EP0957197A1 - Process for treating natural or synthetic polyamide fibrous materials - Google Patents
Process for treating natural or synthetic polyamide fibrous materials Download PDFInfo
- Publication number
- EP0957197A1 EP0957197A1 EP99810385A EP99810385A EP0957197A1 EP 0957197 A1 EP0957197 A1 EP 0957197A1 EP 99810385 A EP99810385 A EP 99810385A EP 99810385 A EP99810385 A EP 99810385A EP 0957197 A1 EP0957197 A1 EP 0957197A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- homo
- parts
- dyes
- fiber material
- 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
- 239000004952 Polyamide Substances 0.000 title claims abstract description 32
- 229920002647 polyamide Polymers 0.000 title claims abstract description 32
- 239000002657 fibrous material Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000000975 dye Substances 0.000 claims abstract description 39
- 229920001577 copolymer Polymers 0.000 claims abstract description 23
- 238000004043 dyeing Methods 0.000 claims abstract description 23
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001000 anthraquinone dye Substances 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract 2
- 125000005395 methacrylic acid group Chemical group 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 23
- 239000000243 solution Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000004744 fabric Substances 0.000 description 16
- -1 alkyl radicals Chemical class 0.000 description 14
- 125000000129 anionic group Chemical group 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 239000000178 monomer Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- XCYWUZHUTJDTGS-UHFFFAOYSA-N 2-methoxy-3,4-dihydro-2h-pyran Chemical compound COC1CCC=CO1 XCYWUZHUTJDTGS-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- IAUGBVWVWDTCJV-UHFFFAOYSA-N 1-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound CCC(S(O)(=O)=O)NC(=O)C=C IAUGBVWVWDTCJV-UHFFFAOYSA-N 0.000 description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 4
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229940078552 o-xylene Drugs 0.000 description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 4
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 4
- KKSNTCYLMGYFFB-UHFFFAOYSA-N (prop-2-enoylamino)methanesulfonic acid Chemical compound OS(=O)(=O)CNC(=O)C=C KKSNTCYLMGYFFB-UHFFFAOYSA-N 0.000 description 3
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- PNLUGRYDUHRLOF-UHFFFAOYSA-N n-ethenyl-n-methylacetamide Chemical compound C=CN(C)C(C)=O PNLUGRYDUHRLOF-UHFFFAOYSA-N 0.000 description 3
- OFESGEKAXKKFQT-UHFFFAOYSA-N n-ethenyl-n-methylformamide Chemical compound C=CN(C)C=O OFESGEKAXKKFQT-UHFFFAOYSA-N 0.000 description 3
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 3
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 210000002268 wool Anatomy 0.000 description 3
- ZLPXFBBKYQYQEA-UHFFFAOYSA-N 1-(prop-2-enoylamino)ethanesulfonic acid Chemical compound OS(=O)(=O)C(C)NC(=O)C=C ZLPXFBBKYQYQEA-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NEYTXADIGVEHQD-UHFFFAOYSA-N 2-hydroxy-2-(prop-2-enoylamino)acetic acid Chemical compound OC(=O)C(O)NC(=O)C=C NEYTXADIGVEHQD-UHFFFAOYSA-N 0.000 description 2
- MXRGSJAOLKBZLU-UHFFFAOYSA-N 3-ethenylazepan-2-one Chemical compound C=CC1CCCCNC1=O MXRGSJAOLKBZLU-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- DGLRDKLJZLEJCY-UHFFFAOYSA-L disodium hydrogenphosphate dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].OP([O-])([O-])=O DGLRDKLJZLEJCY-UHFFFAOYSA-L 0.000 description 2
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 2
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 2
- BBMHARZCALWXSL-UHFFFAOYSA-M sodium dihydrogenphosphate monohydrate Chemical compound O.[Na+].OP(O)([O-])=O BBMHARZCALWXSL-UHFFFAOYSA-M 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 1
- SJQBHNHASPQACB-ONEGZZNKSA-N (e)-1,2-dimethoxyethene Chemical group CO\C=C\OC SJQBHNHASPQACB-ONEGZZNKSA-N 0.000 description 1
- VDSAXHBDVIUOGV-UHFFFAOYSA-N 1-ethenyl-2-methyl-4,5-dihydroimidazole Chemical compound CC1=NCCN1C=C VDSAXHBDVIUOGV-UHFFFAOYSA-N 0.000 description 1
- HXVJQEGYAYABRY-UHFFFAOYSA-N 1-ethenyl-4,5-dihydroimidazole Chemical compound C=CN1CCN=C1 HXVJQEGYAYABRY-UHFFFAOYSA-N 0.000 description 1
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- WXFWXFIWDGJRSC-UHFFFAOYSA-N 2,5-dimethoxy-2,5-dihydrofuran Chemical compound COC1OC(OC)C=C1 WXFWXFIWDGJRSC-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- RPYQPOCMVAEGHP-UHFFFAOYSA-N 2-ethenoxyacetic acid Chemical compound OC(=O)COC=C RPYQPOCMVAEGHP-UHFFFAOYSA-N 0.000 description 1
- GQWNPIKWYPQUPI-UHFFFAOYSA-N 2-methylbut-3-enoic acid Chemical compound C=CC(C)C(O)=O GQWNPIKWYPQUPI-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical compound OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 description 1
- QXWUJRONCAPLLL-UHFFFAOYSA-N 2-prop-2-enoxyacetic acid Chemical compound OC(=O)COCC=C QXWUJRONCAPLLL-UHFFFAOYSA-N 0.000 description 1
- OCXPJMSKLNNYLE-UHFFFAOYSA-N 2-prop-2-enylbutanedioic acid Chemical compound OC(=O)CC(C(O)=O)CC=C OCXPJMSKLNNYLE-UHFFFAOYSA-N 0.000 description 1
- CKSURTJJJBWBOU-UHFFFAOYSA-N 3-[(3-amino-3-imino-2-methylpropyl)diazenyl]-2-methylpropanimidamide;hydrochloride Chemical compound Cl.NC(=N)C(C)CN=NCC(C)C(N)=N CKSURTJJJBWBOU-UHFFFAOYSA-N 0.000 description 1
- ZDZVKPXKLLLOOA-UHFFFAOYSA-N Allylmalonic acid Chemical compound OC(=O)C(C(O)=O)CC=C ZDZVKPXKLLLOOA-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 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
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 241001584775 Tunga penetrans Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229940091181 aconitic acid Drugs 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 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 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- GORGQKRVQGXVEB-UHFFFAOYSA-N n-ethenyl-n-ethylacetamide Chemical compound CCN(C=C)C(C)=O GORGQKRVQGXVEB-UHFFFAOYSA-N 0.000 description 1
- WGESLFUSXZBFQF-UHFFFAOYSA-N n-methyl-n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCN(C)CC=C WGESLFUSXZBFQF-UHFFFAOYSA-N 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-N pent-4-enoic acid Chemical compound OC(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- VEYCPJGKKJULEP-UHFFFAOYSA-N prop-2-enoic acid sulfuric acid Chemical compound OC(=O)C=C.OS(O)(=O)=O VEYCPJGKKJULEP-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- UIERETOOQGIECD-ONEGZZNKSA-N tiglic acid Chemical compound C\C=C(/C)C(O)=O UIERETOOQGIECD-ONEGZZNKSA-N 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 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
- 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
- D06P1/44—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 insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—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 insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- D06P1/525—Polymers of unsaturated carboxylic acids or functional derivatives thereof
- D06P1/5257—(Meth)acrylic acid
-
- 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
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/24—Polyamides; Polyurethanes
- D06P3/241—Polyamides; Polyurethanes using acid dyes
-
- 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
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/02—After-treatment
- D06P5/04—After-treatment with organic compounds
- D06P5/08—After-treatment with organic compounds macromolecular
-
- 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
- Y10S8/924—Polyamide fiber
-
- 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
- Y10S8/93—Pretreatment before dyeing
Definitions
- the present invention relates to a method for the treatment of natural or synthetic polyamide fiber materials to improve the durability of the dyes against exposure to ozone.
- Dyes and prints with dyes often show a high sensitivity to Ozone.
- anthraquinone dyes are easily oxidatively degraded by ozone and in this way change their absorption behavior and thus the color. This Behavior is particularly observed with blue anthraquinone dyes.
- the nuance a trichromatic stain based on blue anthraquinone dyes, for example one Polyamide carpet fabric, is easily changed by exposure to ozone. You meet this deficiency in general by resinating the dyed polyamide fiber material treated on the basis of phenol-formaldehyde condensates.
- improvements in ozone resistance have disadvantages, e.g.
- the present invention therefore relates to a process for improving the resistance of dyes on natural or synthetic polyamide fiber materials to the effects of ozone, characterized in that the fiber material is treated with a liquor containing a homo- or copolymer with recurring structural units before, during or after dyeing of the formula (1) wherein R 1 is optionally substituted C 1 -C 4 alkyl.
- Suitable C 1 -C 4 alkyl for R 1 are, for example, methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, these alkyl radicals being unsubstituted or substituted, for example by halogen, such as fluorine, chlorine or bromine, hydroxy or sulfo.
- R 1 is preferably C 1 -C 4 alkyl and especially methyl.
- They preferably contain according to the invention as agents for improving the Homo- or copolymers used 50 to 100 mol% and ozone resistance in particular 80 to 100 mol% of repeating structural units of the formula (1).
- polymers used according to the invention are copolymers, then come as copolymerizable monomers e.g. anionic or non-ionic groups containing compounds in question.
- the following unsaturated compounds may be mentioned as examples of monomers containing anionic groups: Acrylic acid, maleic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, vinyl acetic acid, vinyl oxyacetic acid, vinyl propionic acid, crotonic acid, aconitic acid, allylacetic acid, allyloxyacetic acid, ⁇ , ⁇ -dimethylacrylic acid, allylmalonic acid, allyloxymaloxy, allylacrylic acid, carboxylate, methacryloyloxyacyl, methacrylate, carboxylate Allyl succinic acid, acrylamidoglycolic acid, vinylsulfonic acid, (meth) allylsulfonic acid, (meth) acrylamidomethylpropanesulfonic acid, (meth) acrylamidopropanesulfonic acid, (meth) acrylamidoethanesulfonic acid, (meth) acrylamidomethanes
- unsaturated compounds may be mentioned as examples of monomers containing nonionic groups: Maleic anhydride, vinylcaprolactam, diallylamine, N-methyldiallylamine, N-ethyldiallylamine, N-vinylpyrrolidone, N-vinylformamide, N-vinyl acetamide, N-vinyl-N-methylformamide, N-vinyl-N-methyl-acetamide, N-vinyl N-ethyl-acetamide, N-vinylimidazole, N-vinyl-N-methyl-imidazole, N-vinylimidazoline, N-vinyl-2-methylimidazoline, N-vinylcaprolactam, vinyl acetate, vinyl propionate, vinyl butyrate, C 1 -C 22 alkyl vinyl ketone, C 1 -C 22 alkyl vinyl ether, olefins such as ethylene, propylene, isobutene, styrene
- Copolymerizable monomers in the polymers used according to the invention Acrylic acid, maleic acid, vinyl acetic acid, acrylamidoglycolic acid, (meth) acrylamidomethanesulfonic acid, vinylsulfonic acid, (meth) allylsulfonic acid, (meth) acrylamidomethylpropanesulfonic acid, (meth) acrylamidopropanesulfonic acid, (meth) acrylamidoethanesulfonic acid, (meth) acrylamidomethanesulfonic acid, sulfopropyl (st) sulfatonic acid, sulfopropyl (meth) acrylate sulfate, Maleic anhydride, N-vinylpyrrolidone, vinylcaprolactam, N-vinylformamide, N-vinyl-N-methylformamide, N-vinyl acetamide, N-vinyl-N-methyl-acetamide
- Very particularly preferred as copolymerizable monomers in the polymers used according to the invention are: Vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 3- (meth) acrylamidopropanesulfonic acid, maleic anhydride, N-vinylpyrrolidone, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methyl-acetamide, N -Vinylimidazole, vinyl acetate, styrene, hydroxyethyl / propyl- (meth) acrylate, (meth) acrylic acid-C 1 -C 6 alkyl ester, (meth) acrylonitrile, (meth) acrylamide, N-mono / N, N-di -C 1 -C 6 alkyl- (meth) acrylamide or 2-methoxy-3,4-dihydro-2H-pyran.
- Particularly important as copolymerizable monomers in the polymers used according to the invention are: Vinylsulfonic acid, 3- (meth) acrylamidopropanesulfonic acid or 2-methoxy-3,4-dihydro-2H-pyran.
- the homopolymers or copolymers used in the process according to the invention have average molecular weight of 1,000 to 1,000,000, preferably 1,000 to 500,000 and in particular 5,000 to 200,000.
- the homopolymers or copolymers containing recurring structural units of the above formula (1) used according to the invention as agents for improving the ozone resistance are prepared in a manner known per se, for example by polymerization of the monomers of the formula (2) initiated ionically or preferably by free radicals.
- R 1 has the meanings and preferences given above, for example in solution, suspension or emulsion, optionally in the presence of the unsaturated compounds mentioned above as examples of copolymerizable monomers.
- the polymerization is preferably carried out in solution with a peroxide, persulfate or an azo compound, for example with sodium persulfate or azo-bis- (2-amidinopropane) hydrochloride, as a free-radical initiator, for example in an amount of 0.005 to 10% by weight, based on the monomers used, is present.
- a peroxide, persulfate or an azo compound for example with sodium persulfate or azo-bis- (2-amidinopropane) hydrochloride, as a free-radical initiator, for example in an amount of 0.005 to 10% by weight, based on the monomers used, is present.
- the homo- or copolymers used in the process according to the invention are regardless of the fleet ratio e.g. in an amount of 0.05 to 10% by weight, preferably 0.1 to 6% by weight and particularly preferably 0.5 to 4% by weight, based on the weight of the polyamide fiber material used.
- Treatment of the polyamide fiber material with the homo- or copolymers can be before, during or after dyeing and preferably during or after dyeing.
- the polyamide fiber material is treated with those used according to the invention Homopolymers or copolymers during the dyeing process, that's how it is done Process according to the invention advantageously such that the polymers of Dyeing liquor is added in the amount specified above and the fiber material in the usual way Way colors.
- the polyamide fiber material is treated with those used according to the invention Homopolymers or copolymers after dyeing, this is done according to the invention Process advantageously such that the polyamide fiber material is first in usually colors and then an aftertreatment with a polymer in the connects the previously specified amount containing fresh aqueous liquor. After that the dyed polyamide fiber material can be dewatered and opened without further rinsing can be dried in the usual way.
- the after-treatment is usually carried out in a fresh one Fleet. However, it can also be carried out directly in the dye bath, provided that the dye bath is at the end largely stripped and is still sufficiently acidic. After the treatment is usually rinsed briefly with water.
- Natural polyamide fiber material such as e.g. Wool or Silk, or synthetic polyamide fiber material, e.g. Polyamide 6 or polyamide 6.6, or fiber mixtures such as Wool / cellulose or polyamide / cellulose mixed fibers or Polyamide / wool mixed fibers into consideration.
- the fiber material is preferred around synthetic polyamide fiber material.
- the textile can be used in any form, e.g. as fiber, yarn, woven or knitted fabric.
- the dyeings are carried out, for example, with anionic dyes, all of the usual anionic dyes, e.g. as in Color Index, 3rd edition (1971) and the Addenda to this are described under the heading "Acid Dyes”.
- Examples are sulfo group-containing monoazo, polyazo, metal complex azo, anthraquinone, Phthalocyanine or formazan dyes.
- the dyeings are preferably carried out using anthraquinone dyes and in particular blue ones Anthraquinone dyes.
- the anionic dyes used to dye the polyamide fiber material lie either in the form of their free sulfonic acid or preferably as their salts.
- the salts include, for example, the alkali, alkaline earth or ammonium salts or the salts an organic amine.
- Examples include sodium, lithium, potassium or ammonium salts or the salt of mono-, di- or triethanolamine.
- the anionic dyes used to dye the polyamide fiber material can other additives, e.g. Cooking salt or dextrin.
- the dyeing of the polyamide fiber material with anionic dyes can be carried out according to the these dyes usual dyeing or printing processes, for example according to Pull-out procedure.
- the dyeing liquors or printing pastes can also Water and the dyes further additives, for example wetting agents, anti-foaming agents, Leveling agents or agents influencing the property of the textile material, e.g. Plasticizers, additives for flame retardant or dirt, water and oil repellent Agents and water softening agents and natural or synthetic Thickeners, e.g. Alginates and cellulose ethers.
- the amounts of anionic dyes in the dye baths or printing pastes can be used within wide limits depending on the desired depth of color fluctuate, in general amounts have from 0.01 to 15% by weight, in particular 0.01 up to 10% by weight, based on the dye material or the printing paste, has proven to be advantageous.
- the dyeing is preferably carried out with anionic dyes at a pH of 3 to 7, in particular 4 to 7, one used in the presence of those according to the invention Homo- or copolymers preferably at a pH of 2 to 7 and especially 4 to 7 colors.
- the liquor ratio can be chosen within a wide range, e.g. from 1: 5 to 1:50, preferably 1: 5 to 1:30. It is preferred to dye at a temperature from 70 to 110 ° C, in particular 80 to 105 ° C, wherein in the presence of the invention homo- or copolymers used preferably at 50 to 100 ° C and in particular is dyed at 80 to 100 ° C.
- the aftertreatment with the homo- or copolymers used according to the invention preferably takes place using the pull-out method.
- the fleet ratio can be within a wide range can be selected and is e.g. 1: 4 to 1: 100, preferably 1:10 to 1:40 and especially 1: 5 to 1:40.
- Dyeing machines e.g. open baths, reel runners, jigger or paddle, jet or Circulators can be used.
- the treatment time can e.g. 10 to 60 minutes and preferably 15 to 40 minutes.
- the pH of the fleet is usually included 2 to 7, preferably 4 to 7 and in particular 4 to 6.
- the liquor can contain other conventional additives, e.g. Electrolytes such as Sodium chloride or sodium sulfate, dispersing and wetting agents and defoamers.
- Electrolytes such as Sodium chloride or sodium sulfate, dispersing and wetting agents and defoamers.
- the process according to the invention gives dyeings or prints of Dyes, e.g. anionic dyes, on polyamide fiber material, which a have significant improvement in ozone fastness, without the color yield, nuance or the light fastness can be negatively affected.
- Dyes e.g. anionic dyes
- a dye bath containing 600 parts of water, 0.0108 parts of a dye of the formula 0.0135 parts of a dye of the formula and 0.033 parts of a dye of the formula is adjusted to a pH of 6.5 with 0.72 parts of sodium dihydrogenphosphate monohydrate and 0.6 part of disodium hydrogenphosphate dodecahydrate.
- This dye bath is mixed with 30 parts of polyamide carpet fabric (polyamide 6) at 30 ° C. The temperature is raised uniformly to the boiling point within 45 minutes and dyeing is then carried out for a further 30 minutes at this temperature. The gray colored carpet is then rinsed.
- the dyed carpet fabric is in a fresh bath from 600 parts of water, 1.5 parts of the polymer solution according to Example 1 (amount of 2 wt .-% polymer based on the carpet fabric), 0.6 parts of sodium acetate and 0.7 parts of acetic acid at a pH of 4.5 and a temperature of 75 ° C for 15 minutes.
- the carpet fabric is then rinsed and dried.
- the ozone fastness of the dyeing obtained is carried out in accordance with the test specification ISO 105-G03. The comparison of the after-treated carpet fabric with a carpet fabric that was not after-treated shows a significant increase in the ozone resistance of the after-treated carpet fabric.
- Example 5 The procedure is as described in Example 5, but instead of 2% by weight, based on the carpet fabric, the polymer according to Example 1, the equivalent amount one of the polymers according to one of Examples 2 to 4, is also a Obtain polyamide carpet fabric with a gray, ozone-resistant color.
- a dye bath containing 600 parts of water, 0.0108 parts of a dye of the formula 0.0135 parts of a dye of the formula and 0.033 parts of a dye of the formula and 1.5 parts of the polymer solution from Example 1 (amount used 2% by weight) is adjusted to a pH of 6.5 using 0.72 part of sodium dihydrogenphosphate monohydrate and 0.6 part of disodium hydrogenphosphate dodecahydrate.
- This dye bath is mixed with 30 parts of polyamide carpet fabric (polyamide 6) at 30 ° C. The temperature is raised uniformly to the boiling point within 45 minutes and dyeing is then carried out for a further 30 minutes at this temperature. The gray colored carpet is then rinsed briefly with cold water and dried.
- the ozone fastness of the dyeing obtained is carried out in accordance with the test specification ISO 105-G03.
- the comparison of the dyed carpet fabric with a carpet fabric which was not dyed in the presence of the polymer solution from Example 1 shows a significant increase in the resistance to ozone.
- Example 6 The procedure is as described in Example 6, but instead of 2% by weight, based on the carpet fabric, the polymer according to Example 1, the equivalent amount one of the polymers according to one of Examples 2 to 4, is also a Obtain polyamide carpet fabric with a gray, ozone-resistant color.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Coloring (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Behandlung von natürlichen oder synthetischen Polyamidfasermaterialien zur Verbesserung der Beständigkeit der Farbstoffe gegen Ozoneinwirkung.The present invention relates to a method for the treatment of natural or synthetic polyamide fiber materials to improve the durability of the dyes against exposure to ozone.
Färbungen und Drucke mit Farbstoffen zeigen oftmals eine hohe Empfindlichkeit gegen Ozon. Beispielsweise werden Anthrachinonfarbstoffe leicht durch Ozon oxidativ abgebaut und verändem auf diese Weise ihr Absorbtionsverhalten und somit die Farbe. Dieses Verhalten wird insbesondere bei blauen Anthrachinonfarbstoffen beobachtet. Die Nuance einer Trichromiefärbung auf der Basis blauer Anthrachinonfarbstoffe, beispielsweise eines Polyamidteppichgewebes, wird leicht durch Ozoneinwirkung verändert. Man begegnet diesem Mangel im allgemeinen, indem man das gefärbte Polyamidfasermaterial mit Harzen auf der Basis von Phenol-Formaldehyd-Kondensaten behandelt. Die bekannten Mittel zur Verbesserung der Ozonbeständigkeit weisen jedoch Nachteile, z.B. eine mangelnde Wirksamkeit oder eine negative Beeinflussung anderer Echtheiten, z.B. der Lichtechtheit auf. Es besteht daher ein Bedarf nach verbesserten Mitteln zur Erhöhung der Ozonbeständigkeit für die Behandlung von insbesondere mit anionischen Farbstoffen gefärbten, natürlichen oder synthetischen Polyamidfasermaterialien, welche die genannten Nachteile nicht aufweisen.Dyes and prints with dyes often show a high sensitivity to Ozone. For example, anthraquinone dyes are easily oxidatively degraded by ozone and in this way change their absorption behavior and thus the color. This Behavior is particularly observed with blue anthraquinone dyes. The nuance a trichromatic stain based on blue anthraquinone dyes, for example one Polyamide carpet fabric, is easily changed by exposure to ozone. You meet this deficiency in general by resinating the dyed polyamide fiber material treated on the basis of phenol-formaldehyde condensates. The known means of However, improvements in ozone resistance have disadvantages, e.g. a lack Effectiveness or a negative influence on other fastness properties, e.g. lightfastness on. There is therefore a need for improved means to increase the Resistance to ozone for the treatment of in particular with anionic dyes dyed, natural or synthetic polyamide fiber materials, the above Do not have disadvantages.
Es wurde nun gefunden, dass man die Beständigkeit von beispielsweise Färbungen anionischer Farbstoffe auf Polyamidfasermaterial ohne negative Beeinflussung anderer Echtheiten verbessern kann, wenn man sie einer Behandlung mit bestimmten Homo- oder Copolymeren unterzieht.It has now been found that the resistance of, for example, dyeings anionic dyes on polyamide fiber material without adversely affecting others Fastness can improve if you treat them with certain homo- or Undergoes copolymers.
Gegenstand der vorliegenden Erfindung ist daher ein Verfahren zur Verbesserung der
Beständigkeit von Farbstoffen auf natürlichen oder synthetischen Polyamidfasermaterialien
gegen Ozoneinwirkung, dadurch gekennzeichnet, dass man das Fasermaterial vor, während
oder nach der Färbung mit einer Flotte behandelt, enthaltend ein Homo- oder Copolymer mit
wiederkehrenden Struktureinheiten der Formel (1)
worin
R1 gegebenenfalls substituiertes C1-C4-Alkyl ist.The present invention therefore relates to a process for improving the resistance of dyes on natural or synthetic polyamide fiber materials to the effects of ozone, characterized in that the fiber material is treated with a liquor containing a homo- or copolymer with recurring structural units before, during or after dyeing of the formula (1) wherein
R 1 is optionally substituted C 1 -C 4 alkyl.
Als C1-C4-Alkyl kommt für R1 beispielsweise Methyl, Aethyl, n- oder iso-Propyl, n-, iso-, sec.- oder tert.-Butyl in Betracht, wobei diese Alkylreste unsubstituiert oder substituiert sind, beispielsweise durch Halogen, wie z.B. Fluor, Chlor oder Brom, Hydroxy oder Sulfo.Suitable C 1 -C 4 alkyl for R 1 are, for example, methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, these alkyl radicals being unsubstituted or substituted, for example by halogen, such as fluorine, chlorine or bromine, hydroxy or sulfo.
R1 ist bevorzugt C1-C4-Alkyl und insbesondere Methyl.R 1 is preferably C 1 -C 4 alkyl and especially methyl.
Bevorzugt enthalten die erfindungsgemäss als Mittel zur Verbesserung der Ozonbeständigkeit verwendeten Homo- oder Copolymere 50 bis 100 Mol-% und insbesondere 80 bis 100 Mol-% wiederkehrende Struktureinheiten der Formel (1).They preferably contain according to the invention as agents for improving the Homo- or copolymers used 50 to 100 mol% and ozone resistance in particular 80 to 100 mol% of repeating structural units of the formula (1).
Handelt es sich bei den erfindungsgemäss verwendeten Polymeren um Copolymere, so kommen als copolymerisierbare Monomere z.B. anionische oder nicht-ionische Gruppen enthaltende Verbindungen in Frage.If the polymers used according to the invention are copolymers, then come as copolymerizable monomers e.g. anionic or non-ionic groups containing compounds in question.
Beispielhaft für anionische Gruppen enthaltende Monomere seien die folgenden
ungesättigten Verbindungen genannt:
Acrylsäure, Maleinsäure, Fumarsäure, Itaconsäure, Mesaconsäure, Citraconsäure,
Vinylessigsäure, Vinyloxyessigsäure, Vinylpropionsäure, Crotonsäure, Aconitsäure,
Allylessigsäure, Allyloxyessigsäure, α,β-Dimethylacrylsäure, Allylmalonsäure,
Allyloxymalonsäure, Methylenmalonsäure, Glutaconsäure, β-Carboxyethylacrylat, Allyloxy-3-hydroxybutansäure,
Allylbemsteinsäure, Acrylamidoglycolsäure, Vinylsulfonsäure,
(Meth)allylsulfonsäure, (Meth)acrylamidomethylpropansulfonsäure, (Meth)acrylamidopropansulfonsäure,
(Meth)acrylamidoethansulfonsäure, (Meth)acrylamidomethansulfonsäure,
Sulfopropyl(meth)acrylat oder Styrolsulfonsäure. The following unsaturated compounds may be mentioned as examples of monomers containing anionic groups:
Acrylic acid, maleic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, vinyl acetic acid, vinyl oxyacetic acid, vinyl propionic acid, crotonic acid, aconitic acid, allylacetic acid, allyloxyacetic acid, α, β-dimethylacrylic acid, allylmalonic acid, allyloxymaloxy, allylacrylic acid, carboxylate, methacryloyloxyacyl, methacrylate, carboxylate Allyl succinic acid, acrylamidoglycolic acid, vinylsulfonic acid, (meth) allylsulfonic acid, (meth) acrylamidomethylpropanesulfonic acid, (meth) acrylamidopropanesulfonic acid, (meth) acrylamidoethanesulfonic acid, (meth) acrylamidomethanesulfonic acid, sulfopropyl (meth) acrylate or styrene sulfonic acid.
Beispielhaft für nicht-ionische Gruppen enthaltende Monomere seien die folgenden
ungesättigten Verbindungen genannt:
Maleinsäureanhydrid, Vinylcaprolactam, Diallylamin, N-Methyldiallylamin, N-Ethyldiallylamin,
N-Vinylpyrrolidon, N-Vinylformamid, N-Vinylacetamid, N-Vinyl-N-methyl-formamid, N-Vinyl-N-methyl-acetamid,
N-Vinyl-N-ethyl-acetamid, N-Vinylimidazol, N-Vinyl-N-methyl-imidazol,
N-Vinylimidazolin, N-Vinyl-2-methylimidazolin, N-Vinylcaprolactam, Vinylacetat,
Vinylpropionat, Vinylbutyrat, C1-C22-Alkylvinylketon, C1-C22-Alkylvinylether, Olefine wie z.B.
Ethylen, Propylen, Isobuten, Styrol oder dessen Derivate, wie z.B. Hydroxystyrol,
1,2-Dimethoxyethylen, Hydroxy-C2-C4-Alkyl-(meth)-acrylat, (Meth)acrylsäure-C1-C22-alkylester,
(Meth)acrolein, (Meth)acrylnitril, (Meth)acrylamid, N-Mono/N,N-Di-C1-C10-Alkyl(meth)acrylamid,
(C1-C4)-Alkoxy-(meth)acrylate, N,N-Di-C1-C2-Alkylamino-C1-C4-alkyl(meth)acrylate,
ungesättigte Acetale, Ketale oder Orthocarbonsäureester wie z.B.
2,5-Dimethoxy-2,5-dihydrofuran oder 2-Methoxy-3,4-dihydro-2H-pyran.The following unsaturated compounds may be mentioned as examples of monomers containing nonionic groups:
Maleic anhydride, vinylcaprolactam, diallylamine, N-methyldiallylamine, N-ethyldiallylamine, N-vinylpyrrolidone, N-vinylformamide, N-vinyl acetamide, N-vinyl-N-methylformamide, N-vinyl-N-methyl-acetamide, N-vinyl N-ethyl-acetamide, N-vinylimidazole, N-vinyl-N-methyl-imidazole, N-vinylimidazoline, N-vinyl-2-methylimidazoline, N-vinylcaprolactam, vinyl acetate, vinyl propionate, vinyl butyrate, C 1 -C 22 alkyl vinyl ketone, C 1 -C 22 alkyl vinyl ether, olefins such as ethylene, propylene, isobutene, styrene or derivatives thereof such as hydroxystyrene, 1,2-dimethoxyethylene, hydroxy-C 2 -C 4 alkyl (meth) acrylate, (meth ) C 1 -C 22 acrylic acid alkyl ester, (meth) acrolein, (meth) acrylonitrile, (meth) acrylamide, N-mono / N, N-di-C 1 -C 10 alkyl (meth) acrylamide, (C 1 -C 4 ) alkoxy- (meth) acrylates, N, N-di-C 1 -C 2 alkylamino-C 1 -C 4 alkyl (meth) acrylates, unsaturated acetals, ketals or orthocarboxylic acid esters such as 2.5 -Dimethoxy-2,5-dihydrofuran or 2-methoxy-3,4-dihydro-2H-pyran.
Bevorzugt als copolymerisierbare Monomere in den erfindungsgemäss verwendeten
Polymeren sind
Acrylsäure, Maleinsäure,Vinylessigsäure, Acrylamidoglycolsäure, (Meth)acrylamidomethansulfonsäure,Vinylsulfonsäure,
(Meth)allylsulfonsäure, (Meth)acrylamidomethylpropansulfonsäure,
(Meth)acrylamidopropansulfonsäure, (Meth)acrylamidoethansulfonsäure,
(Meth)acrylamidomethansulfonsäure, Sulfopropyl(meth)acrylat,
4-Styrolsulfonsäure, Maleinsäureanhydrid, N-Vinylpyrrolidon, Vinylcaprolactam,
N-Vinylformamid, N-Vinyl-N-methyl-formamid, N-Vinylacetamid, N-Vinyl-N-methyl-acetamid,
N-Vinylimidazol, Vinylacetat, Vinylpropionat, Vinylbutyrat, C1-C6Alkylvinylketon,
C1-C6Alkylvinylether, Ethylen, Propylen, Isobuten, Styrol, Hydroxy-ethyl/propyl/butyl(meth)acrylat,
(Meth)acrylsäure-C1-C6-alkylester, (Meth)acrolein, (Meth)acrylnitril,
(Meth)acrylamid, N-Mono/N,N-Di-C1-C6-Alkyl-(meth)acrylamid, 2,5-Dimethoxy-2,5-dihydrofuran
oder 2-Methoxy-3,4-dihydro-2H-pyran.Preferred as copolymerizable monomers in the polymers used according to the invention
Acrylic acid, maleic acid, vinyl acetic acid, acrylamidoglycolic acid, (meth) acrylamidomethanesulfonic acid, vinylsulfonic acid, (meth) allylsulfonic acid, (meth) acrylamidomethylpropanesulfonic acid, (meth) acrylamidopropanesulfonic acid, (meth) acrylamidoethanesulfonic acid, (meth) acrylamidomethanesulfonic acid, sulfopropyl (st) sulfatonic acid, sulfopropyl (meth) acrylate sulfate, Maleic anhydride, N-vinylpyrrolidone, vinylcaprolactam, N-vinylformamide, N-vinyl-N-methylformamide, N-vinyl acetamide, N-vinyl-N-methyl-acetamide, N-vinylimidazole, vinyl acetate, vinyl propionate, vinyl butyrate, C 1 -C 6 alkyl vinyl ketone, C 1 -C 6 alkyl vinyl ether, ethylene, propylene, isobutene, styrene, hydroxyethyl / propyl / butyl (meth) acrylate, (meth) acrylic acid C 1 -C 6 alkyl ester, (meth) acrolein, (meth ) acrylonitrile, (meth) acrylamide, N-mono / N, N-di-C 1 -C 6 -alkyl- (meth) acrylamide, 2,5-dimethoxy-2,5-dihydrofuran or 2-methoxy-3,4 dihydro-2H-pyran.
Ganz besonders bevorzugt als copolymerisierbare Monomere in den erfindungsgemäss
verwendeten Polymeren sind:
Vinylsulfonsäure, 2-Acrylamido-2-methylpropansulfonsäure, 3-(Meth)acrylamidopropansulfonsäure,
Maleinsäureanhydrid, N-Vinylpyrrolidon, N-Vinylformamid, N-Vinyl-N-methylformamid,
N-Vinylacetamid, N-Vinyl-N-methyl-acetamid, N-Vinylimidazol, Vinylacetat, Styrol,
Hydroxy-ethyl/propyl-(meth)acrylat, (Meth)acrylsäure-C1-C6-alkylester, (Meth)acrylnitril,
(Meth)acrylamid, N-Mono/N,N-Di-C1-C6-Alkyl-(meth)acrylamid oder 2-Methoxy-3,4-dihydro-2H-pyran.Very particularly preferred as copolymerizable monomers in the polymers used according to the invention are:
Vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 3- (meth) acrylamidopropanesulfonic acid, maleic anhydride, N-vinylpyrrolidone, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methyl-acetamide, N -Vinylimidazole, vinyl acetate, styrene, hydroxyethyl / propyl- (meth) acrylate, (meth) acrylic acid-C 1 -C 6 alkyl ester, (meth) acrylonitrile, (meth) acrylamide, N-mono / N, N-di -C 1 -C 6 alkyl- (meth) acrylamide or 2-methoxy-3,4-dihydro-2H-pyran.
Besonders wichtig als copolymerisierbare Monomere in den erfindungsgemäss verwendeten
Polymeren sind:
Vinylsulfonsäure, 3-(Meth)acrylamidopropansulfonsäure oder 2-Methoxy-3,4-dihydro-2H-pyran.Particularly important as copolymerizable monomers in the polymers used according to the invention are:
Vinylsulfonic acid, 3- (meth) acrylamidopropanesulfonic acid or 2-methoxy-3,4-dihydro-2H-pyran.
Es können auch Gemische von mehreren der zuvor genannten Homo- oder Copolymere in dem erfindungsgemässen Verfahren verwendet werden.Mixtures of several of the aforementioned homopolymers or copolymers can also be used the inventive method can be used.
Die im erfindungsgemässen Verfahren verwendeten Homo- oder Copolymere weisen ein mittleres Molekulargewicht von 1 000 bis 1 000 000, vorzugsweise 1 000 bis 500 000 und insbesondere 5 000 bis 200 000 auf.The homopolymers or copolymers used in the process according to the invention have average molecular weight of 1,000 to 1,000,000, preferably 1,000 to 500,000 and in particular 5,000 to 200,000.
Die Herstellung der erfindungsgemäss als Mittel zur Verbesserung der Ozonbeständigkeit
verwendeten Homo- oder Copolymere enthaltend wiederkehrende Struktureinheiten der
zuvor angegebenen Formel (1) erfolgt in an sich bekannter Weise, z.B. durch ionisch oder
vorzugsweise radikalisch eingeleitete Polymerisation der Monomeren der Formel (2)
wobei
R1 die oben angegebenen Bedeutungen und Bevorzugungen hat, z.B. in Lösung,
Suspension oder Emulsion, gegebenenfalls in Gegenwart der zuvor beispielhaft als
copolymerisierbare Monomere genannten ungesättigten Verbindungen. Die Polymerisation
erfolgt dabei bevorzugt in Lösung mit einem Peroxid, Persulfat oder einer Azoverbindung,
z.B. mit Natriumpersulfat oder Azo-bis-(2-amidinopropan)-hydrochlorid, als
Radikalkettenstarter, wobei dieser z.B. in einer Menge von 0,005 bis 10 Gew.-%, bezogen
auf die eingesetzten Monomere, anwesend ist. The homopolymers or copolymers containing recurring structural units of the above formula (1) used according to the invention as agents for improving the ozone resistance are prepared in a manner known per se, for example by polymerization of the monomers of the formula (2) initiated ionically or preferably by free radicals. in which
R 1 has the meanings and preferences given above, for example in solution, suspension or emulsion, optionally in the presence of the unsaturated compounds mentioned above as examples of copolymerizable monomers. The polymerization is preferably carried out in solution with a peroxide, persulfate or an azo compound, for example with sodium persulfate or azo-bis- (2-amidinopropane) hydrochloride, as a free-radical initiator, for example in an amount of 0.005 to 10% by weight, based on the monomers used, is present.
Die im erfindungsgemässen Verfahren verwendeten Homo- oder Copolymere werden unabhängig vom Flottenverhältnis z.B. in einer Menge von 0,05 bis 10 Gew.-%, vorzugsweise 0,1 bis 6 Gew.-% und besonders bevorzugt 0,5 bis 4 Gew.-%, bezogen auf das Gewicht des Polyamidfasermaterials, eingesetzt.The homo- or copolymers used in the process according to the invention are regardless of the fleet ratio e.g. in an amount of 0.05 to 10% by weight, preferably 0.1 to 6% by weight and particularly preferably 0.5 to 4% by weight, based on the weight of the polyamide fiber material used.
Die Behandlung des Polyamidfasermaterials mit den erfindungsgemäss verwendeten Homo- oder Copolymeren kann vor, während oder nach dem Färben und vorzugsweise während oder nach dem Färben erfolgen.Treatment of the polyamide fiber material with the homo- or copolymers can be before, during or after dyeing and preferably during or after dyeing.
Erfolgt die Behandlung des Polyamidfasermaterials mit den erfindungsgemäss verwendeten Homo- oder Copolymeren während des Färbevorgangs, so führt man das erfindungsgemässe Verfahren vorteilhafterweise so aus, dass man die Polymere der Färbeflotte in der zuvor angegebenen Menge zusetzt und das Fasermaterial in üblicher Weise färbt.The polyamide fiber material is treated with those used according to the invention Homopolymers or copolymers during the dyeing process, that's how it is done Process according to the invention advantageously such that the polymers of Dyeing liquor is added in the amount specified above and the fiber material in the usual way Way colors.
Erfolgt die Behandlung des Polyamidfasermaterials mit den erfindungsgemäss verwendeten Homo- oder Copolymeren nach dem Färben, so führt man das erfindungsgemässe Verfahren vorteilhafterweise so aus, dass man zunächst das Polyamidfasermaterial in üblicher Weise färbt und anschliessend eine Nachbehandlung mit einer die Polymere in der zuvor angegebenen Menge enthaltenden frischen wässrigen Flotte anschliesst. Danach kann das gefärbte Polyamidfasermaterial ohne weiteren Spülvorgang entwässert und auf übliche Weise getrocknet werden. Die Nachbehandlung erfolgt in der Regel in frischer Flotte. Sie ist aber auch direkt im Färbebad durchführbar, sofern das Färbebad am Ende weitgehend ausgezogen und noch genügend sauer ist. Im Anschluss an die Behandlung wird in der Regel mit Wasser kurz kalt gespült.The polyamide fiber material is treated with those used according to the invention Homopolymers or copolymers after dyeing, this is done according to the invention Process advantageously such that the polyamide fiber material is first in usually colors and then an aftertreatment with a polymer in the connects the previously specified amount containing fresh aqueous liquor. After that the dyed polyamide fiber material can be dewatered and opened without further rinsing can be dried in the usual way. The after-treatment is usually carried out in a fresh one Fleet. However, it can also be carried out directly in the dye bath, provided that the dye bath is at the end largely stripped and is still sufficiently acidic. After the treatment is usually rinsed briefly with water.
Als Polyamidfasermaterial kommt natürliches Polyamidfasermaterial, wie z.B. Wolle oder Seide, oder synthetisches Polyamidfasermaterial, wie z.B. Polyamid 6 oder Polyamid 6.6, oder Fasermischungen wie z.B. Wolle/Cellulose- oder Polyamid/Cellulose-Mischfasern oder Polyamid/Wolle-Mischfasern in Betracht. Bevorzugt handelt es sich bei dem Fasermaterial um synthetisches Polyamidfasermaterial.Natural polyamide fiber material such as e.g. Wool or Silk, or synthetic polyamide fiber material, e.g. Polyamide 6 or polyamide 6.6, or fiber mixtures such as Wool / cellulose or polyamide / cellulose mixed fibers or Polyamide / wool mixed fibers into consideration. The fiber material is preferred around synthetic polyamide fiber material.
Das Textilgut ist in jeglicher Form anwendbar, z.B. als Faser, Garn, Gewebe oder Gewirke. The textile can be used in any form, e.g. as fiber, yarn, woven or knitted fabric.
Die Färbungen erfolgen beispielsweise mit anionischen Farbstoffen, wobei alle üblichen anionischen Farbstoffe, z.B. wie sie in Colour Index, 3. Auflage (1971) sowie den Nachträgen dazu unter den Rubriken "Acid Dyes" beschrieben sind, in Frage kommen.The dyeings are carried out, for example, with anionic dyes, all of the usual anionic dyes, e.g. as in Color Index, 3rd edition (1971) and the Addenda to this are described under the heading "Acid Dyes".
Beispiele sind sulfogruppenhaltige Monoazo-, Polyazo-, Metallkomplexazo-, Anthrachinon-, Phthalocyanin- oder Formazanfarbstoffe.Examples are sulfo group-containing monoazo, polyazo, metal complex azo, anthraquinone, Phthalocyanine or formazan dyes.
Bevorzugt erfolgen die Färbungen mit Anthrachinonfarbstoffen und insbesondere mit blauen Anthrachinonfarbstoffen.The dyeings are preferably carried out using anthraquinone dyes and in particular blue ones Anthraquinone dyes.
Die zum Färben des Polyamidfasermaterials verwendeten anionischen Farbstoffe liegen entweder in der Form ihrer freien Sulfonsäure oder vorzugsweise als deren Salze vor.The anionic dyes used to dye the polyamide fiber material lie either in the form of their free sulfonic acid or preferably as their salts.
Als Salze kommen beispielsweise die Alkali-, Erdalkali- oder Ammoniumsalze oder die Salze eines organischen Amins in Betracht. Als Beispiele seien die Natrium-, Lithium-, Kalium- oder Ammoniumsalze oder das Salz des Mono-, Di- oder Triäthanolamins genannt.The salts include, for example, the alkali, alkaline earth or ammonium salts or the salts an organic amine. Examples include sodium, lithium, potassium or ammonium salts or the salt of mono-, di- or triethanolamine.
Die zum Färben des Polyamidfasermaterials verwendeten anionischen Farbstoffe können weitere Zusätze, wie z.B. Kochsalz oder Dextrin, enthalten.The anionic dyes used to dye the polyamide fiber material can other additives, e.g. Cooking salt or dextrin.
Das Färben des Polyamidfasermaterials mit anionischen Farbstoffen kann gemäss den für diese Farbstoffe üblichen Färbe- bzw. Druckverfahren, beispielsweise nach dem Ausziehverfahren, durchgeführt werden. Die Färbeflotten oder Druckpasten können ausser Wasser und den Farbstoffen weitere Zusätze, beispielsweise Netzmittel, Antischaummittel, Egalisiermittel oder die Eigenschaft des Textilmaterials beeinflussende Mittel wie z.B. Weichmachungsmittel, Zusätze zum Flammfestausrüsten oder schmutz-, wasser- und ölabweisende Mittel sowie wasserenthärtende Mittel und natürliche oder synthetische Verdicker, wie z.B. Alginate und Celluloseäther, enthalten.The dyeing of the polyamide fiber material with anionic dyes can be carried out according to the these dyes usual dyeing or printing processes, for example according to Pull-out procedure. The dyeing liquors or printing pastes can also Water and the dyes further additives, for example wetting agents, anti-foaming agents, Leveling agents or agents influencing the property of the textile material, e.g. Plasticizers, additives for flame retardant or dirt, water and oil repellent Agents and water softening agents and natural or synthetic Thickeners, e.g. Alginates and cellulose ethers.
Die Mengen, in denen anionische Farbstoffe in den Färbebädem oder Druckpasten verwendet werden, können je nach der gewünschten Farbtiefe in weiten Grenzen schwanken, im allgemeinen haben sich Mengen von 0,01 bis 15 Gew.-%, insbesondere 0,01 bis 10 Gew.-%, bezogen auf das Färbegut bzw. die Druckpaste, als vorteilhaft erwiesen. The amounts of anionic dyes in the dye baths or printing pastes can be used within wide limits depending on the desired depth of color fluctuate, in general amounts have from 0.01 to 15% by weight, in particular 0.01 up to 10% by weight, based on the dye material or the printing paste, has proven to be advantageous.
Vorzugsweise erfolgt das Färben mit anionischen Farbstoffen bei einem pH-Wert von 3 bis 7, insbesondere 4 bis 7, wobei man in Gegenwart der erfindungsgemäss verwendeten Homo- oder Copolymeren vorzugsweise bei einem pH-Wert von 2 bis 7 und insbesondere 4 bis 7 färbt. Das Flottenverhältnis kann innerhalb eines weiten Bereichs gewählt werden, z.B. von 1:5 bis 1:50, vorzugsweise 1:5 bis 1:30. Vorzugsweise färbt man bei einer Temperatur von 70 bis 110°C, insbesondere 80 bis 105°C, wobei in Gegenwart der erfindungsgemäss verwendeten Homo- oder Copolymeren vorzugsweise bei 50 bis 100°C und insbesondere bei 80 bis 100°C gefärbt wird.The dyeing is preferably carried out with anionic dyes at a pH of 3 to 7, in particular 4 to 7, one used in the presence of those according to the invention Homo- or copolymers preferably at a pH of 2 to 7 and especially 4 to 7 colors. The liquor ratio can be chosen within a wide range, e.g. from 1: 5 to 1:50, preferably 1: 5 to 1:30. It is preferred to dye at a temperature from 70 to 110 ° C, in particular 80 to 105 ° C, wherein in the presence of the invention homo- or copolymers used preferably at 50 to 100 ° C and in particular is dyed at 80 to 100 ° C.
Die Nachbehandlung mit den erfindungsgemäss verwendeten Homo- oder Copolymeren erfolgt bevorzugt nach dem Ausziehverfahren. Das Flottenverhältnis kann dabei innerhalb eines weiten Bereichs gewählt werden und beträgt z.B. 1:4 bis 1:100, vorzugsweise 1:10 bis 1:40 und insbesondere 1:5 bis 1:40.The aftertreatment with the homo- or copolymers used according to the invention preferably takes place using the pull-out method. The fleet ratio can be within a wide range can be selected and is e.g. 1: 4 to 1: 100, preferably 1:10 to 1:40 and especially 1: 5 to 1:40.
Besondere Vorrichtungen sind nicht erforderlich. Es können z.B. die üblichen Färbeapparate, z.B. offene Bäder, Haspelkufen, Jigger oder Paddel-, Düsen- oder Zirkulationsapparate, verwendet werden.Special devices are not required. For example, the usual Dyeing machines, e.g. open baths, reel runners, jigger or paddle, jet or Circulators can be used.
Man arbeitet zweckmässig bei einer Temperatur von z.B. 20 bis 100°C, vorzugsweise 50 bis 100°C und insbesondere 60 bis 100°C. Die Behandlungszeit kann z.B. 10 bis 60 Minuten und vorzugsweise 15 bis 40 Minuten betragen. Der pH-Wert der Flotte liegt in der Regel bei 2 bis 7, vorzugsweise bei 4 bis 7 und insbesondere bei 4 bis 6.It is convenient to work at a temperature of e.g. 20 to 100 ° C, preferably 50 to 100 ° C and especially 60 to 100 ° C. The treatment time can e.g. 10 to 60 minutes and preferably 15 to 40 minutes. The pH of the fleet is usually included 2 to 7, preferably 4 to 7 and in particular 4 to 6.
Die Flotte kann ausser dem Fixiermittel weitere übliche Zusätze, z.B. Elektrolyte wie z.B. Natriumchlorid oder Natriumsulfat, Dispergier- und Netzmittel sowie Entschäumer, enthalten.In addition to the fixative, the liquor can contain other conventional additives, e.g. Electrolytes such as Sodium chloride or sodium sulfate, dispersing and wetting agents and defoamers.
Man erhält nach dem erfindungsgemässen Verfahren Färbungen oder Drucke von Farbstoffen, z.B. anionischen Farbstoffen, auf Polyamidfasermaterial, welche eine erhebliche Verbesserung der Ozonechtheit aufweisen, ohne dass die Farbausbeute, Nuance oder die Lichtechtheiten negativ beeinflusst werden.The process according to the invention gives dyeings or prints of Dyes, e.g. anionic dyes, on polyamide fiber material, which a have significant improvement in ozone fastness, without the color yield, nuance or the light fastness can be negatively affected.
Die nachfolgenden Beispiele dienen zur Erläuterung der Erfindung. Die Temperaturen sind in Celsiusgraden angegeben, Teile sind Gewichtsteile, die Prozentangaben beziehen sich auf Gewichtsprozente, sofern nicht anders vermerkt. Gewichtsteile stehen zu Volumenteilen im Verhältnis von Kilogramm zu Liter.The following examples serve to explain the invention. The temperatures are stated in degrees Celsius, parts are parts by weight, the percentages refer percentages by weight, unless stated otherwise. Parts by weight relate to parts by volume in the ratio of kilograms to liters.
In einem Reaktor werden 68,8 Teile Methacrylsäure, 4,4 Teile Mercaptoethanol und 146 Teile Wasser vorgelegt. Unter Stickstoff wird die Temperatur auf 75°C gebracht. Man tropft innerhalb von 30 Minuten eine Lösung aus 1 Teil Natriumpersulfat und 10 Teile Wasser zu. Die Reaktion ist exotherm und die Temperatur steigt bis auf 85°C. Man lässt eine Stunde bei 85°C nachpolymerisieren. Bei 80°C gibt man dann 13,8 Teile Wasserstoffperoxyd 30%ig zu und rührt 2 Stunden bei dieser Temperatur. Die Polymerlösung wird abgekühlt, auf einen pH-Wert von 6,5 gebracht und bis zu einem Trockengehalt von 40% aufkonzentriert. Man erhält ca. 210 g einer klaren, hell gelben viskosen Lösung eines Polymeren, das im wesentlichen Struktureinheiten der Formel (101) aufweist und ein Molekulargewicht von ca. 8 000 hat.68.8 parts of methacrylic acid, 4.4 parts of mercaptoethanol and 146 parts of water are placed in a reactor. The temperature is brought to 75 ° C. under nitrogen. A solution of 1 part of sodium persulfate and 10 parts of water is added dropwise within 30 minutes. The reaction is exothermic and the temperature rises to 85 ° C. The mixture is left to polymerize at 85 ° C. for one hour. 13.8 parts of 30% hydrogen peroxide are then added at 80 ° C. and the mixture is stirred for 2 hours at this temperature. The polymer solution is cooled, brought to a pH of 6.5 and concentrated to a dry content of 40%. About 210 g of a clear, light yellow viscous solution of a polymer are obtained which essentially have structural units of the formula (101) and has a molecular weight of about 8,000.
In einem Reaktor werden 65 Teile Isopropanol und 17,5 Teile Wasser vorgelegt und unter Sticktstoff auf 80°C geheizt. Dann wird innerhalb von 120 Minuten eine Lösung aus 64,5 Teilen Methacrylsäure, 10,3 Teilen 2-Acrylamido-2-methyl-propansulfonsäure und 22,5 Teilen Wasser zugetropft. Gleichzeitig wird innerhalb von 150 Minuten eine Lösung von 8,3 Teilen Natriumpersulfat und 25 Teilen Wasser zugetropft. Es wird 3 Stunden bei ca. 80°C nachpolymerisiert. Die Polymerlösung wird mit Wasser verdünnt, das Isopropanol abdestilliert und bis zu einem Trockengehalt von 20% aufkonzentriert. Man erhält ca. 400 g einer trüben, viskosen Lösung eines Polymeren, das im wesentlichen Struktureinheiten der Formel (101) und (102) aufweist, mit einer Brookfieldviskosität von 1600 cP.65 parts of isopropanol and 17.5 parts of water are placed in a reactor and heated to 80 ° C. under nitrogen. A solution of 64.5 parts of methacrylic acid, 10.3 parts of 2-acrylamido-2-methyl-propanesulfonic acid and 22.5 parts of water is then added dropwise within 120 minutes. At the same time, a solution of 8.3 parts of sodium persulfate and 25 parts of water is added dropwise within 150 minutes. It is polymerized for 3 hours at about 80 ° C. The polymer solution is diluted with water, the isopropanol is distilled off and concentrated to a dry content of 20%. About 400 g of a cloudy, viscous solution of a polymer are obtained which essentially have structural units of the formulas (101) and (102) with a Brookfield viscosity of 1600 cP.
In einem Reaktor werden 69,5 Teile Isopropanol und 19 Teile Wasser vorgelegt und unter Sticktstoff auf 80°C geheizt. Dann wird innerhalb von 120 Minuten eine Lösung aus 64,5 Teilen Methacrylsäure, 21,7 Teilen einer 30%igen, wässrigen Vinylsulfonsäure-Natriumsalz-Lösung, 69,3 Teilen Isopropanol und 140,7 Teilen Wasser zugetropft. Gleichzeitig wird innerhalb von 150 Minuten eine Lösung aus 7,5 Teilen Natriumpersulfat und 25 Teilen Wasser zugetropft. Es wird 3 Stunden bei ca. 80°C nachpolymerisiert. Die Polymerlösung wird mit Wasser verdünnt, das Isopropanol abdestilliert und bis einem Trockengehalt von 30% aufkonzentriert. Man erhält ca. 260 g einer trüben, viskosen Lösung eines Polymeren, das im wesentlichen Struktureinheiten der Formel (101) und (103) aufweist,mit einer Brookfieldviskosität von 970 cP.69.5 parts of isopropanol and 19 parts of water are placed in a reactor and heated to 80 ° C. under nitrogen. A solution of 64.5 parts of methacrylic acid, 21.7 parts of a 30% strength aqueous vinylsulfonic acid sodium salt solution, 69.3 parts of isopropanol and 140.7 parts of water is then added dropwise within 120 minutes. At the same time, a solution of 7.5 parts of sodium persulfate and 25 parts of water is added dropwise within 150 minutes. It is polymerized for 3 hours at about 80 ° C. The polymer solution is diluted with water, the isopropanol is distilled off and concentrated to a dry content of 30%. About 260 g of a cloudy, viscous solution of a polymer are obtained which essentially have structural units of the formulas (101) and (103) with a Brookfield viscosity of 970 cP.
In einem Reaktor werden 5,25 Teile 2-Methoxy-3,4-dihydro-2H-pyran und 12 Teile o-Xylol vorgelegt und unter Sticktstoff auf 90°C geheizt. Dann wird innerhalb von 100 Minuten eine Lösung aus 35 Teilen Methacrylsäure und 20 Teile o-Xylol zugetropft. Gleichzeitig werden innerhalb von 120 Minuten 0,8 Teile tert.-Butyl-2-ethyl-perhexanoat und 20 Teile o-Xylol zugetropft. Es wird 2 Stunden bei ca. 90°C nachpolymerisiert. Die Polymerlösung wird mit Wasser verdünnt und das o-Xylol azeotropisch abdestilliert. Die Polymerlösung wird auf einen pH-Wert von 7 eingestellt und bis einem Trockengehalt von 20% aufkonzentriert. Man erhält ca. 180 g einer klaren, leicht viskosen Lösung eines Polymeren, das im wesentlichen Struktureinheiten der Formel (101) und (104) aufweist, mit einer Brookfieldviskosität von 30 cP.5.25 parts of 2-methoxy-3,4-dihydro-2H-pyran and 12 parts of o-xylene are placed in a reactor and heated to 90 ° C. under nitrogen. A solution of 35 parts of methacrylic acid and 20 parts of o-xylene is then added dropwise within 100 minutes. At the same time, 0.8 part of tert-butyl 2-ethyl perhexanoate and 20 parts of o-xylene are added dropwise within 120 minutes. It is polymerized for 2 hours at about 90 ° C. The polymer solution is diluted with water and the o-xylene is distilled off azeotropically. The polymer solution is adjusted to a pH of 7 and concentrated to a dry content of 20%. About 180 g of a clear, slightly viscous solution of a polymer are obtained which essentially have structural units of the formulas (101) and (104) has a Brookfield viscosity of 30 cP.
Ein Färbebad enthaltend 600 Teile Wasser,
0,0108 Teile eines Farbstoffs der Formel
0,0135 Teile eines Farbstoffs der Formel
und 0,033 Teile eines Farbstoffs der Formel
wird mit 0,72 Teilen Natriumdihydrogenphosphat-monohydrat und 0,6 Teilen
Dinatriumhydrogenphosphat-dodecahydrat auf einen pH von 6,5 eingestellt. In dieses
Färbebad geht man bei 30°C mit 30 Teilen Polyamidteppichgewebe (Polyamid 6) ein. Die
Temperatur wird gleichmässig innerhalb von 45 Minuten bis zum Siedepunkt erhöht und
man färbt anschliessend noch 30 Minuten bei dieser Temperatur. Der grau gefärbte Teppich
wird danach gespült. Das gefärbte Teppichgewebe wird in einem frischen Bad aus 600
Teilen Wasser, 1,5 Teilen der Polymerlösung gemäss Beispiel 1 (Einsatzmenge 2 Gew.-%
Polymer bezogen auf das Teppichgewebe), 0,6 Teilen Natriumacetat und 0,7 Teilen
Essigsäure bei einem pH von 4,5 und einer Temperatur von 75°C 15 Minuten
nachbehandelt. Das Teppichgewebe wird anschliessend gespült und getrocknet. Die
Ozonechtheit der erhaltenen Färbung wird nach der Prüfvorschrift ISO 105-G03
durchgeführt. Der Vergleich des nachbehandelten Teppichgewebes mit einem
Teppichgewebe, das nicht nachbehandelt wurde, zeigt eine deutliche Erhöhung der
Ozonbeständigkeit des nachbehandelten Teppichgewebes.A dye bath containing 600 parts of water,
0.0108 parts of a dye of the formula 0.0135 parts of a dye of the formula and 0.033 parts of a dye of the formula is adjusted to a pH of 6.5 with 0.72 parts of sodium dihydrogenphosphate monohydrate and 0.6 part of disodium hydrogenphosphate dodecahydrate. This dye bath is mixed with 30 parts of polyamide carpet fabric (polyamide 6) at 30 ° C. The temperature is raised uniformly to the boiling point within 45 minutes and dyeing is then carried out for a further 30 minutes at this temperature. The gray colored carpet is then rinsed. The dyed carpet fabric is in a fresh bath from 600 parts of water, 1.5 parts of the polymer solution according to Example 1 (amount of 2 wt .-% polymer based on the carpet fabric), 0.6 parts of sodium acetate and 0.7 parts of acetic acid at a pH of 4.5 and a temperature of 75 ° C for 15 minutes. The carpet fabric is then rinsed and dried. The ozone fastness of the dyeing obtained is carried out in accordance with the test specification ISO 105-G03. The comparison of the after-treated carpet fabric with a carpet fabric that was not after-treated shows a significant increase in the ozone resistance of the after-treated carpet fabric.
Verfährt man wie in Beispiel 5 beschrieben, verwendet jedoch anstelle von 2 Gew.-%, bezogen auf das Teppichgewebe, des Polymeren gemäss Beispiel 1 die äquivalente Menge eines der Polymeren gemäss einem der Beispiele 2 bis 4, so wird ebenfalls ein Polyamidteppichgewebe mit einer grauen, ozonechten Färbung erhalten.The procedure is as described in Example 5, but instead of 2% by weight, based on the carpet fabric, the polymer according to Example 1, the equivalent amount one of the polymers according to one of Examples 2 to 4, is also a Obtain polyamide carpet fabric with a gray, ozone-resistant color.
Ein Färbebad enthaltend 600 Teile Wasser,
0,0108 Teile eines Farbstoffs der Formel
0,0135 Teile eines Farbstoffs der Formel
und 0,033 Teile eines Farbstoffs der Formel
und 1,5 Teile der Polymerlösung aus Beispiel 1 (Einsatzmenge 2 Gew.-%) wird mit 0,72
Teilen Natriumdihydrogenphosphat-monohydrat und 0,6 Teilen Dinatriumhydrogenphosphat-dodecahydrat
auf einen pH von 6,5 eingestellt. In dieses Färbebad geht man bei 30°C mit 30
Teilen Polyamidteppichgewebe (Polyamid 6) ein. Die Temperatur wird gleichmässig
innerhalb von 45 Minuten bis zum Siedepunkt erhöht und man färbt anschliessend noch 30
Minuten bei dieser Temperatur. Der grau gefärbte Teppich wird danach kurz kalt gespült und
getrocknet. Die Ozonechtheit der erhaltenen Färbung wird nach der Prüfvorschrift ISO 105-G03
durchgeführt. Der Vergleich des gefärbten Teppichgewebes mit einem Teppichgewebe,
das nicht in Gegenwart der Polymerlösung aus Beispiel 1 gefärbt wurde, zeigt eine deutliche
Erhöhung der Ozonbeständigkeit.A dye bath containing 600 parts of water,
0.0108 parts of a dye of the formula 0.0135 parts of a dye of the formula and 0.033 parts of a dye of the formula and 1.5 parts of the polymer solution from Example 1 (amount used 2% by weight) is adjusted to a pH of 6.5 using 0.72 part of sodium dihydrogenphosphate monohydrate and 0.6 part of disodium hydrogenphosphate dodecahydrate. This dye bath is mixed with 30 parts of polyamide carpet fabric (polyamide 6) at 30 ° C. The temperature is raised uniformly to the boiling point within 45 minutes and dyeing is then carried out for a further 30 minutes at this temperature. The gray colored carpet is then rinsed briefly with cold water and dried. The ozone fastness of the dyeing obtained is carried out in accordance with the test specification ISO 105-G03. The comparison of the dyed carpet fabric with a carpet fabric which was not dyed in the presence of the polymer solution from Example 1 shows a significant increase in the resistance to ozone.
Verfährt man wie in Beispiel 6 beschrieben, verwendet jedoch anstelle von 2 Gew.-%, bezogen auf das Teppichgewebe, des Polymeren gemäss Beispiel 1 die äquivalente Menge eines der Polymeren gemäss einem der Beispiele 2 bis 4, so wird ebenfalls ein Polyamidteppichgewebe mit einer grauen, ozonechten Färbung erhalten.The procedure is as described in Example 6, but instead of 2% by weight, based on the carpet fabric, the polymer according to Example 1, the equivalent amount one of the polymers according to one of Examples 2 to 4, is also a Obtain polyamide carpet fabric with a gray, ozone-resistant color.
Claims (11)
R1 gegebenenfalls substituiertes C1-C4-Alkyl ist.Process for improving the resistance of dyes on natural or synthetic polyamide fiber materials to the effects of ozone, characterized in that the fiber material is treated with a liquor before, during or after dyeing, containing a homo- or copolymer with recurring structural units of the formula (1) wherein
R 1 is optionally substituted C 1 -C 4 alkyl.
R1 C1-C4-Alkyl und insbesondere Methyl ist.A method according to claim 1, characterized in that
R 1 is C 1 -C 4 alkyl and especially methyl.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP99810385A EP0957197B1 (en) | 1998-05-13 | 1999-05-04 | Process for treating natural or synthetic polyamide fibrous materials |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP98810433 | 1998-05-13 | ||
EP98810433 | 1998-05-13 | ||
EP99810385A EP0957197B1 (en) | 1998-05-13 | 1999-05-04 | Process for treating natural or synthetic polyamide fibrous materials |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0957197A1 true EP0957197A1 (en) | 1999-11-17 |
EP0957197B1 EP0957197B1 (en) | 2006-06-21 |
Family
ID=8236082
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99810385A Expired - Lifetime EP0957197B1 (en) | 1998-05-13 | 1999-05-04 | Process for treating natural or synthetic polyamide fibrous materials |
Country Status (8)
Country | Link |
---|---|
US (1) | US6280482B1 (en) |
EP (1) | EP0957197B1 (en) |
JP (1) | JP4443669B2 (en) |
AU (1) | AU751951B2 (en) |
CA (1) | CA2271873A1 (en) |
DE (1) | DE59913578D1 (en) |
DK (1) | DK0957197T3 (en) |
ZA (1) | ZA993274B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003041639A2 (en) * | 2001-10-30 | 2003-05-22 | Microbiotix, Inc. | Methods and compositions for treating rotavirus-mediated disease |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0957197B1 (en) * | 1998-05-13 | 2006-06-21 | Ciba SC Holding AG | Process for treating natural or synthetic polyamide fibrous materials |
US20030165404A1 (en) * | 2000-06-05 | 2003-09-04 | Takeshi Omatsu | Ozone indicator and method of measuring ozone concentration |
US7090704B2 (en) * | 2001-12-05 | 2006-08-15 | Ciba Specialty Chemicals Corporation | Method of treating natural or synthetic polyamide fibre materials |
JP2007321247A (en) * | 2006-05-30 | 2007-12-13 | Seiren Co Ltd | Polyamide-based fiber structure |
CN110882680A (en) * | 2019-12-05 | 2020-03-17 | 广东海纳新材料科技有限公司 | Preparation method of hydrophobic mineralized waste fiber adsorption material |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1254743A (en) * | 1969-06-16 | 1971-11-24 | Textilmaschb Zittau Veb | Application of dyestuffs to napped and pile textiles |
US3984202A (en) * | 1972-02-14 | 1976-10-05 | Allied Chemical Corporation | Alkanolamines to reduce ozone attack on dyes in polyamide fibers |
US4097546A (en) * | 1976-03-30 | 1978-06-27 | Allied Chemical Corporation | Ozone resistant, cationic dyeable nylon containing lithium, magnesium or calcium salts of sulfonated polystyrene copolymers |
GB2024874A (en) * | 1978-07-07 | 1980-01-16 | Sandoz Ltd | After treatment of cellulosic fibres dyed with reactive dyes |
WO1989007519A1 (en) * | 1988-02-17 | 1989-08-24 | The Dow Chemical Company | Polymer salt complex for fiber or fabric treatment |
US5464452A (en) * | 1994-05-10 | 1995-11-07 | Henkel Corporation | Process for fixing dyes in textile materials |
EP0824155A1 (en) * | 1996-08-15 | 1998-02-18 | Clariant Finance (BVI) Limited | Concentrated aqueous solutions of sodium salts of polycarboxylic acids, their preparation and their use |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4937123A (en) | 1988-03-11 | 1990-06-26 | Minnesota Mining And Manufacturing Company | Process for providing polyamide materials with stain resistance |
US4822373A (en) | 1988-03-11 | 1989-04-18 | Minnesota Mining And Manufacturing Company | Process for providing polyamide materials with stain resistance with sulfonated novolak resin and polymethacrylic acd |
EP0812949A3 (en) | 1996-06-11 | 1998-07-22 | Ciba SC Holding AG | Process for the treatment of dyed fibrous cellulosic materials |
US5851236A (en) | 1996-08-15 | 1998-12-22 | Clariant Finance (Bvi) Limited | Aqueous, concentrated polycarboxylic acid sodium salt solutions, their production and use |
US5948125A (en) | 1997-05-20 | 1999-09-07 | Ciba Specialty Chemicals Corporation | Method of treating dyed, natural or synthetic polyamide fibre materials |
EP0957197B1 (en) * | 1998-05-13 | 2006-06-21 | Ciba SC Holding AG | Process for treating natural or synthetic polyamide fibrous materials |
-
1999
- 1999-05-04 EP EP99810385A patent/EP0957197B1/en not_active Expired - Lifetime
- 1999-05-04 DK DK99810385T patent/DK0957197T3/en active
- 1999-05-04 DE DE59913578T patent/DE59913578D1/en not_active Expired - Lifetime
- 1999-05-11 CA CA002271873A patent/CA2271873A1/en not_active Abandoned
- 1999-05-11 JP JP12942399A patent/JP4443669B2/en not_active Expired - Fee Related
- 1999-05-12 ZA ZA9903274A patent/ZA993274B/en unknown
- 1999-05-12 AU AU28102/99A patent/AU751951B2/en not_active Ceased
-
2000
- 2000-07-05 US US09/609,955 patent/US6280482B1/en not_active Expired - Fee Related
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1254743A (en) * | 1969-06-16 | 1971-11-24 | Textilmaschb Zittau Veb | Application of dyestuffs to napped and pile textiles |
US3984202A (en) * | 1972-02-14 | 1976-10-05 | Allied Chemical Corporation | Alkanolamines to reduce ozone attack on dyes in polyamide fibers |
US4097546A (en) * | 1976-03-30 | 1978-06-27 | Allied Chemical Corporation | Ozone resistant, cationic dyeable nylon containing lithium, magnesium or calcium salts of sulfonated polystyrene copolymers |
GB2024874A (en) * | 1978-07-07 | 1980-01-16 | Sandoz Ltd | After treatment of cellulosic fibres dyed with reactive dyes |
WO1989007519A1 (en) * | 1988-02-17 | 1989-08-24 | The Dow Chemical Company | Polymer salt complex for fiber or fabric treatment |
US5464452A (en) * | 1994-05-10 | 1995-11-07 | Henkel Corporation | Process for fixing dyes in textile materials |
EP0824155A1 (en) * | 1996-08-15 | 1998-02-18 | Clariant Finance (BVI) Limited | Concentrated aqueous solutions of sodium salts of polycarboxylic acids, their preparation and their use |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003041639A2 (en) * | 2001-10-30 | 2003-05-22 | Microbiotix, Inc. | Methods and compositions for treating rotavirus-mediated disease |
WO2003041639A3 (en) * | 2001-10-30 | 2003-07-24 | Microbiotix Inc | Methods and compositions for treating rotavirus-mediated disease |
Also Published As
Publication number | Publication date |
---|---|
US6280482B1 (en) | 2001-08-28 |
DE59913578D1 (en) | 2006-08-03 |
AU2810299A (en) | 1999-11-25 |
AU751951B2 (en) | 2002-09-05 |
JPH11350354A (en) | 1999-12-21 |
DK0957197T3 (en) | 2006-10-09 |
EP0957197B1 (en) | 2006-06-21 |
JP4443669B2 (en) | 2010-03-31 |
CA2271873A1 (en) | 1999-11-13 |
ZA993274B (en) | 1999-11-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE1066022B (en) | Process for the production of acrylic nitrile mixers | |
EP0879916B1 (en) | Process for the treatment of fibrous materials made from natural or synthetic polyamide | |
EP0376151B1 (en) | Process for dyeing textile materials with pigment dyes | |
EP0957197B1 (en) | Process for treating natural or synthetic polyamide fibrous materials | |
EP0590460A2 (en) | Highly concentrated aqueous poly(acrylonitrile) emulsions and process for their preparation | |
DE1619478A1 (en) | Process for dyeing and printing fiber substrates | |
EP0812949A2 (en) | Process for the treatment of dyed fibrous cellulosic materials | |
EP0277580B1 (en) | Modification of the wet fastness of sulphur dyeings | |
DE1619638A1 (en) | Process for dyeing or printing fibers | |
CH690401A5 (en) | A method for the treatment of dyed cellulose fiber material. | |
DE2240291A1 (en) | ACRYLIC NITRILE CO-POLYMERS, FIBERS MANUFACTURED FROM THEM AND THE PROCESS FOR THE PRODUCTION THEREOF | |
DE60212449T2 (en) | PROCESS FOR TREATING NATURAL OR SYNTHETIC POLYAMIDE FIBER MATERIALS | |
DE2837500A1 (en) | METHOD FOR COLORING CELLULOSE-CONTAINING TEXTILE MATERIAL AND NEW DYES | |
DE4112228A1 (en) | METHOD FOR COLORING CELLULOSE WITH SULFUR DYES | |
DE1619662A1 (en) | Process for the production of prints on fiber material | |
EP0582550B1 (en) | Process for dyeing of wool-containing fibrous materials | |
DE2500882A1 (en) | METHOD OF DYING ACRYLIC FIBERS | |
DE1469618C3 (en) | Process for improving the fastness properties of dyed cellulose fiber material | |
EP0013540A1 (en) | Process for the dyeing and printing of fibrous material with polymerized quaternary ammonium salts as auxiliary agents | |
DE2659422B2 (en) | Liquid dye compositions, their preparation and use | |
DE1770741A1 (en) | Non-flammable acrylonitrile copolymers with high absorption capacity for acid dyes and processes for their production | |
DE930025C (en) | Process for printing on fibrous materials | |
DE1619334C (en) | Aid for fixing cationic dyes on acrylonitrile polymer fibers | |
DE1282600B (en) | Process for the production of prints on fiber material | |
EP0566537A1 (en) | Process for printing of synthetic fibrous material with transfer-printing |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): BE CH DE DK ES FR GB IT LI NL |
|
AX | Request for extension of the european patent |
Free format text: AL;LT;LV;MK;RO;SI |
|
AKX | Designation fees paid | ||
17P | Request for examination filed |
Effective date: 20000410 |
|
RBV | Designated contracting states (corrected) |
Designated state(s): BE CH DE DK ES FR GB IT LI NL |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: 8566 |
|
17Q | First examination report despatched |
Effective date: 20040206 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE CH DE DK ES FR GB IT LI NL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20060621 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 20060712 |
|
REF | Corresponds to: |
Ref document number: 59913578 Country of ref document: DE Date of ref document: 20060803 Kind code of ref document: P |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20061002 |
|
REG | Reference to a national code |
Ref country code: DK Ref legal event code: T3 |
|
ET | Fr: translation filed | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20070322 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070531 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070531 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DK Payment date: 20090408 Year of fee payment: 11 |
|
REG | Reference to a national code |
Ref country code: DK Ref legal event code: EBP |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100531 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20110511 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20110523 Year of fee payment: 13 Ref country code: GB Payment date: 20110421 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20110622 Year of fee payment: 13 Ref country code: IT Payment date: 20110525 Year of fee payment: 13 Ref country code: DE Payment date: 20110531 Year of fee payment: 13 |
|
BERE | Be: lapsed |
Owner name: *CIBA SPECIALTY CHEMICALS HOLDING INC. Effective date: 20120531 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: V1 Effective date: 20121201 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20120504 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20120504 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20120531 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20130131 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 59913578 Country of ref document: DE Effective date: 20121201 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20121201 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20120504 Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20120531 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20121201 |