JP2009161694A - Ordinary-pressure cation-dyeable polyester - Google Patents
Ordinary-pressure cation-dyeable polyester Download PDFInfo
- Publication number
- JP2009161694A JP2009161694A JP2008002398A JP2008002398A JP2009161694A JP 2009161694 A JP2009161694 A JP 2009161694A JP 2008002398 A JP2008002398 A JP 2008002398A JP 2008002398 A JP2008002398 A JP 2008002398A JP 2009161694 A JP2009161694 A JP 2009161694A
- Authority
- JP
- Japan
- Prior art keywords
- polyester
- acid
- sulfoisophthalic acid
- copolymerized
- copolyester
- 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 76
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229920001634 Copolyester Polymers 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
- 239000000835 fiber Substances 0.000 claims abstract description 26
- 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 19
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 16
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical group C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000002091 cationic group Chemical group 0.000 claims description 31
- -1 phosphonium ion Chemical class 0.000 claims description 23
- 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 13
- 238000002074 melt spinning Methods 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 3
- 238000004043 dyeing Methods 0.000 abstract description 20
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 10
- 125000001931 aliphatic group Chemical group 0.000 abstract description 6
- 150000004714 phosphonium salts Chemical class 0.000 abstract description 6
- 230000014509 gene expression Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 20
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000006068 polycondensation reaction Methods 0.000 description 11
- 239000000975 dye Substances 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 10
- 239000001361 adipic acid Substances 0.000 description 8
- 235000011037 adipic acid Nutrition 0.000 description 8
- 238000009987 spinning Methods 0.000 description 8
- 208000012886 Vertigo Diseases 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 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
- 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 6
- 230000007423 decrease Effects 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 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
- 230000000694 effects 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
- 238000005809 transesterification reaction Methods 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
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 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
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 3
- 150000003609 titanium compounds Chemical class 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- 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 2
- 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
- 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
- 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
- 238000007796 conventional method Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 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
- 238000005259 measurement Methods 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
- 239000000047 product Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 229940087562 sodium acetate trihydrate Drugs 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
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 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
- 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
- YGJADSHWEIOSSM-UHFFFAOYSA-K CC(CCC[P+](CCCC)(CCCC)CC1=CC=CC=C1)C.S(=O)(=O)([O-])C=1C=C(C=C(C(=O)[O-])C1)C(=O)[O-].CC(CCC[P+](CC1=CC=CC=C1)(CCCC)CCCC)C.CC(CCC[P+](CC1=CC=CC=C1)(CCCC)CCCC)C Chemical compound CC(CCC[P+](CCCC)(CCCC)CC1=CC=CC=C1)C.S(=O)(=O)([O-])C=1C=C(C=C(C(=O)[O-])C1)C(=O)[O-].CC(CCC[P+](CC1=CC=CC=C1)(CCCC)CCCC)C.CC(CCC[P+](CC1=CC=CC=C1)(CCCC)CCCC)C YGJADSHWEIOSSM-UHFFFAOYSA-K 0.000 description 1
- BLQLTDMPFVGBSB-UHFFFAOYSA-K CC([N+](C)(C)C)C.S(=O)(=O)([O-])C=1C=C(C=C(C(=O)[O-])C1)C(=O)[O-].CC(C)[N+](C)(C)C.CC(C)[N+](C)(C)C Chemical compound CC([N+](C)(C)C)C.S(=O)(=O)([O-])C=1C=C(C=C(C(=O)[O-])C1)C(=O)[O-].CC(C)[N+](C)(C)C.CC(C)[N+](C)(C)C BLQLTDMPFVGBSB-UHFFFAOYSA-K 0.000 description 1
- AWGNQRKJANPBJF-UHFFFAOYSA-K CC=1C(=C(C=CC1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)C.S(=O)(=O)([O-])C=1C=C(C=C(C(=O)[O-])C1)C(=O)[O-].CC=1C(=C(C=CC1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)C.CC=1C(=C(C=CC1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)C Chemical compound CC=1C(=C(C=CC1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)C.S(=O)(=O)([O-])C=1C=C(C=C(C(=O)[O-])C1)C(=O)[O-].CC=1C(=C(C=CC1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)C.CC=1C(=C(C=CC1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)C AWGNQRKJANPBJF-UHFFFAOYSA-K 0.000 description 1
- OHVCVVIUSBHHSP-UHFFFAOYSA-K C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.[O-]C(=O)c1cc(cc(c1)S([O-])(=O)=O)C([O-])=O Chemical compound C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.[O-]C(=O)c1cc(cc(c1)S([O-])(=O)=O)C([O-])=O OHVCVVIUSBHHSP-UHFFFAOYSA-K 0.000 description 1
- FBGQXOAGVSNDOW-UHFFFAOYSA-K C[N+](C)(C)Cc1ccccc1.C[N+](C)(C)Cc1ccccc1.C[N+](C)(C)Cc1ccccc1.[O-]C(=O)c1cc(cc(c1)S([O-])(=O)=O)C([O-])=O Chemical compound C[N+](C)(C)Cc1ccccc1.C[N+](C)(C)Cc1ccccc1.C[N+](C)(C)Cc1ccccc1.[O-]C(=O)c1cc(cc(c1)S([O-])(=O)=O)C([O-])=O FBGQXOAGVSNDOW-UHFFFAOYSA-K 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 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
- 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
- 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
- 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
- 239000002131 composite material Substances 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
- 239000000986 disperse dye 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
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 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
- 229920001519 homopolymer Polymers 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 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
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 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
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Chemical group 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001223 polyethylene 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
- 238000012545 processing Methods 0.000 description 1
- 150000003297 rubidium Chemical class 0.000 description 1
- 230000001953 sensory effect Effects 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
- 239000002904 solvent 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
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- 230000007704 transition Effects 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
- 229940086542 triethylamine Drugs 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Landscapes
- Artificial Filaments (AREA)
- Polyesters Or Polycarbonates (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性ポリエステル及びそれよりなる繊維に関する。 The present invention relates to a normal pressure cationic dyeable polyester which is dyeable to a cationic dye under normal pressure, and a 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、特許文献７参照。）。 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, patent document 6, 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は、スルホイソフタル酸の金属塩のみを共重合した場合よりも染着速度は速くなり、常圧下でのカチオン可染性は向上するものの、カチオン染料とイオン結合する部分は従来品と変わらず、染着が不十分である上、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 normal pressure cationic dyeable polyester obtained by melt spinning the polyester obtained by any of these methods has a higher dyeing speed than the case where only the metal salt of sulfoisophthalic acid is copolymerized, and is under normal pressure. Although the cation dyeability at this point is improved, the portion ion-bonded to the cationic dye is the same as the conventional product, and the dyeing is insufficient and the strength of the fiber is lowered, so that the tear strength of the resulting fabric is increased. There have been problems such as a decrease in color fastness and low dyeing fastness.
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、且つ糸の強度が高く、さらに風合の良好な常圧カチオン可染性ポリエステル及びそれよりなる常圧カチオン可染性ポリエステル繊維を提供することである。 The present invention solves the above-mentioned problems, and is capable of cationic dyeing under normal pressure, has high yarn strength, and has a good texture. It is to provide dyeable polyester fibers.
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、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り、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共重合され、並びに下記式（ＩＩ）で表される化合物を共重合ポリエステルを構成する全酸成分を基準として２〜１０モル％共重合された共重合ポリエステルであり、該共重合ポリエステル中のジエチレングリコール含有量が２．５重量％以下であり、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常圧カチオン可染性ポリエステルであり、この発明により上記課題を解決することができる。 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 copolyester in which the main repeating unit is composed of ethylene terephthalate, and is represented by the metal salt of sulfoisophthalic acid (A) and the following formula (I) in the acid component constituting the copolyester. The compound (B) is copolymerized in a state satisfying the following mathematical formulas (1) and (2), and the compound represented by the following formula (II) is 2 based on the total acid components constituting the copolymer polyester. 10 mol% copolymerized polyester, diethylene glycol content in the copolymerized polyester is 2.5 wt% or less, and the intrinsic viscosity of the obtained copolymerized polyester is 0.55 to 1.00 dL / It is a normal pressure cationic dyeable polyester characterized by being in the range of g, and the above-described problems can be solved by the present invention.
１．５≦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。］
1.5 ≦ 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. ]
本発明によれば、常圧下でのカチオン染料を用いた染色操作による染着性が良好で、従来のカチオン可染性ポリエステルよりも強度が高く、布帛にした際の風合いも良好な常圧カチオン可染性ポリエステル及び常圧カチオン可染性ポリエステル繊維を提供することができる。 According to the present invention, normal pressure cation has good dyeing property by dyeing operation using a cationic dye under normal pressure, higher strength than conventional cationic dyeable polyester, and good texture when made into a fabric. Dyeable polyesters and atmospheric pressure cationic dyeable polyester fibers 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共重合され、並びに下記式（ＩＩ）であらわされる化合物を共重合ポリエステルを構成する全酸成分を基準として２〜１０モル％共重合された共重合ポリエステルであり、該共重合ポリエステル中のジエチレングリコール含有量が２．５重量％以下であり、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. As a component, a metal salt of sulfoisophthalic acid (A) and a compound (B) represented by the following formula (I) are copolymerized while satisfying the following mathematical formulas (1) and (2), and the following formula (II) ) Is a copolymerized polyester obtained by copolymerizing 2 to 10 mol% based on the total acid components constituting the copolymerized polyester, and the diethylene glycol content in the copolymerized polyester is 2.5% by weight or less. And the intrinsic viscosity of the resulting copolyester is in the range of 0.55 to 1.00 dL / g. Is Riesuteru.
１．５≦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。］
1.5 ≦ 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１．５〜５．０モル％の範囲である必要がある。１．５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１．５モル％を超え４．５モル％以下であり、より好ましくは１．７〜４．０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 1.5 to 5.0 mol%. When the amount is less than 1.5 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 more than 1.5 mol% and 4.5 mol% or less, More preferably, it is 1.7-4.0 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を両立させ、且つ風合いが良好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 within a specific range, the present inventors have found that it has both a sufficient dyeability with a cationic dye and a high fiber strength and also has physical properties such as a good texture.
（上記式（ＩＩ）で表される化合物について）
本発明で使用される上記式（ＩＩ）で表される脂肪族ジカルボン酸成分として好ましく用いられるものとしては、アジピン酸、セバシン酸、デカンジカルボン酸などの脂肪族ジカルボン酸が例示できる。これらは単独又は２種類以上を併用することもできる。
上記脂肪族ジカルボン酸成分の共重合量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２〜１０モル％の範囲にある必要があるが、脂肪族ジカルボン酸の共重合により共重合ポリエステルのガラス転移温度が低下するため、低温での染色性が向上すると共に、ソフトな風合になる効果がある。脂肪族ジカルボン酸の共重合量が２モル％未満では染着性並びに風合の向上効果が小さく、１０モル％を越えると共重合ポリエステルの融点の低下による耐熱性の低下などが問題となるため好ましくない。好ましい共重合量の範囲は３〜７モル％である。
(About the compound represented by the above formula (II))
Preferred examples of the aliphatic dicarboxylic acid component represented by the above formula (II) used in the present invention include aliphatic dicarboxylic acids such as adipic acid, sebacic acid and decanedicarboxylic acid. These can be used alone or in combination of two or more.
The amount of copolymerization of the aliphatic dicarboxylic acid component needs to be in the range of 2 to 10 mol% based on the total acid components constituting the copolymerized polyester, but the glass of the copolymerized polyester is obtained by copolymerization of the aliphatic dicarboxylic acid. Since the transition temperature is lowered, the dyeability at low temperatures is improved, and a soft texture is obtained. If the copolymerization amount of the aliphatic dicarboxylic acid is less than 2 mol%, the effect of improving the dyeing property and texture is small, and if it exceeds 10 mol%, the heat resistance decreases due to the decrease in the melting point of the copolymerized polyester. It is not preferable. The range of preferable copolymerization amount is 3-7 mol%.
（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％以下であることが必要である。より好ましくは２．２重量％以下、更により好ましくは１．６５〜２．２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 needs to be 2.5% by weight or less. More preferably, it is 2.2 weight% or less, More preferably, it is 1.65 to 2.2 weight%. 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.
（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.
（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。）、化合物（Ｂ）及び上記式（ＩＩ）で表される化合物（脂肪族ジカルボン酸と称することがある。）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））並びに上記式（ＩＩ）で表される化合物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)
Production of the copolyester in the present invention is not particularly limited, and is represented by a metal salt of sulfoisophthalic acid (A) (hereinafter sometimes abbreviated as compound A), compound (B) and the above formula (II). A polyester production method known in the art is used except that the compound (sometimes referred to as an aliphatic dicarboxylic acid) satisfies the condition described in claim 1. 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. 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) and a compound represented by the above formula (II) Ordinarily known production methods can be used. 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.
（その他添加剤について）
また、本発明における共重合ポリエステルは、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 copolymer polyester in the present invention contains a small amount of additives as necessary, for example, antioxidants, fluorescent whitening agents, antistatic agents, antibacterial agents, ultraviolet absorbers, light stabilizers, heat stabilizers, and light-shielding agents. Or a matting agent etc. may be included. In particular, antioxidants and matting agents are particularly preferably added.
（溶融紡糸について）
本発明における共重合ポリエステルの製糸方法は、特に制限は無く、従来公知の方法が採用される。すなわち、乾燥した共重合ポリエステルを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 copolyester in this invention, A conventionally well-known method is employ | adopted. That is, it is preferable to produce the dried copolyester by melt spinning at a temperature in the range of 270 ° C. to 300 ° C., and the spinning speed of the melt spinning is preferably 400 to 5000 m / min. When the spinning speed is in this range, the polyester fiber obtained 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.
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。（ア）固有粘度：
ポリエステル試料を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と称する。
（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。
（ウ）ポリエステル繊維の引張強度（破断強度）・引張伸度（破断伸度）：
ＪＩＳ Ｌ１０１３：１９９９ ８．５に記載の方法に準拠して測定を行った。
（エ）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溶性染料）、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で染色を行い、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。
（オ）風合：
常圧下でカチオン染色した編地を１０人で官能評価を実施し、柔らかさを評価した。定法で製造したポリエチレンテレフタレートホモポリマーから得られた編地を基準とし、柔らかい風合のものは○、硬い風合のものは×と判定した。
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. (A) Intrinsic viscosity:
A dilute solution obtained by dissolving a polyester sample in orthochlorophenol at 100 ° C. for 60 minutes was determined from a value measured at 35 ° C. using an Ubbelohde viscometer. The intrinsic viscosity of the tip is referred to as ηC, and the intrinsic viscosity of the undrawn yarn after spinning is referred to as ηF.
(A) Diethylene glycol (DEG) content:
The polyester sample chip was decomposed using hydrazine hydrate (hydrated hydrazine), and the content of diethylene glycol in the decomposition product was measured using gas chromatography (manufactured by Hewlett-Packard (HP 6850)).
(C) Tensile strength (breaking strength) and tensile elongation (breaking elongation) of polyester fiber:
The measurement was performed according to the method described in JIS L1013: 1999 8.5.
(D) Cationic dyeability:
CATILON BLUE CD-FRLH) 0.2 g / L, CD-FBLH 0.2 g / L (both cation-soluble dyes manufactured by Hodogaya Chemical Co., Ltd.), sodium sulfate 3 g / L, acetic acid 0.3 g / L The dyeing was performed 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 be good dyeability.
(E) Feel:
Sensory evaluation was carried out by 10 people on a knitted fabric that was cationically dyed under normal pressure, and the softness was evaluated. Based on a knitted fabric obtained from a polyethylene terephthalate homopolymer produced by a conventional method, a soft texture was judged as ◯, and a hard texture as x.
［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。
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重量部を添加し、さらにアジピン酸２．２５重量部を添加して重縮合槽に移し、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。
このようにして得られたポリエステルチップを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。共重合ポリエステルの製造条件と評価結果の詳細を表１に示した。
[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.
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 and 0.003 parts by weight of triethylamine were added to the reaction product, 2.25 parts by weight of adipic acid was added, transferred to a polycondensation tank, heated to 285 ° C., a polycondensation reaction was performed at a high vacuum of 30 Pa or less, and the value of the agitator power in the polycondensation tank reached a predetermined power The reaction was terminated at the stage where the reaction was performed or when a predetermined time had elapsed, and the chip was formed according to a conventional method.
After the polyester chip thus obtained was dried at 140 ° C. for 5 hours, a raw yarn of 330 dtex / 36 filament was produced at a spinning temperature of 285 ° C. and a winding speed of 400 m / min, and was stretched 4.0 times to obtain 83 dtex / 36. A filament drawn yarn was obtained. Details of the production conditions and evaluation results of the copolyester are shown in Table 1.
［実施例２〜４、比較例１〜１０］
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並びにアジピン酸の添加量を表１となるように変更した事以外は実施例１と同様に実施した。共重合ポリエステル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 10]
The same procedure as in Example 1 was performed except that the addition amounts of sodium 5-sulfoisophthalate, sodium 5-sulfoisophthalate tetrabutylphosphonate and adipic acid were changed to those shown in Table 1. Details of the production conditions and evaluation results of the copolyester are shown in Table 1.
［実施例５］
実施例１において、アジピン酸の代わりにセバシン酸に変更し、添加量を表１となるようにした事以外は実施例１と同様に実施した。共重合ポリエステルの製造条件と評価結果の詳細を表１に示した。
[Example 5]
In Example 1, it replaced with the sebacic acid instead of adipic acid, and implemented similarly to Example 1 except having made it the addition amount into Table 1. FIG. Details of the production conditions and evaluation results of the copolyester are shown in Table 1.
［比較例１１］
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並びにアジピン酸の添加量を表１となるように変更し、重縮合反応での攪拌機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１と同様に実施した。共重合ポリエステルの製造条件と評価結果の詳細を表１に示した。
[Comparative Example 11]
In Example 1, the amount of sodium 5-sulfoisophthalate, sodium 5-sulfoisophthalate tetrabutylphosphonate and adipic acid was changed as shown in Table 1, and the reaction was performed at a stage where the stirrer power value in the polycondensation reaction was low. The same operation as in Example 1 was performed except for termination. Details of the production conditions and evaluation results of the copolyester are shown in Table 1.
［比較例１２］
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並びにアジピン酸の添加量を表１となるように変更し、酢酸ナトリウム三水和物、水酸化テトラエチルアンモニウム、トリエチルアミンを添加しないこと以外は実施例１と同様に実施した。共重合ポリエステルの製造条件と評価結果の詳細を表１に示した。
[Comparative Example 12]
In Example 1, the addition amount of sodium 5-sulfoisophthalate and sodium 5-sulfoisophthalate tetrabutylphosphonate and adipic acid was changed as shown in Table 1, and sodium acetate trihydrate, tetraethylammonium hydroxide and triethylamine were added. It implemented like Example 1 except not adding. Details of the production conditions and evaluation results of the copolyester are shown in Table 1.
本発明によれば、常圧下でのカチオン染料を用いた染色操作による染着性が良好で、従来のカチオン可染性ポリエステルよりも強度が高く、布帛にした際の風合いも良好な常圧カチオン可染性ポリエステル及び常圧カチオン可染性ポリエステル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, normal pressure cation has good dyeing property by dyeing operation using a cationic dye under normal pressure, higher strength than conventional cationic dyeable polyester, and good texture when made into a fabric. Dyeable polyesters and atmospheric pressure cationic dyeable polyester fibers can be provided. Its industrial significance is extremely great.
Claims (4)
１．５≦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。］
1.5 ≦ 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. ]
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| JP2011196006A (en) * | 2010-02-26 | 2011-10-06 | Toray Ind Inc | Polyester dyeable with cationic dye at normal pressure and fiber comprising the same |
| JP2013019078A (en) * | 2011-07-13 | 2013-01-31 | Mitsubishi Rayon Textile Co Ltd | Woven fabric having crepe |
| JP2013018802A (en) * | 2011-07-07 | 2013-01-31 | Mitsubishi Rayon Textile Co Ltd | Polyester resin composition, method for producing the same, polyester fiber composed of the same, and fiber product of the polyester fiber |
| JP2013181259A (en) * | 2012-03-01 | 2013-09-12 | Mitsubishi Rayon Textile Co Ltd | Cationic dye dyeable flame-retardant polyester fiber, and textile product thereof |
| KR20210055380A (en) * | 2019-11-07 | 2021-05-17 | 주식회사 휴비스 | Cationic-dyeable polyester-based elastic resin and cationic-dyeable polyester-based elastic fiber with improved dyeing property using the same |
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