EP0746648A1 - Verfahren zum anfärben von fasern des polytrimethylenterephthalats sowie verwendung von nach diesem verfahren erhältlichen gefärbten fasern - Google Patents
Verfahren zum anfärben von fasern des polytrimethylenterephthalats sowie verwendung von nach diesem verfahren erhältlichen gefärbten fasernInfo
- Publication number
- EP0746648A1 EP0746648A1 EP95909689A EP95909689A EP0746648A1 EP 0746648 A1 EP0746648 A1 EP 0746648A1 EP 95909689 A EP95909689 A EP 95909689A EP 95909689 A EP95909689 A EP 95909689A EP 0746648 A1 EP0746648 A1 EP 0746648A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fibers
- temperature
- dyeing
- dye
- liquor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 polytrimethylene terephthalate Polymers 0.000 title claims abstract description 96
- 229920002215 polytrimethylene terephthalate Polymers 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 37
- 230000008569 process Effects 0.000 title claims abstract description 28
- 238000004043 dyeing Methods 0.000 title claims description 82
- 239000000835 fiber Substances 0.000 claims abstract description 144
- 238000009835 boiling Methods 0.000 claims abstract description 17
- 238000004040 coloring Methods 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000000975 dye Substances 0.000 claims description 81
- 239000000986 disperse dye Substances 0.000 claims description 22
- 239000004744 fabric Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000002759 woven fabric Substances 0.000 claims description 2
- 229920000874 polytetramethylene terephthalate Polymers 0.000 claims 7
- 239000003086 colorant Substances 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 49
- 239000005020 polyethylene terephthalate Substances 0.000 description 48
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 30
- 238000006068 polycondensation reaction Methods 0.000 description 27
- 239000003054 catalyst Substances 0.000 description 24
- 229920000642 polymer Polymers 0.000 description 23
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 21
- 238000009987 spinning Methods 0.000 description 21
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 20
- 229940035437 1,3-propanediol Drugs 0.000 description 20
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 20
- 229920000728 polyester Polymers 0.000 description 18
- 238000005809 transesterification reaction Methods 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 14
- MHXFWEJMQVIWDH-UHFFFAOYSA-N 1-amino-4-hydroxy-2-phenoxyanthracene-9,10-dione Chemical compound C1=C(O)C=2C(=O)C3=CC=CC=C3C(=O)C=2C(N)=C1OC1=CC=CC=C1 MHXFWEJMQVIWDH-UHFFFAOYSA-N 0.000 description 12
- JSFUMBWFPQSADC-UHFFFAOYSA-N Disperse Blue 1 Chemical compound O=C1C2=C(N)C=CC(N)=C2C(=O)C2=C1C(N)=CC=C2N JSFUMBWFPQSADC-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 10
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 9
- 238000009792 diffusion process Methods 0.000 description 9
- 229920001707 polybutylene terephthalate Polymers 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000004753 textile Substances 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 239000000969 carrier Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 150000002009 diols Chemical class 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000010186 staining Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 6
- 238000010411 cooking Methods 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 102000002508 Peptide Elongation Factors Human genes 0.000 description 3
- 108010068204 Peptide Elongation Factors Proteins 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000008033 biological extinction Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- WIHMDCQAEONXND-UHFFFAOYSA-M butyl-hydroxy-oxotin Chemical compound CCCC[Sn](O)=O WIHMDCQAEONXND-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical group OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229920006240 drawn fiber Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 238000009940 knitting Methods 0.000 description 2
- 238000002074 melt spinning Methods 0.000 description 2
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- OOSZCNKVJAVHJI-UHFFFAOYSA-N 1-[(4-fluorophenyl)methyl]piperazine Chemical compound C1=CC(F)=CC=C1CN1CCNCC1 OOSZCNKVJAVHJI-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- LYTNHFVPHUPKGE-UHFFFAOYSA-N 2-(1,3-dioxan-2-yl)ethanol Chemical compound OCCC1OCCCO1 LYTNHFVPHUPKGE-UHFFFAOYSA-N 0.000 description 1
- XZAXQWXHBDKYJI-UHFFFAOYSA-N 2-[(6-oxobenzo[c][2,1]benzoxaphosphinin-6-yl)methyl]butanedioic acid Chemical compound C1=CC=C2P(CC(CC(=O)O)C(O)=O)(=O)OC3=CC=CC=C3C2=C1 XZAXQWXHBDKYJI-UHFFFAOYSA-N 0.000 description 1
- WBBFBHOZKCHJHN-UHFFFAOYSA-N 2-amino-1-hydroxyanthracene-9,10-dione Chemical class C1=CC=C2C(=O)C3=C(O)C(N)=CC=C3C(=O)C2=C1 WBBFBHOZKCHJHN-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- SGPZSOQUJLFTMQ-UHFFFAOYSA-N 4-o-ethyl 1-o-methyl benzene-1,4-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OC)C=C1 SGPZSOQUJLFTMQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241001366278 Leptotes marina Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 230000003542 behavioural effect Effects 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 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
- ZHVZTRUUPYIJTQ-UHFFFAOYSA-N bis(3-hydroxypropyl) benzene-1,4-dicarboxylate Chemical compound OCCCOC(=O)C1=CC=C(C(=O)OCCCO)C=C1 ZHVZTRUUPYIJTQ-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 239000001005 nitro dye Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- VFTQJKSRDCKVQA-UHFFFAOYSA-N oxan-3-ylmethanol Chemical compound OCC1CCCOC1 VFTQJKSRDCKVQA-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229940074545 sodium dihydrogen phosphate dihydrate Drugs 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001370 static light scattering Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/34—Material containing ester groups
- D06P3/52—Polyesters
- D06P3/54—Polyesters using dispersed dyestuffs
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/0004—General aspects of dyeing
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/0032—Determining dye recipes and dyeing parameters; Colour matching or monitoring
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/16—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dispersed, e.g. acetate, dyestuffs
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/92—Synthetic fiber dyeing
- Y10S8/922—Polyester fiber
Definitions
- the invention relates to a process for dyeing fibers of polytrimethylene terephthalate with disperse dyes in an aqueous liquor at or below the boiling temperature of the liquor and the use of the fibers dyed according to the invention.
- Polytrimethylene terephthalate is a polyester that has 1,3-propanediol as the diol component and terephthalic acid as the dicarboxylic acid component.
- Large-scale polyester syntheses can basically be carried out according to two different processes (H.-D. Schumann in Chemiefaser / Textilind. 40/92 (1990), p. 1058ff).
- dimethyl terephthalate is mixed with 1,3-
- a composite fiber made of polyethylene terephthalate and polytrimethylene terephthalate is described in GB 1075689 Bei
- the representation of the polytrimethylene terephthalate is based on dimethyl terephthalate and 1,3-propanediol and titanium tetrabutylate is used as the transesterification and polycondensation catalyst.
- German Offenlegungsschrift 19 54 527 on catalysts for the production of polyesters describes another possibility for catalysis in the production of
- Manganese (II) acetate tetrahydrate is used as the transesterification catalyst and hexagonal crystalline germanium dioxide with a
- These catalysts can also be used to prepare dipolymers from terephthalic acid, 1,2-ethanediol and 1,3-propanediol.
- Catalytic system described Again starting from Dimethyl terephthalate and 1,3-propanediol are added as titanium tetrabutylate as a catalyst. In addition, p-toluenesulfonic acid is added as a promoter so that a higher molecular weight is achieved.
- polyester fibers e.g. B. polyethylene terephthalate fibers
- dyeing Behavioral It is known (Herlinger, Gutmann and Jiang in CTI, chemical fibers / textile industry. 37 J89 . , February 1987, pp. 144-150) that the use of polyethylene terephthalate in textile technology was always associated with certain problems with regard to dyeings.
- polyester can only be used with carriers or under so-called HT conditions - i.e. H. at elevated temperature, e.g. B. 130 ° C in pressure vessels - optimally stain with disperse dyes (Bela v. Falkai in "Synthesemaschine", Verlag Chemie, Weinheim, 1981, p. 176).
- Carriers are special aids that have to be added to the dye liquors in order to enable dye absorption in practice.
- Examples of carriers that can also be referred to as fiber swelling agents include a. o-hydroxybiphenyl or
- Polyester-wool blends (wool cannot be dyed using the HT process) led to the development of carrier-free dyeable polyester fibers at cooking temperature.
- polyester chemically or physically (Herlinger et al. In: Chemical fiber / textile industry CTI 37/89, pp. 144 - 150, in chemical fiber / textile industry CTI 37/89, pp. 806 - 814 and in chemical fiber / textile industry CTI 40/92 , February 1990).
- ether modification was carried out . rtes polyethylene terephthalate.
- polyether blocks consisting of polyethylene glycol (PEG) units were built into the PETP chains, which, because of their mobility, make it easier to pull up the dye.
- PEG polyethylene glycol
- the glass transition temperature is also lower in these types of polyester and the dyeing behavior is significantly improved.
- Polyethylene terephthalate and polybutylene terephthalate granules were produced.
- Dye is added. In any case, the result is light shades with low color intensity. This generally applies to all disperse dyes, including those that have a high diffusion coefficient.
- Dyeing process for polyester fibers in which carrier-free and pressure-free dyeing is carried out with dispersion dyes from an aqueous bath at 25 to 100 ° C.
- this general statement is severely restricted in the description of US 3,841,831, on the one hand on PET fibers, on the other hand to only extremely small amounts of dye in the dyebath, and in addition the dyeing process indicated always includes an additional fixing step in order to allow the dye to penetrate somewhat more deeply to allow in the fiber. All this further supports the fact that the use of PET in textile technology has so far not allowed carrier-free, pressure-free and optimal staining.
- the dyed fibers should always have an increased resistance to dyeing when using the fibers and textile products made therefrom where there can be increased abrasion on the fiber surface.
- PTMT fibers polytrimethylene terephthalate fibers
- the process is carried out without pressure, with the dyeing at a liquor temperature between 20 and 50 ° C is started, the temperature within 20 - 90 min, preferably within 45 min, brought to the boiling temperature of the liquor or to a dyeing temperature which is at most 20 ° C below the boiling temperature of the liquor, the dyeing at least
- Polytrimethylene terephthalate was to be expected.
- Esters are well above 200 ° C. However, the melting points of the esters from diols with odd-numbered methylene groups in the diol are generally below the melting points of the esters with the next higher even-numbered methylene groups in the diol. However, this effect can only be seen clearly with the higher methylene group numbers. In the case of polytrimethylene and polybutylene terephthalate, the melting points are almost identical. Also with regard to the glass transition temperature, which should be as low as possible for good coloring properties at cooking temperature without the addition of a carrier, the prior art did not provide any clear indication of its suitability for carrier-free staining for the polytrimethylene terephthalate. So there is very different information from different authors. G. Farrow et al. in Makromol. Chem. 38 (1960), p. 147 settle the glass transition temperature at 95 ° C above that of polybutylene terephthalate, while in US Pat. No. 3,681,188 for polytrimethylene terephthalate
- Polytrimethylene terephthalate fibers which are obtainable from polytrimethylene terephthalate, which are preferred using a single catalyst, are particularly preferably dyed in the invention
- Titanium compounds for the transesterification and the subsequent polycondensation. It is particularly advantageous here that the transesterification catalyst does not have to be converted into an ineffective form before the polycondensation. Furthermore, the catalytically effective one
- species are only generated in the reaction mixture and it can remain in the polymer at the end of the reaction.
- fibers can be made from the PTMT material obtained by all methods familiar to the person skilled in the art getting produced. This is preferred
- Polytrimethylene terephthalate for fiber production is subjected to a melt spinning process, the polymer material preferably being dried beforehand at temperatures around 165 ° C. to water contents of less than 0.02% by weight.
- the polyester staple fibers obtained can optionally be hot-drawn before dyeing with a stretching system known to the person skilled in the art at temperatures of 110 ° C. (heating mandrel) and 90 ° C. (block heater).
- Disperse dyes are not limited to specific compounds, but rather include all dyes with low water solubility, which are able to dye hydrophobic fibers from an aqueous dispersion.
- the disperse dyestuffs in question are familiar to the person skilled in the art, examples being dyestuff classes of the azo series, amino or aminohydroxyanthraquinones or nitro dyes.
- monoazo dyes which have several nitro or cyano substituents, and heterocyclic azo and
- Polymethine dyes Representatives of these classes of dyes can be used alone or in a mixture of several, representatives of different classes also being able to be mixed with one another, for example to produce green or black shades. Also conceivable in the sense of the invention are dyestuffs for dyeing processes, such as are used in principle for dyeing cotton, in which a diaminoazo compound is dyed by the dispersion process, diazotized on the fiber and turned into black with a suitable coupling component
- Trisazo body implements.
- the invention also includes all so-called coloring variants for disperse dyes.
- the disperse dyes are present in an aqueous liquor. They spread out when staining between the aqueous liquor and the fiber treated with it, such as between two immiscible or limitedly miscible liquids, and finally, if the reaction is carried out appropriately and the substance is selected, are drawn onto the fiber.
- Polytrimethylene terephthalate fibers used a liquor which has between 3.0 and 7.0 g of disperse dye per kg of PTMT fiber to be dyed.
- the liquor used contains between 4.5 and 5.5 g of disperse dye per kg of PTMT fiber.
- the disperse dye amounts mentioned relate in each case to the pure dye contained in the commercial dye.
- dyeing is carried out according to the invention without a carrier without pressure at the boiling temperature of the aqueous liquor or at temperatures below it.
- the boiling point of the liquor can also be above 100.degree.
- the dyeing is carried out according to the invention without pressure, ie without using a special pressure vessel, however, for example in a closed dyeing cup.
- the boiling temperature of a dyeing liquor is generally changed only slightly by the addition of dye and / or auxiliary agents.
- the PTMT fibers are therefore treated at a dyeing temperature between approximately 80 and approximately 110 ° C.
- the treatment temperatures are very particularly preferably between 90 and 100 ° C.
- the dyes in the fiber are particularly advantageously completely dyed under the dyeing conditions according to the invention, in contrast to polyethylene terephthalate fibers, which are dyed only in a ring in comparison under identical dyeing conditions.
- Dyed PTMT fibers obtainable by the dyeing process according to the invention can be used in many ways. Basically, they can be used in all sectors that were also open to previously known colored polyester fibers.
- the dyed PTMT fibers obtainable in a process according to the invention are preferably used for the production of woven fabrics, knitted fabrics or knitted fabrics. Because of the excellent mechanical properties of colored PTMT fibers, especially the high ones Elasticity and restorability are also preferred for use in heavily used textiles or as highly elastic fabrics.
- Figure 1 an exemplary temperature and pressure curve in the synthesis of polytrimethylene terephthalate
- FIG. 2 for the dye C.
- I. Disperse Blue 139 the dye absorption as a function of the dyeing temperature for polytrimethylene and polyethylene terephthalate fibers;
- Figure 4 Staining pattern of PTMT and PET fiber polymers with the same dyeing time with C.I. Disperse Blue 139 depending on the dyeing temperature, represented by shades of gray;
- Figure 5 Staining pattern of PTMT and PET fiber polymers with the same dyeing time with C.I. Disperse Red 60 depending on the dyeing temperature, represented by shades of gray;
- Figure 6 Fiber cross sections of fibers dyed at 95 ° C with C.I. Disperse Blue 139; Polytrimethylene terephthalate (left) and polyethylene terephthalate (right);
- Figure 7 Cross-sections of fibers with at 120 ° C
- CI Disperse Blue 139 are colored; Polytrimethylene terephthalate (left) and polyethylene terephthalate (right); and
- Figure 8 the penetration depth of the dye C. I. Disperse Blue 139 as a function of the dyeing temperature for polytrimethylene and polyethylene terephthalate.
- the production of the polytrimethylene terephthalate was carried out on polycondensation plants with 2 or 20 dm ⁇ capacity.
- the batch size is 45 mol, based on the dimethyl terephthalate used, the ratio 1,3-propanediol
- dimethyl terephthalate (Diol batch D with a 1,3-propanediol content of 99.96%, 0.011% 3-hydroxymethyltetrahydropyran content, 0.005% 2-hydroxyethyl-1, 3-dioxane content, 0.02% carbonyls and 0.04% water content) to dimethyl terephthalate is added 1: 2.25 selected and titanium tetrabutylate comes as 10 wt .-%
- Catalyst solution in n-butanol in a concentration of 600 ppm with respect to dimethyl terephthalate Catalyst solution in n-butanol in a concentration of 600 ppm with respect to dimethyl terephthalate.
- Dimethyl terephthalate, 1, 3-propanediol and the catalyst solution are introduced into the polycondensation apparatus and heated to 140 ° C. under a constant gentle stream of nitrogen. After that Dimethyl terephthalate has melted, the stirrer is switched on and the temperature is raised to 220 ° C. The methanol released during the transesterification is distilled off until the calculated amount is almost reached.
- the pressure in the polycondensation apparatus is gradually reduced and the 1,3-propanediol used in excess and the 1,3-propanediol formed during the condensation are distilled off.
- the temperature is slowly increased to 270 ° C and the pressure is further reduced until finally oil pump vacuum (p ⁇ 0.05 mbar) is reached.
- the end of polycondensation is reached when the dropping rate of the 1,3-propanediol has dropped below 0.5 drops per minute. This information applies to the 2 dm 3 polycondensation plant.
- the agitator motor was used in the 2 dm 3 system as an indirect measure of the progressive condensation.
- the torque is determined as a measure of the progress of the polycondensation.
- the vacuum in the polycondensation apparatus is released and the finished polytrimethylene terephthalate under
- Nitrogen excess pressure is discharged into a water bath with a gear pump, drawn off with a draw-off device and immediately granulated.
- the reproducible temperature control during the synthesis is guaranteed by a microprocessor-controlled temperature program.
- the other conditions such as pressure and stirrer speed are changed manually according to the same time program.
- the predetermined end temperature of the polycondensation apparatus is 240 ° C. This temperature is reached 75 minutes before the end of the polycondensation and then kept constant until the end of the polycondensation. However, as can be seen from FIG. 1, the melting temperature rises to the end of the
- Polycondensation continues continuously up to 267 ° C.
- the heat required for this is not supplied from the outside by the heating, but is generated by the heat of stirring in the apparatus itself.
- the fact that this effect only occurs towards the end of the polycondensation can be explained by the steadily increasing viscosity of the polycondensation melt.
- the weight average molecular weight is determined using static light scattering.
- polymer solutions of concentrations 2, 4, 6, 8 and 10 g / 1 in 1, 1, 1, 3, 3, 3-hexafluoroisopropanol are prepared.
- Toluene is used as the standard for determining the optical constant and for tempering the samples.
- the scattered light intensities are in
- the refractive index increment is determined using the Wyatt Opilab 903 Interferometric Refractometer Technology Corporation.
- the color of the polymers is specified using the CIELAB color values.
- the polymer granules are measured with the Minolta CR 310, whose spectral sensitivity is closely matched to the CIE 2 ° normal observer function.
- the measuring field diameter is 5 cm and the calibration is carried out using a white standard.
- the polymers are dried in batches of about 25 kg each in a tumble dryer with a capacity of 100 dm 3 from Henkhaus Apparatebau.
- Table 2 shows the drying conditions.
- the temperatures given in square brackets refer to the drying of polyethylene terephthalate, which is processed into fibers under conditions similar to those of polytrimethylene terephthalate.
- the tumble dryer is then allowed to cool to room temperature over 12 hours and aerated with nitrogen.
- the water contents of the dried polymers are below 0.0025%, so that significant polymer degradation in the melt spinning process can be ruled out.
- Winding speed 2000 to 5000 m / min When an aqueous preparation 'emulsion of 10% Limanol PVK and 1.6% Ukanol R is used.
- the preparation overlay is about 0.5%.
- the density of the polymer melt must be known in order to produce defined spinning titers. The same applies to a defined preparation pad:
- polytrimethylene terephthalate In addition to polytrimethylene terephthalate, commercially available polyethylene terephthalate was also spun in the spinning tests.
- the spinning speeds are varied at a spinning titer of 16 tex with 32 individual filaments in the range from 2000 to 5000 m / min.
- the spinning titer is varied at a constant spinning speed of 3500 m / min in the range from 9.6 to 22.4 tex with 32 individual filaments each. This corresponds to a fineness of 0.3 to
- the spinning temperature is varied in the range between 240 and 270 ° C, with the best results being achieved at 250 ° C.
- different spinnerets with nozzle hole diameters of 200 to 350 ⁇ are used for polytrimethylene terephthalate. The best results are achieved with a 200 ⁇ m nozzle.
- the staple fibers obtained are drawn on a stretching system from Diens Apparatebau.
- the stretching factors are chosen so that the drawn fiber has about 25% elongation.
- the mechanical properties of the staple fibers and the drawn fibers made of polytrimethylene and polyethylene terephthalate are listed below:
- Polyethylene terephthalate staple fiber Polyethylene terephthalate staple fiber
- the glass transition temperature of the polymers in aqueous medium is of greater importance for the dyeing behavior of the synthetic fibers.
- DR Buchanan and JP Walters, text. Res. J., 42 (1977), 398 define a color transition temperature.
- the dye absorption of the synthetic fibers is determined as a function of the temperature.
- the temperature at which the dye absorption is 50% of the equilibrium value is defined as the coloring transition temperature.
- the dyeing transition temperature depends on the dyeing time and the dye structure.
- Knitted fabrics made from the following fibers are used for the dyeing tests:
- PET 3500 19.0 1.55 126
- the fibers are knitted on a
- the knitted fabric is washed as follows:
- thermofixed knitted fabrics show the
- Polytrimethylene terephthalate has a greater surface shrinkage than with polyethylene terephthalate.
- the extinction coefficient of the pure dye must be known for the quantitative determination of the dye absorption.
- the cleaning of the above-mentioned disperse dyes is described in detail by E. M. Schnaith (dissertation 1979, Univ. Stuttgart).
- the dyeing temperatures are varied between 60 ° C and 140 ° C.
- the coloring is always started at 40 ° C and the heating rate selected so that after 45 minutes
- the cooling rate is always 1 K / min until the bath temperature reaches 40 ° C.
- Dyeing machine Ahiba Polymat dyeing time: 60 min liquor ratio 1:20 liquor: 1 g / 1 dye
- the dyeings are reductively treated to remove the dye that has deposited on the fiber surface.
- the heating rate of the reduction liquor is 2 K / min, the cooling rate is 1 K / min.
- the knitted fabric is acidified with 5% formic acid.
- the fibers dyed at different temperatures are extracted exhaustively with chlorobenzene.
- the extracts are diluted to a defined volume and the extinctions of the solution are determined with the aid of a Lambda 7 UV / VIS spectrophotometer from Perkin Elmer in Bodensee. From the extinction of the extraction solution at the characteristic wavelength
- the dye content can be determined using the corresponding calibration line.
- the dye content FG in g / kg of goods is determined using the numerical equations:
- Figures 2 and 3 show the dye uptake of polytrimethylene terephthalate fibers as a function of the dyeing temperature in comparison to polyethylene terephthalate fibers.
- the horizontal line marks the amount of dye in the dye liquor based on the amount of substrate used.
- Fig. 2 also shows that at a dyeing temperature of 100 ° C, the entire dye from the dye liquor on the polytrimethylene terephthalate fiber. On the other hand, at a dyeing temperature of 100 ° C, only about 15% of the dye offered is absorbed by the polyethylene terephthalate fiber.
- the dyeing temperature must be increased to 130 ° C in order for the dye to be completely absorbed onto the polyethylene terephthalate fiber. This has the consequence that the bath-exhausting dyeing of the polyethylene terephthalate fiber must be carried out in closed vessels under pressure (HT dyeing conditions).
- C.I. Disperse Red 60 a disperse dye with a higher diffusion coefficient, an almost identical course of dye uptake with the dyeing temperature can be observed as with C.I. Disperse Blue 139.
- Dyes with C.I. Disperse Red 60 show a maximum dye absorption of the polytrimethylene terephthalate fiber from a dyeing temperature of 95 ° C.
- Polyethylene terephthalate are therefore: PTMT PET
- the dye transition temperature is about 7 K lower than in the case of dyeing both polymers with C.I. Disperse Red 60, due to its higher diffusion coefficient
- Dyeing temperature The difference in dye absorption is best seen here.
- the color intensity differences are represented by shades of gray.
- the dye distribution in the fiber can be assessed using fiber cross-sections.
- Fiber cross sections are obtained by embedding the fibers in acrylic acid esters and cutting them to a thickness of 10 ⁇ m with a Minot microtome from Jung. The cross-sectional images are taken with a Zeiss Axioplan microscope. The authenticity of a dyeing, when the dyed fabric is subjected to abrasion, is higher in the case of dyeing through than in the case of ring dyeing, in which the dye is only embedded in the outer layer of the fiber.
- stains with CI Disperse Blue 139 were chosen because this dye is very has low diffusion coefficients. When using other dyes with higher diffusion coefficients, a full coloration can be expected even at lower dyeing temperatures.
- 6 and 7 show cross sections of polytrimethylene and polyethylene terephthalate fibers which are dyed at 95 ° C. and 120 ° C. with C.I. Disperse Blue 139.
- the titanium dioxide particles with which the polymer granulate used is matted can be seen.
- the cross sections of the fibers show that the dye can penetrate the interior of the polytrimethylene terephthalate fiber more quickly than is the case with the polyethylene terephthalate fiber.
- Fig. 8 shows that related to the fiber diameter
- the polytrimethylene terephthalate fiber can be any polytrimethylene terephthalate fiber.
- the fiber absorbs all of the dye offered in the dyeing liquor.
- the dye concentration is highest in the peripheral areas. In the case of HT dyeing, the dye diffusion is accelerated so that a uniform dyeing can be observed over the entire fiber cross section.
- the dye absorption of the polyethylene terephthalate fiber at cooking temperature is significantly lower.
- the dye absorption of the fiber is only 10% of the dye offered in the dye liquor.
- the polyethylene terephthalate fiber can also be used under HT conditions stain well. All of the dye on offer penetrates the fiber, but there is no discoloration of the fiber with CI Disperse Blue 139.
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Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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DE4405407 | 1994-02-21 | ||
DE4405407 | 1994-02-21 | ||
PCT/EP1995/000455 WO1995022650A1 (de) | 1994-02-21 | 1995-02-09 | Verfahren zum anfärben von fasern des polytrimethylenterephthalats sowie verwendung von nach diesem verfahren erhältlichen gefärbten fasern |
Publications (2)
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EP0746648A1 true EP0746648A1 (de) | 1996-12-11 |
EP0746648B1 EP0746648B1 (de) | 1998-01-14 |
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EP95909689A Revoked EP0746648B1 (de) | 1994-02-21 | 1995-02-09 | Verfahren zum anfärben von fasern des polytrimethylenterephthalats sowie verwendung von nach diesem verfahren erhältlichen gefärbten fasern |
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US (1) | US5782935A (de) |
EP (1) | EP0746648B1 (de) |
JP (1) | JP4213202B2 (de) |
KR (1) | KR100355721B1 (de) |
CN (1) | CN1080349C (de) |
AT (1) | ATE162242T1 (de) |
CA (1) | CA2183736C (de) |
DE (2) | DE59501289D1 (de) |
DK (1) | DK0746648T3 (de) |
ES (1) | ES2112046T3 (de) |
GR (1) | GR3026379T3 (de) |
MX (1) | MX9603276A (de) |
MY (1) | MY130115A (de) |
TW (1) | TW318192B (de) |
WO (1) | WO1995022650A1 (de) |
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US6652964B1 (en) | 1997-08-18 | 2003-11-25 | Asahi Kasei Kabushiki Kaisha | Polyester fiber and fabric prepared therefrom |
US6110405A (en) * | 1997-09-15 | 2000-08-29 | Wellman, Inc. | Melt spinning colored polycondensation polymers |
EP1043428B1 (de) * | 1997-12-22 | 2006-06-07 | Asahi Kasei Kabushiki Kaisha | Fasern für elektrische beflockung und elektrisch beflockte artikeln |
EP1115926A1 (de) * | 1998-09-14 | 2001-07-18 | Deutsche Institute Für Textil- Und Faserforschung Stuttgart | Garne aus polymermischungsfasern oder -filamenten auf der basis von polyethylen-, polybutylen- und polytrimethylenterephthalat sowie deren verwendung |
EP1153953B1 (de) | 1998-10-23 | 2008-11-05 | Toyo Boseki Kabushiki Kaisha | Polymerisationskatalysator zur herstellung von polyester, polyester und verfahren zu seiner herstellung |
TW475013B (en) * | 1999-03-30 | 2002-02-01 | Asahi Chemical Ind | Warp beam, sizing method and beaming method |
US6297315B1 (en) * | 1999-05-11 | 2001-10-02 | Shell Oil Company | Process for preparing polytrimethylene terephthalate |
DE19934551A1 (de) * | 1999-07-22 | 2001-01-25 | Lurgi Zimmer Ag | PTT-Stapelfasern und Verfahren zu ihrer Herstellung |
ATE283882T1 (de) | 1999-08-24 | 2004-12-15 | Toyo Boseki | Polymerisationskatalysatoren für polyester, damit hergestellte polyester und verfahren zur herstellung von polyester |
US6576340B1 (en) * | 1999-11-12 | 2003-06-10 | E. I. Du Pont De Nemours And Company | Acid dyeable polyester compositions |
AU2402401A (en) | 2000-01-05 | 2001-07-16 | Toyo Boseki Kabushiki Kaisha | Polymerization catalyst for polyesters, polyesters produced with the same and process for producing polyesters |
US6312805B1 (en) | 2000-02-11 | 2001-11-06 | E.I. Du Pont De Nemours And Company | Cationic dyeability modifier for use with polyester and polyamide |
US6663806B2 (en) | 2000-03-03 | 2003-12-16 | E. I. Du Pont De Nemours And Company | Processes for making poly (trimethylene terephthalate) yarns |
US6287688B1 (en) | 2000-03-03 | 2001-09-11 | E. I. Du Pont De Nemours And Company | Partially oriented poly(trimethylene terephthalate) yarn |
US6685859B2 (en) | 2000-03-03 | 2004-02-03 | E. I. Du Pont De Nemours And Company | Processes for making poly(trimethylene terephthalate) yarn |
US6926962B2 (en) | 2000-05-18 | 2005-08-09 | Asahi Kasei Kabushiki Kaisha | Dyed yarn |
US6458455B1 (en) * | 2000-09-12 | 2002-10-01 | E. I. Du Pont De Nemours And Company | Poly(trimethylene terephthalate) tetrachannel cross-section staple fiber |
US6872352B2 (en) | 2000-09-12 | 2005-03-29 | E. I. Du Pont De Nemours And Company | Process of making web or fiberfill from polytrimethylene terephthalate staple fibers |
WO2002022707A1 (fr) * | 2000-09-12 | 2002-03-21 | Toyo Boseki Kabushiki Kaisha | Catalyseur de polymerisation pour polyester, polyester ainsi obtenu, et procede de production de polyester |
US6702864B2 (en) * | 2000-10-11 | 2004-03-09 | Shell Oil Company | Process for making high stretch and elastic knitted fabrics from polytrimethylene terephthalate |
KR100748290B1 (ko) | 2001-02-23 | 2007-08-09 | 토요 보세키 가부시기가이샤 | 폴리에스테르 중합촉매 및 이를 사용하여 제조된폴리에스테르 및 폴리에스테르의 제조방법 |
US6644070B2 (en) * | 2001-03-29 | 2003-11-11 | Asahi Kasei Kabushiki Kaisha | Three-dimensional fabric for seat |
KR100431784B1 (ko) * | 2001-11-01 | 2004-05-17 | 주식회사 효성 | 폴리트리메틸렌 테레프탈레이트 카페트의 연속 염색법 |
CN1205381C (zh) * | 2001-06-27 | 2005-06-08 | 株式会社晓星 | 聚对苯二甲酸丙二酯地毯的连续染色方法 |
US6923925B2 (en) | 2002-06-27 | 2005-08-02 | E. I. Du Pont De Nemours And Company | Process of making poly (trimethylene dicarboxylate) fibers |
US6921803B2 (en) * | 2002-07-11 | 2005-07-26 | E.I. Du Pont De Nemours And Company | Poly(trimethylene terephthalate) fibers, their manufacture and use |
US7578957B2 (en) * | 2002-12-30 | 2009-08-25 | E. I. Du Pont De Nemours And Company | Process of making staple fibers |
US20050272336A1 (en) * | 2004-06-04 | 2005-12-08 | Chang Jing C | Polymer compositions with antimicrobial properties |
US7196125B2 (en) * | 2004-06-10 | 2007-03-27 | E. I. Du Pont De Nemours And Company | Poly(trimethylene terephthalate) fibers useful in high-UV exposure end uses |
DE102005035767A1 (de) * | 2005-07-29 | 2007-02-01 | Deutsche Institute für Textil- und Faserforschung Stuttgart | Polyester von Terephthalsäure, ein Verfahren zu deren Herstellung und deren Verwendung |
CN102080335B (zh) * | 2009-11-30 | 2013-09-18 | 东丽纤维研究所(中国)有限公司 | 一种聚对苯二甲酸丙二酯织物的染整加工方法 |
CN106884349B (zh) * | 2017-04-28 | 2019-01-18 | 泉州市众科专利技术标准化研究院有限责任公司 | 一种涤纶雪纺印染工艺 |
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FR1490766A (fr) * | 1965-07-31 | 1967-08-04 | Benckiser Gmbh Joh A | Procédé de teinture de fibres de polyesters |
DE2221197A1 (de) * | 1971-05-03 | 1972-11-23 | Sandoz Ag | Verfahren zur Herstellung von Ausziehfaerbungen |
US3841831A (en) * | 1972-11-29 | 1974-10-15 | Cpc International Inc | Process for dyeing polyester fiber |
JPS58104216A (ja) * | 1981-12-14 | 1983-06-21 | Teijin Ltd | ポリトリメチレンテレフタレ−ト繊維の製造法 |
DE3643752A1 (de) * | 1986-12-20 | 1988-06-23 | Hoechst Ag | Verfahren zum einbandig/einstufigen faerben von mischungen aus carrierfrei faerbbaren polyesterfasern und cellulosefasern |
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1995
- 1995-02-09 CA CA002183736A patent/CA2183736C/en not_active Expired - Lifetime
- 1995-02-09 US US08/696,995 patent/US5782935A/en not_active Expired - Lifetime
- 1995-02-09 JP JP52154995A patent/JP4213202B2/ja not_active Expired - Lifetime
- 1995-02-09 KR KR1019960704656A patent/KR100355721B1/ko not_active IP Right Cessation
- 1995-02-09 MX MX9603276A patent/MX9603276A/es not_active IP Right Cessation
- 1995-02-09 DE DE59501289T patent/DE59501289D1/de not_active Revoked
- 1995-02-09 WO PCT/EP1995/000455 patent/WO1995022650A1/de not_active Application Discontinuation
- 1995-02-09 ES ES95909689T patent/ES2112046T3/es not_active Expired - Lifetime
- 1995-02-09 CN CN95191598A patent/CN1080349C/zh not_active Expired - Lifetime
- 1995-02-09 EP EP95909689A patent/EP0746648B1/de not_active Revoked
- 1995-02-09 AT AT95909689T patent/ATE162242T1/de not_active IP Right Cessation
- 1995-02-09 DK DK95909689T patent/DK0746648T3/da active
- 1995-02-17 TW TW084101450A patent/TW318192B/zh not_active IP Right Cessation
- 1995-02-18 DE DE19505576A patent/DE19505576A1/de not_active Withdrawn
- 1995-02-21 MY MYPI95000429A patent/MY130115A/en unknown
-
1998
- 1998-03-17 GR GR980400575T patent/GR3026379T3/el unknown
Non-Patent Citations (1)
Title |
---|
See references of WO9522650A1 * |
Also Published As
Publication number | Publication date |
---|---|
TW318192B (de) | 1997-10-21 |
MY130115A (en) | 2007-06-29 |
CA2183736C (en) | 2001-07-31 |
US5782935A (en) | 1998-07-21 |
JP4213202B2 (ja) | 2009-01-21 |
CN1154728A (zh) | 1997-07-16 |
DK0746648T3 (da) | 1998-09-14 |
GR3026379T3 (en) | 1998-06-30 |
JPH09509225A (ja) | 1997-09-16 |
EP0746648B1 (de) | 1998-01-14 |
WO1995022650A1 (de) | 1995-08-24 |
DE59501289D1 (de) | 1998-02-19 |
KR100355721B1 (ko) | 2003-01-06 |
KR970701285A (ko) | 1997-03-17 |
ES2112046T3 (es) | 1998-03-16 |
ATE162242T1 (de) | 1998-01-15 |
DE19505576A1 (de) | 1995-08-24 |
MX9603276A (es) | 1997-03-29 |
CN1080349C (zh) | 2002-03-06 |
CA2183736A1 (en) | 1995-08-24 |
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