decomposition tends to occur inside, there is a problem that the thermal decomposition reaction tends to proceed when the amount of copolymerization is increased, and it is still difficult to increase the fiber strength. In the copolymerized polyester of the present invention, the metal salt (A) of sulfoisophthalic acid and the compound (B) are used in combination, the copolymerization amount of both compounds, the copolymerization ratio, the glass transition temperature of the copolymerized polyester and the intrinsic property. By setting the viscosity to a specific range, it is possible to achieve both high dye viscosity properties sufficient to obtain sufficient dyeability and high fiber strength, and sharpness and deep colorability when dyed into fibers. It has been found that the above-mentioned physical properties are also provided, and the present invention has been achieved.
（ガラス転移温度について）
本発明の共重合ポリエステルは、ＤＳＣ（示差走査熱量測定）法による測定方法（昇温速度＝２０℃／ｍｉｎ）でのガラス転移温度（Ｔｇ）が７０〜８５℃の範囲である必要がある。Ｔｇが７０℃以下の場合、溶融紡糸による得られたポリエステル繊維の熱セット性が悪化し、仮撚捲縮加工性が悪化し、撚りがかからない状態となるため、該共重合ポリエステルからなるポリエステル繊維から得られる布帛の風合いが悪化する。ガラス転移温度を下げる方法としては、アジピン酸、セバシン酸、ジエチレングリコール、ポリエチレングリコールなどを共重合することで成されるが、本発明においてはこれら共重合成分が、上記のガラス転移温度の条件を満足する範囲であれば微量共重合されていても良い。Ｔｇの好ましい値の範囲は７１〜８２℃であり、より好ましくは７５〜８０℃である。
(Glass transition temperature)
The copolyester of the present invention needs to have a glass transition temperature (Tg) in the range of 70 to 85 ° C. in a measuring method by DSC (differential scanning calorimetry) method (temperature increase rate = 20 ° C./min). When the Tg is 70 ° C. or lower, the heat setting property of the polyester fiber obtained by melt spinning is deteriorated, the false twist crimping processability is deteriorated, and the polyester fiber is made of the copolymer polyester. The texture of the fabric obtained from is deteriorated. As a method for lowering the glass transition temperature, adipic acid, sebacic acid, diethylene glycol, polyethylene glycol and the like are copolymerized. In the present invention, these copolymer components satisfy the above glass transition temperature conditions. As long as it is within the range, it may be minutely copolymerized. The range of the preferable value of Tg is 71-82 degreeC, More preferably, it is 75-80 degreeC.
一方通常、ポリエチレンテレフタレートのガラス転移温度は７０〜８０℃くらいであることが知られているので、本発明の共重合ポリエステルにおいては、上述のように他の共重合成分が共重合されていても良いが、共重合した結果ガラス転移温度を著しく降下させる成分については共重合させることは好ましくない。ガラス転移温度を上記の値の範囲にするには、例えば上述の共重合ポリエステルの説明の項で挙げた共重合されても良い化合物の種類・共重合率を適宜調整して共重合させることを挙げる事ができる。 On the other hand, since it is generally known that the glass transition temperature of polyethylene terephthalate is about 70 to 80 ° C., the copolymer polyester of the present invention may be copolymerized with other copolymer components as described above. Although it is good, it is not preferable to copolymerize a component that significantly lowers the glass transition temperature as a result of copolymerization. In order to set the glass transition temperature within the above range, for example, the type and copolymerization ratio of the compounds that may be copolymerized listed in the description of the above-described copolymerized polyester are appropriately adjusted for copolymerization. I can list them.
（固有粘度について）
本発明の共重合ポリエステルの固有粘度（溶媒：オルトクロロフェノール、測定温度：３５℃）は０．５５〜１．００ｄＬ／ｇの範囲であることが好ましい。固有粘度が０．５５ｄＬ／ｇ以下である場合、得られるポリエステル繊維の強度が不足し、一方、１．００ｄＬ／ｇ以上とする場合、溶融粘度が高くなりすぎて溶融成型が困難になるため好ましくなく、また、溶融重合法に引続いて固相重合法により共重合ポリエステルの重縮合工程での生産コストが大幅に増大するため好ましくない。常圧カチオン可染性ポリエステルの固有粘度としては、０．６０〜０．９０ｄＬ／ｇの範囲が更に好ましい。共重合ポリエステルの固有粘度を０．５５〜１．００ｄＬ／ｇの範囲するためには、溶融重合を行う際の最終の重合温度、重合時間を調整したり、溶融重合法のみでは困難な場合には固相重合を行って適宜調整することができる。本発明においては、スルホイソフタル酸の金属塩（Ａ）及び化合物（Ｂ）を上記数式（１）及び（２）を満たすようにポリエチレンテレフタレートに対して共重合を行うことで上述のような手法により固有粘度を０．５５〜１．００ｄＬ／ｇにすることが可能となる。
(About intrinsic viscosity)
The intrinsic viscosity (solvent: orthochlorophenol, measurement temperature: 35 ° C.) of the copolyester of the present invention is preferably in the range of 0.55 to 1.00 dL / g. When the intrinsic viscosity is 0.55 dL / g or less, the strength of the resulting polyester fiber is insufficient. On the other hand, when the intrinsic viscosity is 1.00 dL / g or more, the melt viscosity becomes too high and melt molding becomes difficult. Further, it is not preferable because the production cost in the polycondensation step of the copolyester is greatly increased by the solid phase polymerization method following the melt polymerization method. The intrinsic viscosity of the normal pressure cationic dyeable polyester is more preferably in the range of 0.60 to 0.90 dL / g. In order to make the intrinsic viscosity of the copolyester in the range of 0.55 to 1.00 dL / g, it is difficult to adjust the final polymerization temperature and polymerization time during the melt polymerization, or when it is difficult only by the melt polymerization method. Can be appropriately adjusted by solid phase polymerization. In the present invention, the metal salt (A) of sulfoisophthalic acid and the compound (B) are copolymerized with polyethylene terephthalate so as to satisfy the above formulas (1) and (2), and the above-described method is used. It becomes possible to make an intrinsic viscosity into 0.55-1.00 dL / g.
（ＤＥＧ含有量について）
本発明における常圧カチオン可染性ポリエステルに含有されるジエチレングリコールは、２．５重量％以下であることが好ましい。より好ましくは２．２重量％以下、更により好ましくは１．８５〜２．２重量％である。一般にカチオン可染性ポリエステルを製造する際には、ポリエステルの製造工程において副生するジエチレングリコール（ＤＥＧ）量を抑制するために、ＤＥＧ抑制剤として少量のアルカリ金属塩、アルカリ土類金属塩、水酸化テトラアルキルホスホニウム、水酸化テトラアルキルアンモニウム、トリアルキルアミンなどの少なくとも１種類を、使用するカチオン可染性モノマー（本発明の場合はスルホイソフタル酸の金属塩（Ａ）及び化合物（Ｂ）の全モル量）に対して、１〜２０モル％程度を添加することが好ましい。
(DEG content)
The diethylene glycol contained in the normal pressure cationic dyeable polyester in the present invention is preferably 2.5% by weight or less. More preferably, it is 2.2 wt% or less, and still more preferably 1.85 to 2.2 wt%. In general, when producing a cationic dyeable polyester, a small amount of alkali metal salt, alkaline earth metal salt, hydroxide is used as a DEG inhibitor to suppress the amount of diethylene glycol (DEG) by-produced in the polyester production process. At least one kind such as tetraalkylphosphonium, tetraalkylammonium hydroxide, and trialkylamine is used, and in the case of the present invention, the total moles of the metal salt (A) of sulfoisophthalic acid and the compound (B) are used. It is preferable to add about 1 to 20 mol% with respect to the amount.
（不活性粒子の種類について）
本発明の常圧カチオン可染性ポリエステル組成物は上記の常圧カチオン可染性ポリエステルに、更に平均粒子径が０．０１〜０．５μｍの範囲であって、かつ粒子径が０．５μｍを超える粒子の頻度分布率が２０重量％以下である不活性粒子を常圧カチオン可染性ポリエステル組成物の全重量を基準として０．１〜５．０重量％含有している必要がある。ここで不活性とは後述する共重合ポリエステルの製造方法の工程、繊維その他の成形品を製造する工程において共重合ポリエステル鎖を構成している基と化学反応を起こすことがないことを示している。
(Inert particle types)
The normal pressure cationic dyeable polyester composition of the present invention has an average particle size in the range of 0.01 to 0.5 μm and a particle size of 0.5 μm to the normal pressure cationic dyeable polyester. It is necessary to contain 0.1 to 5.0% by weight of inert particles having a frequency distribution rate of particles exceeding 20% by weight based on the total weight of the atmospheric pressure cationic dyeable polyester composition. The term “inert” as used herein means that no chemical reaction is caused with a group constituting the copolymerized polyester chain in the process for producing the copolyester described later, and the process for producing a fiber or other molded article. .
その不活性粒子としては、炭酸カルシウム、リン酸カルシウム、珪酸カルシウム、酸化ケイ素、酸化アルミニウム、シリコーンパウダー、カオリナイト、硫酸バリウム、酸化チタン等が挙げられ、これらよりなる群から少なくとも１つに該当する不活性粒子ことが好ましい。また、不活性粒子は単一種であっても、複数種を併用しても良い。更にこれらの中でも特に炭酸カルシウム、リン酸カルシウム、シリカゾルが好ましく使用される。また、リン酸カルシウムとしては活性水素原子を持たない第三リン酸カルシウムが特に好ましく使用される。 Examples of the inert particles include calcium carbonate, calcium phosphate, calcium silicate, silicon oxide, aluminum oxide, silicone powder, kaolinite, barium sulfate, titanium oxide, and the like. Particles are preferred. Further, the inert particles may be a single type or a combination of multiple types. Of these, calcium carbonate, calcium phosphate, and silica sol are particularly preferably used. Further, as calcium phosphate, tricalcium phosphate having no active hydrogen atom is particularly preferably used.
（不活性粒子の粒子径について）
本発明における不活性粒子は、平均粒子径が０．０１〜０．５μｍの範囲である必要がある。平均粒子径が０．５μｍを超えると、ゾル又は共重合ポリエステル反応原液等の製造工程中で沈降しやすく、安定に供給・分散する事ができない。一方、平均粒子径が０．０１μｍ未満では、粒子の比表面積が大きすぎ、共重合ポリエステル製造工程の反応中に容易に凝集粒子を形成し、得られた常圧カチオン可染性ポリエステル組成物を溶融紡糸により製糸を行う時に断糸が増大するため好ましくない。該不活性粒子の平均粒子径は０．０２〜０．４μｍの範囲が好ましく、０．０３〜０．３μｍの範囲が更に好ましい。
(About particle size of inert particles)
The inert particles in the present invention need to have an average particle diameter in the range of 0.01 to 0.5 μm. When the average particle diameter exceeds 0.5 μm, it tends to settle during the production process of sol or copolymer polyester reaction stock solution and cannot be stably supplied and dispersed. On the other hand, when the average particle diameter is less than 0.01 μm, the specific surface area of the particles is too large, and aggregate particles are easily formed during the reaction of the copolymer polyester manufacturing process, and the obtained atmospheric pressure cationic dyeable polyester composition is obtained. Undesirably, the yarn breakage increases when the yarn is produced by melt spinning. The average particle diameter of the inert particles is preferably in the range of 0.02 to 0.4 μm, and more preferably in the range of 0.03 to 0.3 μm.
本発明における不活性粒子においては、粒径が０．５μｍを超える粒子の頻度分布率が２０重量％以下である必要がある。粒径が０．５μｍを超える粒子の頻度分布率が２０重量％を超えると、得られた常圧カチオン可染性ポリエステル組成物を製糸化後、アルカリ減量しても繊維表面に形成される微細孔が大きくなり、染色時の深色効果が得られないので好ましくない。該不活性粒子中の粒径が０．５μｍを超える粒子（粗大粒子）の頻度分布率は１５重量％以下の範囲が好ましく１０重量％以下の範囲が更に好ましい。 In the inert particles in the present invention, the frequency distribution rate of particles having a particle size exceeding 0.5 μm needs to be 20% by weight or less. When the frequency distribution ratio of particles having a particle size exceeding 0.5 μm exceeds 20% by weight, fine particles formed on the fiber surface even if the amount of alkali is reduced after threading the obtained normal pressure cationic dyeable polyester composition. This is not preferable because the pores become large and a deep color effect at the time of dyeing cannot be obtained. The frequency distribution ratio of particles (coarse particles) having a particle diameter exceeding 0.5 μm in the inert particles is preferably in the range of 15% by weight or less, and more preferably in the range of 10% by weight or less.
（不活性粒子の含有量について）
本発明における不活性粒子含有量は、常圧カチオン可染性ポリエステル組成物の全重量を基準として０．１〜５．０重量％の範囲にある必要がある。該含有量が０．１重量％未満の場合、最終的に得られる繊維の深色染色性が不十分となり、また、５．０重量％を超える場合は得られるポリエステル繊維の強度や耐熱性、耐光性が低下する為好ましくない。該粒子含有量は０．１５〜３．０重量％の範囲が好ましく、０．２〜１．０重量％の範囲が更に好ましい。
(About the content of inert particles)
The content of inert particles in the present invention needs to be in the range of 0.1 to 5.0% by weight based on the total weight of the atmospheric pressure cationic dyeable polyester composition. When the content is less than 0.1% by weight, the deep color dyeability of the finally obtained fiber becomes insufficient, and when it exceeds 5.0% by weight, the strength and heat resistance of the obtained polyester fiber, Undesirably, light resistance is lowered. The particle content is preferably in the range of 0.15 to 3.0% by weight, and more preferably in the range of 0.2 to 1.0% by weight.
（共重合ポリエステルの製造方法について）
本発明における共重合ポリエステルの製造は特に限定されず、スルホイソフタル酸の金属塩（Ａ）（以下化合物Ａと略称することがある。）及び化合物（Ｂ）を請求項１に記載の条件を満たすように留意する他は、通常知られているポリエステルの製造方法が用いられる。すなわち、テレフタル酸とエチレングリコールの直接エステル化反応させる、あるいはテレフタル酸ジメチルに代表されるテレフタル酸のエステル形成性誘導体とエチレングリコールとをエステル交換反応させて低重合体を製造する。次いでこの反応生成物を重縮合触媒の存在下で減圧加熱して所定の重合度になるまで重縮合反応させることにより製造される。スルホイソフタル酸を含有する芳香族ジカルボン酸及び／又はそのエステル誘導体（スルホイソフタル酸の金属塩（Ａ）及び化合物（Ｂ））を共重合する方法についても通常知られている製造方法を用いる事ができる。これらの化合物の反応工程への添加時期は、エステル交換反応又はエステル化反応の開始当初から重縮合反応の開始までの任意の時期に添加することができる。
(About the production method of copolyester)
The production of the copolyester in the present invention is not particularly limited, and the metal salt (A) of sulfoisophthalic acid (hereinafter sometimes abbreviated as compound A) and the compound (B) satisfy the condition described in claim 1. Other than this, a conventionally known polyester production method is used. That is, a low polymer is produced by a direct esterification reaction between terephthalic acid and ethylene glycol, or by an ester exchange reaction between an ester-forming derivative of terephthalic acid represented by dimethyl terephthalate and ethylene glycol. Next, this reaction product is produced by heating under reduced pressure in the presence of a polycondensation catalyst to carry out a polycondensation reaction until a predetermined polymerization degree is reached. It is possible to use a production method that is generally known for a method of copolymerizing an aromatic dicarboxylic acid containing sulfoisophthalic acid and / or an ester derivative thereof (metal salt (A) and compound (B) of sulfoisophthalic acid). it can. These compounds can be added to the reaction step at any time from the beginning of the transesterification or esterification reaction to the start of the polycondensation reaction.
またエステル交換反応時の触媒についても通常のエステル交換反応を行う際に用いられる触媒化合物を用いる事ができる。重縮合触媒についても通常用いられるアンチモン化合物、ゲルマニウム化合物、チタン化合物を用いる事ができる。またチタン化合物と芳香族多価カルボン酸又はその無水物との反応生成物、チタン化合物とリン化合物の反応生成物を用いても良い。 Moreover, the catalyst compound used when performing a normal transesterification reaction can also be used about the catalyst at the time of transesterification. As the polycondensation catalyst, commonly used antimony compounds, germanium compounds, and titanium compounds can be used. Further, a reaction product of a titanium compound and an aromatic polyvalent carboxylic acid or an anhydride thereof, or a reaction product of a titanium compound and a phosphorus compound may be used.
また上記の不活性粒子は上記の共重合ポリエステルの製造方法の工程において任意の工程で添加することによって本発明の常圧カチオン可染性ポリエステル組成物を製造することができる。具体的には直接エステル化反応工程若しくはエステル交換反応工程の当初から終わりまでの段階、重縮合反応工程の当初から終わりまでの段階、又は一旦重縮合反応工程が終わった後で共重合ポリエステルを再溶融した段階で不活性粒子を溶融状態で添加・溶融混練することができる。 Further, the above-mentioned inert particles can be added in an optional step in the above-described method for producing a copolyester, whereby the atmospheric pressure cationic dyeable polyester composition of the present invention can be produced. Specifically, the copolyester is recycled after the direct esterification reaction step or the transesterification reaction step from the beginning to the end, the polycondensation reaction step from the beginning to the end, or once the polycondensation reaction step is completed. Inactive particles can be added and melt kneaded in a molten state at the stage of melting.
（その他添加剤について）
また、本発明における常圧カチオン可染性ポリエステル組成物は、必要に応じて少量の添加剤、例えば酸化防止剤、蛍光増白剤、帯電防止剤、抗菌剤、紫外線吸収剤、光安定剤、熱安定剤、遮光剤又は艶消し剤などを含んでいても良い。特に酸化防止剤、艶消し剤などは特に好ましく添加される。
(About other additives)
In addition, the atmospheric pressure cationic dyeable polyester composition in the present invention, if necessary, a small amount of additives, such as antioxidants, fluorescent whitening agents, antistatic agents, antibacterial agents, ultraviolet absorbers, light stabilizers, A heat stabilizer, a light-shielding agent or a matting agent may be included. In particular, antioxidants and matting agents are particularly preferably added.
（溶融紡糸について）
本発明における常圧カチオン可染性ポリエステル組成物の製糸方法は、特に制限は無く、従来公知の方法が採用される。すなわち、乾燥した常圧カチオン可染性ポリエステル組成物を２７０℃〜３００℃の範囲で溶融紡糸して製造することが好ましく、溶融紡糸の引取り速度は４００〜５０００ｍ／分で紡糸することが好ましい。紡糸速度がこの範囲にあると、得られる常圧カチオン可染性を有するポリエステル繊維の強度も十分なものであると共に、安定して巻取りを行うこともできる。さらに、上述の方法で得られた未延伸糸若しくは部分延伸糸を、延伸工程にて１．２倍〜６．０倍程度の範囲で延伸することが好ましい。この延伸は未延伸ポリエステル繊維を一旦巻き取ってから行ってもよく、一旦巻き取ることなく連続的に行ってもよい。また、紡糸時に使用する口金の形状についても特に制限は無く、円形、三角形・四角形等の多角形、３以上の多葉形、Ｃ型断面、Ｈ型断面、Ｘ型断面、中空断面のいずれであってもよい。
(About melt spinning)
There is no restriction | limiting in particular in the spinning method of the normal pressure cationic dyeable polyester composition in this invention, A conventionally well-known method is employ | adopted. That is, it is preferable to produce a dried normal pressure cationic dyeable polyester composition by melt spinning in the range of 270 ° C. to 300 ° C., and it is preferable to spin at a take-up speed of 400 to 5000 m / min. . When the spinning speed is within this range, the resulting polyester fiber having normal pressure cationic dyeability has sufficient strength and can be wound stably. Furthermore, it is preferable that the undrawn yarn or the partially drawn yarn obtained by the above-described method is drawn in a range of about 1.2 to 6.0 times in the drawing step. This stretching may be performed after winding the unstretched polyester fiber once, or may be performed continuously without winding. Also, there is no particular limitation on the shape of the die used at the time of spinning, and any of polygons such as circles, triangles / quadrangles, three or more multilobes, C-shaped sections, H-shaped sections, X-shaped sections, and hollow sections. There may be.
（アルカリ減量加工）
本発明のポリエステル繊維は繊維に微細孔を有する構造を発現させるため、アルカリ減少処理を施したのち、常圧下でカチオン染料による染色を行うこともできる。アルカリ減量処理ならびにカチオン染色処理は公知の方法を採用する事ができるが、前述の手法により得られたポリエステル繊維を用いて織編物の状態にした後に、アルカリ減量処理を施すことにより、繊維微細孔を有する構造にすることができる。その結果、ポリエステル繊維表面での光散乱効果、並びに繊維内部までカチオン染料が浸透することにより、繊維断面内部まで染色することが可能になり、これにより本発明の課題である深色性を向上させることが可能となる。
(Alkaline weight loss processing)
Since the polyester fiber of the present invention develops a structure having fine pores in the fiber, it can be dyed with a cationic dye under normal pressure after an alkali reduction treatment. The alkali weight reduction treatment and the cationic dyeing treatment can employ known methods, but after making the woven or knitted fabric using the polyester fiber obtained by the above-mentioned method, the fiber fine pores can be obtained by performing the alkali weight loss treatment. It can be made the structure which has. As a result, the light scattering effect on the surface of the polyester fiber and the penetration of the cationic dye into the inside of the fiber makes it possible to dye the inside of the fiber cross section, thereby improving the deep color property that is the subject of the present invention. It becomes possible.
以下、実施例を挙げて本発明を具体的に説明するが、本発明はこれらの実施例に制限されるものではない。なお、実施例中の分析項目などは、下記記載の方法により測定した。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not restrict | limited to these Examples. In addition, the analysis item etc. in an Example were measured by the method of the following description.
（ア）固有粘度：
ポリエステル組成物試料を１００℃、６０分間でオルトクロロフェノールに溶解した希薄溶液を、３５℃でウベローデ粘度計を用いて測定した値から求めた。なお、チップの固有粘度をηＣ、紡糸後の未延伸糸の固有粘度をηＦとする。なお希薄溶液中に存在している不活性粒子は、希薄溶液を粘度計に移す前にろ過により取り除いた。
(A) Intrinsic viscosity:
A dilute solution obtained by dissolving a polyester composition sample in orthochlorophenol at 100 ° C. for 60 minutes was determined from the value measured at 35 ° C. using an Ubbelohde viscometer. The intrinsic viscosity of the tip is ηC, and the intrinsic viscosity of the undrawn yarn after spinning is ηF. The inert particles present in the dilute solution were removed by filtration before transferring the dilute solution to the viscometer.
（イ）ジエチレングリコール（ＤＥＧ）含有量：
ヒドラジンヒドラート（抱水ヒドラジン）を用いてポリエステル組成物試料チップを分解し、この分解生成物中のジエチレングリコールの含有量をガスクロマトグラフィー（ヒューレットパッカード社製（ＨＰ６８５０型））を用いて測定した。
(A) Diethylene glycol (DEG) content:
The polyester composition sample chip was decomposed using hydrazine hydrate (hydrated hydrazine), and the content of diethylene glycol in the decomposition product was measured using gas chromatography (HP Hewlett-Packard (HP 6850)).
（ウ）カチオン可染性：
ＣＡＴＨＩＬＯＮ ＢＬＵＥ ＣＤ−ＦＲＬＨ）０．２ｇ／Ｌ、ＣＤ−ＦＢＬＨ０．２ｇ／Ｌ（いずれも保土ヶ谷化学株式会社製のカチオン可染性染料）、硫酸ナトリウム３ｇ／Ｌ、酢酸０．３ｇ／Ｌの染色液中にて１００℃で１時間、浴比１：５０で染色し、次式により染着率を求めた。
染着率＝（ＯＤ０−ＯＤ１）／ＯＤ０
ＯＤ０：染色前の染液の５７６ｎｍの吸光度
ＯＤ１：染色後の染液の５７６ｎｍの吸光度
本発明の実施例では、染着率９８％以上のものを可染性良好と判断した。
(C) Cationic dyeability:
CATHILON BLUE CD-FRLH) 0.2 g / L, CD-FBLH 0.2 g / L (both cation dyeable dyes manufactured by Hodogaya Chemical Co., Ltd.), sodium sulfate 3 g / L, acetic acid 0.3 g / L It was dyed at 100 ° C. for 1 hour at a bath ratio of 1:50, and the dyeing rate was determined by the following formula.
Dyeing rate = (OD 0 −OD 1 ) / OD 0
OD 0 : Absorbance at 576 nm of the dye solution before dyeing OD 1 : Absorbance at 576 nm of the dye solution after dyeing In the examples of the present invention, those having a dyeing rate of 98% or more were judged to have good dyeability.
（エ）深色染色性評価：
ポリエステル繊維試料を布帛に形成した試験片を、濃度１０ｇ／Ｌ、１００℃の水酸化ナトリウム水溶液中に浴比３０で浸して所定減量率となるようにアルカリ減量処理を施した布帛を水洗後、住友化学工業株式会社製分散染料Ｓｕｍｉｋａｒｏｎ Ｎａｖｙ Ｂｌｕｅ Ｓ−２ＧＬの２％ｏｗｆ溶液で浴比１：５０に調製し、１３０℃で１時間染色した。染色布をグレタマクベス社製測色色差計（ＣＥ−３０００型）により測色し、クベルカ・ムンクの式により、深色度（Ｋ／Ｓ）を求めた。
Ｋ／Ｓ＝ｍａｘ［（１−Ｒ）２／２Ｒ］
上記数式中、Ｋは吸収係数、Ｓは散乱係数である。Ｒは分光反射率を示し、このスペクトルを測定し、最大値を深色度とする。本発明では、Ｋ／Ｓが２０以上のものを深色性良好と判断した。
(D) Evaluation of deep color dyeability:
After the test piece in which the polyester fiber sample is formed on the cloth is immersed in an aqueous solution of sodium hydroxide having a concentration of 10 g / L and 100 ° C. at a bath ratio of 30, the cloth subjected to the alkali weight reduction treatment so as to have a predetermined weight loss rate is washed with water. A 1% bath ratio solution of Sumikaron Navy Blue S-2GL, a disperse dye manufactured by Sumitomo Chemical Co., Ltd., was prepared at a bath ratio of 1:50 and dyed at 130 ° C. for 1 hour. The dyed cloth was measured with a colorimetric color difference meter (CE-3000 type) manufactured by Greta Macbeth Co., and the deep chromaticity (K / S) was determined by the Kubelka-Munk equation.
K / S = max [(1-R) 2 / 2R]
In the above formula, K is an absorption coefficient and S is a scattering coefficient. R represents spectral reflectance, this spectrum is measured, and the maximum value is defined as deep chromaticity. In the present invention, those having K / S of 20 or more were judged to have good deep color properties.
［実施例１］
テレフタル酸ジメチル１００重量部、５−ナトリウムスルホイソフタル酸ジメチル４．１重量部とエチレングリコール６０重量部の混合物に、酢酸マンガン０．０３重量部、酢酸ナトリウム三水和物０．１２重量部を添加し、１４０℃から２４０℃まで徐々に昇温しつつ、反応の結果生成するメタノールを系外に留出させながらエステル交換反応を行った。その後、正リン酸０．０３重量部を添加し、エステル交換反応を終了させた。
[Example 1]
Add 0.03 parts by weight of manganese acetate and 0.12 parts by weight of sodium acetate trihydrate to a mixture of 100 parts by weight of dimethyl terephthalate, 4.1 parts by weight of dimethyl 5-sodium sulfoisophthalate and 60 parts by weight of ethylene glycol. Then, the temperature was gradually raised from 140 ° C. to 240 ° C., and the ester exchange reaction was performed while distilling out the methanol produced as a result of the reaction out of the system. Thereafter, 0.03 part by weight of normal phosphoric acid was added to complete the transesterification reaction.
その後、反応生成物に三酸化アンチモン０．０５重量部と５−スルホイソフタル酸テトラブチルホスホネート２．８重量部と水酸化テトラエチルアンモニウム０．３重量部とトリエチルアミン０．００３重量部、及び不活性粒子として平均粒子径０．０６μｍの第三リン酸カルシウムの２０重量％エチレングリコールスラリー２．６重量部を添加した後、重縮合槽に移し、２８５℃まで昇温し、３０Ｐａ以下の高真空にて重縮合反応を行い、重縮合槽の攪拌機電力の値が所定電力に到達した段階若しくは所定時間を経過した段階で反応を終了させ、常法に従いチップ化した。 Thereafter, 0.05 parts by weight of antimony trioxide, 2.8 parts by weight of tetrabutylphosphonate 5-sulfoisophthalate, 0.3 parts by weight of tetraethylammonium hydroxide, 0.003 parts by weight of triethylamine, and inert particles were added to the reaction product. After adding 2.6 parts by weight of 20 wt% ethylene glycol slurry of tribasic calcium phosphate having an average particle size of 0.06 μm, it was transferred to a polycondensation tank, heated to 285 ° C., and polycondensed at a high vacuum of 30 Pa or less. The reaction was performed, and the reaction was terminated when the value of the stirrer power in the polycondensation tank reached a predetermined power or when a predetermined time had elapsed, and the chip was formed according to a conventional method.
このようにして得られたポリエステル組成物チップを１４０℃、５時間乾燥後、紡糸温度２８５℃巻取り速度４００ｍ／ｍｉｎで３３０ｄｔｅｘ／３６フィラメントの原糸を作り、４．０倍に延伸して８３ｄｔｅｘ／３６フィラメントの延伸糸を得た。次いで得られたポリエステル原糸を経糸及び緯糸に使用して平織物を製織し、この布帛を常法により精錬、乾燥したのち、１８０℃でヒートセットした。また、その一部を常法により、減量率が２０重量％となるようにアルカリ減量処理を行った。ポリエステル組成物の製造条件と評価結果の詳細を表１に示した。 After the polyester composition chip thus obtained was dried at 140 ° C. for 5 hours, a raw yarn of 330 dtex / 36 filaments was prepared at a spinning temperature of 285 ° C. and a winding speed of 400 m / min, and the yarn was stretched 4.0 times to obtain 83 dtex. A drawn yarn of / 36 filaments was obtained. Next, a plain woven fabric was woven using the obtained polyester yarn for warp and weft, and this fabric was refined and dried by a conventional method, and then heat-set at 180 ° C. Further, a part of the sample was subjected to alkali weight reduction treatment by a conventional method so that the weight loss rate was 20% by weight. Details of the production conditions and evaluation results of the polyester composition are shown in Table 1.
［実施例２〜４、比較例１〜８］
実施例１において、５−スルホイソフタル酸ナトリウム及び５−スルホイソフタル酸テトラブチルホスホネートの添加量を表１となるように変更したこと以外は実施例１と同様に実施した。ポリエステル組成物の製造条件と評価結果の詳細を表１に示した。
[Examples 2 to 4, Comparative Examples 1 to 8]
The same procedure as in Example 1 was performed except that the addition amounts of sodium 5-sulfoisophthalate and tetrabutylphosphonate of 5-sulfoisophthalate were changed to those shown in Table 1. Details of the production conditions and evaluation results of the polyester composition are shown in Table 1.
［実施例５〜６、比較例１１］
実施例１において、添加する不活性粒子を表１の性状のものに変更したこと以外は実施例１と同様に実施した。ポリエステル組成物の製造条件と評価結果の詳細を表１に示した。
[Examples 5 to 6, Comparative Example 11]
In Example 1, it carried out similarly to Example 1 except having changed the inert particle to add to the thing of the property of Table 1. Details of the production conditions and evaluation results of the polyester composition are shown in Table 1.
［比較例９］
実施例４において、重縮合反応での攪拌電力の値が低い段階で反応終了させること以外は実施例４と同様に実施した。ポリエステル組成物の製造条件と評価結果の詳細を表１に示した。
[Comparative Example 9]
In Example 4, it carried out like Example 4 except making it complete | finish a reaction in the stage where the value of the stirring electric power in a polycondensation reaction is low. Details of the production conditions and evaluation results of the polyester composition are shown in Table 1.
［比較例１０］
実施例１において、不活性粒子を添加しないこと以外は実施例４と同様に実施した。ポリエステル組成物の製造条件と評価結果の詳細を表１に示した。
[Comparative Example 10]
In Example 1, it implemented like Example 4 except not adding an inert particle. Details of the production conditions and evaluation results of the polyester composition are shown in Table 1.
本発明によれば、常圧下でのカチオン染色による染着性が良好で、且つ鮮明性、染色時に深色染色性が発現される常圧カチオン可染性ポリエステル組成物及びそれよりなる繊維を提供することができる。その産業上の意義はきわめて大きい。 According to the present invention, there is provided a normal pressure cationic dyeable polyester composition that exhibits good dyeability by cationic dyeing under normal pressure, and that exhibits vividness and deep color dyeability during dyeing, and fibers comprising the same. can do. Its industrial significance is extremely great.
Claims (8)
該常圧カチオン可染性ポリエステルが主たる繰返し単位がエチレンテレフタレートより構成される共重合ポリエステルであって、該共重合ポリエステルを構成する酸成分中にスルホイソフタル酸の金属塩（Ａ）及び下記式（Ｉ）で表される化合物（Ｂ）を下記数式（１）及び（２）を同時に満足する状態で含有する共重合ポリエステルであって、該共重合ポリエステルのガラス転移温度が７０〜８５℃の範囲にあり、且つ得られる共重合ポリエステルの固有粘度が０．５５〜１．００ｄＬ／ｇの範囲にある常圧カチオン可染性ポリエステルであり、
３．０≦Ａ＋Ｂ≦５．０ （１）
０．２≦Ｂ／（Ａ＋Ｂ）≦０．７ （２）
［上記数式中、Ａは共重合ポリエステルを構成する全酸成分を基準とするスルホイソフタル酸の金属塩（Ａ）の共重合量（モル％）、Ｂは共重合ポリエステルを構成する全酸成分を基準とする上記式（Ｉ）で表される化合物（Ｂ）の共重合量（モル％）を表す。］
且つ平均粒子径が０．０１〜０．５μｍの範囲であって粒子径が０．５μｍを越える粒子の頻度分布率が不活性粒子全重量を基準として２０重量％以下である不活性粒子を常圧カチオン可染性ポリエステル組成物の重量を基準にして０．１〜５．０重量％含有する常圧カチオン可染性ポリエステル組成物。 An atmospheric pressure cationic dyeable polyester composition comprising an atmospheric pressure cationic dyeable polyester and inert particles,
The atmospheric pressure cationic dyeable polyester is a copolymerized polyester in which the main repeating unit is composed of ethylene terephthalate, and in the acid component constituting the copolymerized polyester, a metal salt of sulfoisophthalic acid (A) and the following formula ( I) a copolyester containing the compound (B) represented by the following formulas (1) and (2) at the same time, wherein the glass transition temperature of the copolyester is in the range of 70 to 85 ° C. And an atmospheric pressure cationic dyeable polyester in which the intrinsic viscosity of the resulting copolyester is in the range of 0.55 to 1.00 dL / g,
3.0 ≦ A + B ≦ 5.0 (1)
0.2 ≦ B / (A + B) ≦ 0.7 (2)
[In the above formula, A is the copolymerization amount (mol%) of the metal salt of sulfoisophthalic acid (A) based on the total acid component constituting the copolyester, and B is the total acid component constituting the copolyester. This represents the copolymerization amount (mol%) of the compound (B) represented by the above formula (I) as a reference. ]
Inactive particles having an average particle size in the range of 0.01 to 0.5 μm and a frequency distribution ratio of particles having a particle size exceeding 0.5 μm of 20% by weight or less based on the total weight of the inert particles are usually used. A normal pressure cationic dyeable polyester composition containing 0.1 to 5.0% by weight based on the weight of the pressure cationic dyeable polyester composition.
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| WO2011048888A1 (en) | 2009-10-20 | 2011-04-28 | 帝人ファイバー株式会社 | Polyester fibers, process for production of the polyester fibers, cloth, fiber product, and polyester molded article |
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| WO2011048888A1 (en) | 2009-10-20 | 2011-04-28 | 帝人ファイバー株式会社 | Polyester fibers, process for production of the polyester fibers, cloth, fiber product, and polyester molded article |
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