EP0957197B1 - Process for treating natural or synthetic polyamide fibrous materials - Google Patents
Process for treating natural or synthetic polyamide fibrous materials Download PDFInfo
- Publication number
- EP0957197B1 EP0957197B1 EP99810385A EP99810385A EP0957197B1 EP 0957197 B1 EP0957197 B1 EP 0957197B1 EP 99810385 A EP99810385 A EP 99810385A EP 99810385 A EP99810385 A EP 99810385A EP 0957197 B1 EP0957197 B1 EP 0957197B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- meth
- parts
- acid
- homopolymer
- copolymer
- 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.)
- Expired - Lifetime
Links
- 239000004952 Polyamide Substances 0.000 title claims description 31
- 229920002647 polyamide Polymers 0.000 title claims description 31
- 238000000034 method Methods 0.000 title claims description 28
- 239000002657 fibrous material Substances 0.000 title description 23
- 239000000975 dye Substances 0.000 claims description 28
- 229920001577 copolymer Polymers 0.000 claims description 23
- 238000004043 dyeing Methods 0.000 claims description 23
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 14
- 239000000835 fiber Substances 0.000 claims description 11
- 229920001519 homopolymer Polymers 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 239000001000 anthraquinone dye Substances 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 2
- 229920000642 polymer Polymers 0.000 description 24
- 239000000243 solution Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- -1 ammonium cations Chemical class 0.000 description 17
- 239000004744 fabric Substances 0.000 description 16
- 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
- XCYWUZHUTJDTGS-UHFFFAOYSA-N 2-methoxy-3,4-dihydro-2h-pyran Chemical compound COC1CCC=CO1 XCYWUZHUTJDTGS-UHFFFAOYSA-N 0.000 description 8
- 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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 7
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 235000002639 sodium chloride Nutrition 0.000 description 6
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 5
- 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 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 5
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 5
- PNLUGRYDUHRLOF-UHFFFAOYSA-N n-ethenyl-n-methylacetamide Chemical compound C=CN(C)C(C)=O PNLUGRYDUHRLOF-UHFFFAOYSA-N 0.000 description 5
- OFESGEKAXKKFQT-UHFFFAOYSA-N n-ethenyl-n-methylformamide Chemical compound C=CN(C)C=O OFESGEKAXKKFQT-UHFFFAOYSA-N 0.000 description 5
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 5
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229940078552 o-xylene Drugs 0.000 description 4
- 150000003839 salts Chemical class 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
- KKSNTCYLMGYFFB-UHFFFAOYSA-N (prop-2-enoylamino)methanesulfonic acid Chemical compound OS(=O)(=O)CNC(=O)C=C KKSNTCYLMGYFFB-UHFFFAOYSA-N 0.000 description 3
- WXFWXFIWDGJRSC-UHFFFAOYSA-N 2,5-dimethoxy-2,5-dihydrofuran Chemical compound COC1OC(OC)C=C1 WXFWXFIWDGJRSC-UHFFFAOYSA-N 0.000 description 3
- 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 3
- MXRGSJAOLKBZLU-UHFFFAOYSA-N 3-ethenylazepan-2-one Chemical compound C=CC1CCCCNC1=O MXRGSJAOLKBZLU-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 3
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007787 solid Substances 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
- VDSAXHBDVIUOGV-UHFFFAOYSA-N 1-ethenyl-2-methyl-4,5-dihydroimidazole Chemical compound CC1=NCCN1C=C VDSAXHBDVIUOGV-UHFFFAOYSA-N 0.000 description 2
- HXVJQEGYAYABRY-UHFFFAOYSA-N 1-ethenyl-4,5-dihydroimidazole Chemical compound C=CN1CCN=C1 HXVJQEGYAYABRY-UHFFFAOYSA-N 0.000 description 2
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 2
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical compound OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001412 amines 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
- 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
- 125000003010 ionic group Chemical group 0.000 description 2
- GORGQKRVQGXVEB-UHFFFAOYSA-N n-ethenyl-n-ethylacetamide Chemical compound CCN(C=C)C(C)=O GORGQKRVQGXVEB-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002360 preparation method 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
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011780 sodium chloride Substances 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
- 239000000758 substrate Substances 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
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 description 1
- SJQBHNHASPQACB-ONEGZZNKSA-N (e)-1,2-dimethoxyethene Chemical group CO\C=C\OC SJQBHNHASPQACB-ONEGZZNKSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- SJQBHNHASPQACB-UHFFFAOYSA-N 1,2-dimethoxyethene Chemical compound COC=COC SJQBHNHASPQACB-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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- PSZAEHPBBUYICS-UHFFFAOYSA-N 2-methylidenepropanedioic acid Chemical compound OC(=O)C(=C)C(O)=O PSZAEHPBBUYICS-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
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 1
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-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
- 239000004129 EU approved improving agent Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-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
- 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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-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
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 241001584775 Tunga penetrans Species 0.000 description 1
- 238000005299 abrasion 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
- GTZCVFVGUGFEME-UHFFFAOYSA-N aconitic acid Chemical compound OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 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
- 238000004040 coloring Methods 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
- 239000006185 dispersion Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 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
- 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
- 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
- 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
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 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
- 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
- 239000003921 oil Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-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
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 150000003254 radicals Chemical group 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
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin 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
- 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
- 239000002689 soil Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000013589 supplement Substances 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
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-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 process for the treatment of natural or synthetic polyamide fiber materials for improving the resistance of the dyes to ozone.
- Dyeing and printing with dyes often show high sensitivity to ozone.
- anthraquinone dyes are readily degraded by ozone oxidative and change in this way their Absorbtions and thus the color. This behavior is especially observed with blue anthraquinone dyes.
- the nuance of trichromatic dyeing based on blue anthraquinone dyes, for example a polyamide carpet fabric, is easily altered by ozone exposure. This deficiency is generally addressed by treating the dyed polyamide fiber material with phenol-formaldehyde condensate-based resins.
- the known ozone-resistance improving agents have disadvantages, e.g.
- Document WO-A-8 907 519 describes a process for fiber treatment to modify the fiber properties, in particular to increase the abrasion resistance of the material.
- the process is carried out in alkaline pH west, with a copolymer having latent carboxylic acid groups being applied to the substrate.
- the carboxyl groups of the polymer are complexed with di- or trivalent metal cations, amines or ammonium cations.
- the substrate is treated with an alkaline dispersion of the copolymer.
- the present invention therefore provides a process for improving the resistance of dyes to natural or synthetic polyamide fiber materials to ozone, characterized in that before, during or after dyeing the fiber material is treated with a liquor containing a homo- or copolymer having repeating structural units of the formula (1) wherein R 1 is optionally substituted C 1 -C 4 alkyl.
- R 1 may be, 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.
- the homopolymers or copolymers used according to the invention as agents for improving ozone resistance preferably contain from 50 to 100 mol% and in particular from 80 to 100 mol% of recurring structural units of the formula (1).
- the copolymerizable monomers used are, for example, anionic or non-ionic group-containing compounds in question.
- Preferred as copolymerizable monomers in the polymers used in the invention are Acrylic acid, maleic acid, vinylacetic acid, acrylamidoglycolic acid, (meth) acrylamidomethanesulfonic acid, vinylsulfonic acid, (meth) allylsulfonic acid, (meth) acrylamidomethylpropanesulfonic acid, (meth) acrylamidopropanesulfonic acid, (meth) acrylamidoethane-sulfonic acid, (meth) acrylamidomethanesulfonic acid, sulfopropyl (meth) acrylate, 4- Styrenesulfonic acid, maleic anhydride, N-vinylpyrrolidone, vinylcaprolactam, N-vinylformamide, N-vinyl-N-methyl-formamide, N-vinylacetamide, N-vinyl-N-methyl-acetamide, N-vinylimidazole, vinyl a
- the homopolymers or copolymers used in the process according to the invention have an average molecular weight of from 1 000 to 1 000 000, preferably from 1 000 to 500 000 and in particular from 5 000 to 200 000.
- the preparation of the homo- or copolymers used according to the invention as ozone-resistant agents containing recurring structural units of the formula (1) given above is carried out in a manner known per se, for example by ionic or preferably free-radical initiated polymerization of the monomers of the formula (2) in which R 1 has the meanings and preferences given above, for example in solution, suspension or emulsion, if appropriate in the presence of the unsaturated compounds mentioned above by way of example as copolymerizable monomers.
- the polymerization is preferably carried out in solution with a peroxide, persulfate or an azo compound, for example with sodium persulfate or azobis (2-amidinopropane) hydrochloride, as a radical chain initiator, this being, for example, in an amount of 0.005 to 10 wt.% on the monomers used, is present.
- a peroxide, persulfate or an azo compound for example with sodium persulfate or azobis (2-amidinopropane) hydrochloride, as a radical chain initiator, this being, for example, in an amount of 0.005 to 10 wt.% on the monomers used, is present.
- the homopolymers or copolymers used in the process according to the invention are used independently of the liquor ratio, e.g. in an amount of 0.05 to 10 wt .-%, preferably 0.1 to 6 wt .-% and particularly preferably 0.5 to 4 wt .-%, based on the weight of the polyamide fiber material used.
- the treatment of the polyamide fiber material with the homo- or copolymers used according to the invention can be carried out before, during or after the dyeing and preferably during or after the dyeing.
- the process according to the invention is advantageously carried out by adding the polymers to the dyeing liquor in the amount indicated above and dyeing the fiber material in the usual way.
- the process according to the invention is advantageously carried out by first dyeing the polyamide fiber material in a conventional manner and then aftertreating with a polymer containing the amount specified above fresh aqueous liquor. Thereafter, the dyed polyamide fiber material can be dewatered without further rinsing and dried in the usual way.
- the aftertreatment is usually done in fresh liquor. However, it can also be carried out directly in the dyebath, provided that the dyebath is at the end extensively stripped and still sufficiently acidic. After the treatment, water is usually rinsed briefly with cold water.
- polyamide fiber material natural polyamide fiber material such as e.g. Wool or silk, or synthetic polyamide fiber material, such as e.g. Polyamide 6 or polyamide 6.6, or fiber blends such as e.g. Wool / cellulose or polyamide / cellulose Mischfasem or polyamide / wool blended fibers into consideration.
- the fiber material is synthetic polyamide fiber material.
- the textile material can be used in any form, for example as fiber, yarn, woven or knitted fabric.
- the dyeings are carried out, for example, with anionic dyes, all conventional anionic dyes, e.g. as described in Color Index, 3rd edition (1971) and the supplements under the headings "Acid Dyes" are eligible.
- Examples are sulfo-containing monoazo, polyazo, metal complex azo, anthraquinone, phthalocyanine or formazan dyes.
- the dyeings are preferably carried out with anthraquinone dyes and in particular with blue anthraquinone dyes.
- the anionic dyes used to dye the polyamide fiber material are either in the form of their free sulfonic acid or, preferably, as their salts.
- suitable salts are the alkali metal, alkaline earth metal or ammonium salts or the salts of an organic amine. Examples which may be mentioned are the sodium, lithium, potassium or ammonium salts or the salt of mono-, di- or triethanolamine.
- the anionic dyes used to dye the polyamide fiber material may contain other additives, e.g. Common salt or dextrin.
- the dyeing of the polyamide fiber material with anionic dyes can be carried out according to the dyeing or printing processes customary for these dyes, for example by the exhaustion process.
- the dyeing liquors or printing pastes can, in addition to water and the dyes, other additives, such as wetting agents, anti-foaming agents, leveling agents or the property of the textile material influencing agents such.
- anionic dyes used in the Därbebädem or printing pastes, depending on the desired color depth can vary within wide limits, in general, amounts of 0.01 to 15 wt .-%, in particular 0.01 to 10 wt. %, based on the Klarbegut or the printing paste, proved to be advantageous.
- Dyeing with anionic dyes takes place at a pH of from 2 to 7, in particular from 4 to 7, dyeing in the presence of the homo- or copolymers used according to the invention at a pH of from 2 to 7 and in particular from 4 to 7.
- the liquor ratio can be chosen within a wide range, e.g. from 1: 5 to 1:50, preferably 1: 5 to 1:30.
- the aftertreatment with the homo- or copolymers used according to the invention is preferably carried out by the exhaustion process.
- the liquor ratio can be chosen within a wide range and is e.g. 1: 4 to 1: 100, preferably 1:10 to 1:40 and especially 1: 5 to 1:40.
- Special devices are not required. It can e.g. the usual dyeing machines, e.g. open baths, winch skids, jiggers or paddles, jet or circulating apparatus.
- the treatment time may e.g. 10 to 60 minutes and preferably 15 to 40 minutes.
- the pH of the liquor is from 2 to 7, preferably from 4 to 7 and in particular from 4 to 6.
- the liquor may contain, besides the fixing agent, other usual additives, e.g. Electrolytes such as e.g. Sodium chloride or sodium sulfate, dispersing and wetting agents and defoamers.
- Electrolytes such as e.g. Sodium chloride or sodium sulfate, dispersing and wetting agents and defoamers.
- Example 1 68.8 parts of methacrylic acid, 4.4 parts of mercaptoethanol and 146 parts of water are placed in a reactor. Under nitrogen, the temperature is brought to 75 ° C. 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 postpolymerized at 85 ° C. for one hour. At 80 ° C is then added 13.8 parts of hydrogen peroxide 30% and stirred for 2 hours at this temperature. The polymer solution is cooled, brought to a pH of 6.5 and concentrated to a solids content of 40%. 210 g of a clear, light yellow viscous solution of a polymer which essentially contains structural units of the formula (101) are obtained. and has a molecular weight of about 8,000.
- EXAMPLE 2 A reactor is charged with 65 parts of isopropanol and 17.5 parts of water and heated under nitrogen to 80.degree. Then, 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 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 postpolymerized for 3 hours at about 80 ° C. The polymer solution is diluted with water, the isopropanol distilled off and concentrated to a solids content of 20%. About 400 g of a cloudy, viscous solution of a polymer which consists essentially of structural units of the formulas (101) and (102) are obtained. having a Brookfield viscosity of 1600 cP.
- Example 3 69.5 parts of isopropanol and 19 parts of water are placed in a reactor and heated to 80 ° C. under nitrogen. Then, a solution of 64.5 parts of methacrylic acid, 21.7 parts of a 30% aqueous vinylsulfonic acid sodium salt solution, 69.3 parts of isopropanol and 140.7 parts of water is 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 postpolymerized for 3 hours at about 80 ° C. The polymer solution is diluted with water, the isopropanol distilled off and concentrated to a solids content of 30%. About 260 g of a cloudy, viscous solution of a polymer which comprises essentially structural units of the formulas (101) and (103) are obtained. having a Brookfield viscosity of 970 cP.
- Example 4 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. Then, a solution of 35 parts of methacrylic acid and 20 parts of o-xylene is added dropwise within 100 minutes. At the same time 0.8 parts of tert-butyl 2-ethyl-perhexanoate and 20 parts of o-xylene are added dropwise within 120 minutes. It is postpolymerized for 2 hours at about 90 ° C. The polymer solution is diluted with water and the o-xylene distilled off azeotropically.
- the polymer solution is adjusted to a pH of 7 and to a dry content of 20% concentrated.
- About 180 g of a clear, slightly viscous solution of a polymer comprising essentially structural units of the formulas (101) and (104) are obtained. having a Brookfield viscosity of 30 cP.
- Example 5 A dyebath 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 part of sodium dihydrogen phosphate monohydrate and 0.6 part of disodium hydrogen phosphate dodecahydrate.
- this dyebath is at 30 ° C with 30 parts of polyamide carpet fabric (polyamide 6). The temperature is increased uniformly within 45 minutes to the boiling point and then dyed for a further 30 minutes at this temperature. The gray-colored carpet is then rinsed.
- the dyed carpet fabric is washed in a fresh bath of 600 parts of water, 1.5 parts of the polymer solution according to Example 1 (amount used 2 wt .-% polymer based on the carpet fabric), 0.6 parts of sodium acetate and 0.7 parts of acetic acid at pH of 4.5 and a temperature of 75 ° C treated for 15 minutes.
- the carpet fabric is then rinsed and dried.
- the ozone fastness of the dyeing obtained is carried out according to the test specification ISO 105-G03.
- the comparison of the aftertreated carpet fabric with a carpet fabric that has not been post-treated shows a significant increase in the ozone resistance of the aftertreated carpet fabric.
- Example 5 The procedure is as described in Example 5, but instead of 2 wt .-%, based on the carpet fabric, of the polymer according to Example 1, the equivalent amount one of the polymers according to one of Examples 2 to 4, so also a polyamide carpet fabric is obtained with a gray, ozoneraum coloring.
- Example 6 A dyebath containing 600 parts of water,
- Example 6 If the procedure described in Example 6, but instead of 2 wt .-%, based on the carpet fabric, of the polymer according to Example 1, the equivalent amount of one of the polymers according to one of Examples 2 to 4, so also a polyamide carpet fabric with a gray Obtained ozone fast staining.
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)
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 process for the treatment of natural or synthetic polyamide fiber materials for improving the resistance of the dyes to ozone.
Färbungen und Drucke mit Farbstoffen zeigen oftmals eine hohe Empfindlichkeit gegen Ozon. Beispielsweise werden Anthrachinonfarbstoffe leicht durch Ozon oxidativ abgebaut und verändern 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 Uchtechtheit 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.Dyeing and printing with dyes often show high sensitivity to ozone. For example, anthraquinone dyes are readily degraded by ozone oxidative and change in this way their Absorbtionsverhalten and thus the color. This behavior is especially observed with blue anthraquinone dyes. The nuance of trichromatic dyeing based on blue anthraquinone dyes, for example a polyamide carpet fabric, is easily altered by ozone exposure. This deficiency is generally addressed by treating the dyed polyamide fiber material with phenol-formaldehyde condensate-based resins. However, the known ozone-resistance improving agents have disadvantages, e.g. a lack of efficacy or a negative impact on other fastness properties, e.g. the authenticity. There is therefore a need for improved ozone-resistance enhancing agents for the treatment of natural or synthetic polyamide fiber materials, in particular those dyed with anionic dyes, which do not have the disadvantages mentioned.
Dokument WO-A-8 907 519 beschreibt ein Verfahren zur Faserbehandlung um die Fasereigenschaften zu modifieieren, insbesondere die Abriebfestigkeit des Materials zu erhöhen. Das Verfahren wird bei alkalischen pH-Westen durchgeführt, wobei ein Copolymer mit latenten Carbonsäuregruppen auf das Substrat aufgebracht wird. Die Carboxylgruppen des Polymeren werden mit zwei-oder dreiwertigen Metallkationen, Aminen oder Ammonium-Kationen Komplexiert. Das Substrat wird einen alkalischen Dispersion des Copolymers behandelt.Document WO-A-8 907 519 describes a process for fiber treatment to modify the fiber properties, in particular to increase the abrasion resistance of the material. The process is carried out in alkaline pH west, with a copolymer having latent carboxylic acid groups being applied to the substrate. The carboxyl groups of the polymer are complexed with di- or trivalent metal cations, amines or ammonium cations. The substrate is treated with an alkaline dispersion of the copolymer.
Es wurde nun gefunden, dass man die Beständigkeit von beispielsweise Färbungen anionischer Farbstoffe auf Polyamidfasermaterial ohne negative Beeinflussung anderer Echtheiten verbessem kann, wenn man sie einer Behandlung mit bestimmten Homo- oder Copolymeren unterzieht.It has now been found that one can improve the stability of, for example, dyeings of anionic dyes on polyamide fiber material without adversely affecting other fastness properties, when subjected to a treatment with certain homo- or 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)
R1 gegebenenfalls substituiertes C1-C4-Alkyl ist.The present invention therefore provides a process for improving the resistance of dyes to natural or synthetic polyamide fiber materials to ozone, characterized in that before, during or after dyeing the fiber material is treated with a liquor containing a homo- or copolymer having repeating structural units of the formula (1)
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.As C 1 -C 4 -alkyl, R 1 may be, 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).The homopolymers or copolymers used according to the invention as agents for improving ozone resistance preferably contain from 50 to 100 mol% and in particular from 80 to 100 mol% of recurring 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, the copolymerizable monomers used are, for example, anionic or non-ionic group-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 Styrotsulfonsäure.
- Acrylic, maleic, fumaric, itaconic, mesaconic, citraconic, vinylacetic, vinyloxyacetic, vinylpropionic, crotonic, aconitic, allylacetic, allyloxyacetic, α, β-dimethylacrylic, allylmalonic, allyloxymalonic, methylenemalonic, glutaconic, β-carboxyethyl, allyloxy-3-hydroxybutanoic, Allylsuccinic acid, acrylamidoglycolic acid, vinylsulfonic acid, (meth) allylsulfonic acid, (meth) acrylamidomethylpropanesulfonic acid, (meth) acrylamidopropanesulfonic acid, (meth) acrylamidoethanesulfonic acid, (meth) acrylamidomethanesulfonic acid, sulfopropyl (meth) acrylate or styrotrulfonic 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.
- Maleic anhydride, vinylcaprolactam, diallylamine, N-methyldiallylamine, N-ethyldiallylamine, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinyl-N-methyl-formamide, N-vinyl-N-methyl-acetamide, N-vinyl N-ethylacetamide, N-vinylimidazole, N-vinyl-N-methylimidazole, 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 ethers, olefins such as ethylene, propylene, isobutene, styrene or its derivatives, such as hydroxystyrene, 1,2-dimethoxyethylene, hydroxy-C 2 -C 4 alkyl (meth) acrylate, (meth ) acrylic acid-C 1 -C 22 -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)acrylamidoethan-sulfonsäure, (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-MonolN,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 in the invention are
Acrylic acid, maleic acid, vinylacetic acid, acrylamidoglycolic acid, (meth) acrylamidomethanesulfonic acid, vinylsulfonic acid, (meth) allylsulfonic acid, (meth) acrylamidomethylpropanesulfonic acid, (meth) acrylamidopropanesulfonic acid, (meth) acrylamidoethane-sulfonic acid, (meth) acrylamidomethanesulfonic acid, sulfopropyl (meth) acrylate, 4- Styrenesulfonic acid, maleic anhydride, N-vinylpyrrolidone, vinylcaprolactam, N-vinylformamide, N-vinyl-N-methyl-formamide, N-vinylacetamide, 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 ethers, ethylene, propylene, isobutene, styrene, hydroxyethyl / propyl / butyl (meth) acrylate, (meth) acrylic acid C 1 -C 6 alkyl esters, (meth) acrolein , (Meth) acrylonitrile, (meth) acrylamide, N-monolN, 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-methyl-formamid, 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.
- Vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 3- (meth) acrylamidopropanesulfonic acid, maleic anhydride, N-vinylpyrrolidone, N-vinylformamide, N-vinyl-N-methyl-formamide, 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.
- 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.It is also possible to use mixtures of several of the abovementioned homo- or copolymers in the process according to the invention.
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 an average molecular weight of from 1 000 to 1 000 000, preferably from 1 000 to 500 000 and in particular from 5 000 to 200 000.
Die Herstellung der efindungsgemäss 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)
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 preparation of the homo- or copolymers used according to the invention as ozone-resistant agents containing recurring structural units of the formula (1) given above is carried out in a manner known per se, for example by ionic or preferably free-radical initiated polymerization of the monomers of the formula (2)
R 1 has the meanings and preferences given above, for example in solution, suspension or emulsion, if appropriate in the presence of the unsaturated compounds mentioned above by way of example as copolymerizable monomers. The polymerization is preferably carried out in solution with a peroxide, persulfate or an azo compound, for example with sodium persulfate or azobis (2-amidinopropane) hydrochloride, as a radical chain initiator, this being, for example, in an amount of 0.005 to 10 wt.% 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 homopolymers or copolymers used in the process according to the invention are used independently of the liquor ratio, e.g. in an amount of 0.05 to 10 wt .-%, preferably 0.1 to 6 wt .-% and particularly preferably 0.5 to 4 wt .-%, 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.The treatment of the polyamide fiber material with the homo- or copolymers used according to the invention can be carried out before, during or after the dyeing and preferably during or after the 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.If the treatment of the polyamide fiber material with the homo- or copolymers used according to the invention takes place during the dyeing process, the process according to the invention is advantageously carried out by adding the polymers to the dyeing liquor in the amount indicated above and dyeing the fiber material in the usual way.
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.If the treatment of the polyamide fiber material with the homo- or copolymers used according to the invention after dyeing, the process according to the invention is advantageously carried out by first dyeing the polyamide fiber material in a conventional manner and then aftertreating with a polymer containing the amount specified above fresh aqueous liquor. Thereafter, the dyed polyamide fiber material can be dewatered without further rinsing and dried in the usual way. The aftertreatment is usually done in fresh liquor. However, it can also be carried out directly in the dyebath, provided that the dyebath is at the end extensively stripped and still sufficiently acidic. After the treatment, water is usually rinsed briefly with cold 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-Mischfasem oder Polyamid/Wolle-Mischfasern in Betracht. Bevorzugt handelt es sich bei dem Fasermaterial um synthetisches Polyamidfasermaterial.As the polyamide fiber material, natural polyamide fiber material such as e.g. Wool or silk, or synthetic polyamide fiber material, such as e.g. Polyamide 6 or polyamide 6.6, or fiber blends such as e.g. Wool / cellulose or polyamide / cellulose Mischfasem or polyamide / wool blended fibers into consideration. Preferably, the fiber material is synthetic polyamide fiber material.
Das Textilgut ist in jeglicher Form anwendbar, z.B. als Faser, Garn, Gewebe oder Gewirke.The textile material can be used in any form, for example 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 conventional anionic dyes, e.g. as described in Color Index, 3rd edition (1971) and the supplements under the headings "Acid Dyes" are eligible.
Beispiele sind sulfogruppenhaltige Monoazo-, Polyazo-, Metallkomplexazo-, Anthrachinon-, Phthalocyanin- oder Formazanfarbstoffe.Examples are sulfo-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 with anthraquinone dyes and in particular with blue 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 are 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.Examples of suitable salts are the alkali metal, alkaline earth metal or ammonium salts or the salts of an organic amine. Examples which may be mentioned are the 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 may contain other additives, e.g. Common 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 dyeing or printing processes customary for these dyes, for example by the exhaustion process. The dyeing liquors or printing pastes can, in addition to water and the dyes, other additives, such as wetting agents, anti-foaming agents, leveling agents or the property of the textile material influencing agents such. Softening agents, flame retardant additives or soil, water and oil repellents; 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 in which anionic dyes are used in the Därbebädem or printing pastes, depending on the desired color depth can vary within wide limits, in general, amounts of 0.01 to 15 wt .-%, in particular 0.01 to 10 wt. %, based on the Färbegut or the printing paste, proved to be advantageous.
Das Färben mit anionischen Farbstoffen erfolgt bei einem pH-Wert von 2 bis 7, insbesondere 4 bis 7, wobei man in Gegenwart der erfindungsgemäss verwendeten Homo- oder Copolymeren 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.Dyeing with anionic dyes takes place at a pH of from 2 to 7, in particular from 4 to 7, dyeing in the presence of the homo- or copolymers used according to the invention at a pH of from 2 to 7 and in particular from 4 to 7. The liquor ratio can be chosen within a wide range, e.g. from 1: 5 to 1:50, preferably 1: 5 to 1:30. Preferably dyed at a temperature of 70 to 110 ° C, in particular 80 to 105 ° C, wherein in the presence of the inventively used homo- or copolymers preferably at 50 to 100 ° C and in particular at 80 to 100 ° C is dyed.
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 is preferably carried out by the exhaustion process. The liquor ratio can be chosen within a wide range 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. It can e.g. the usual dyeing machines, e.g. open baths, winch skids, jiggers or paddles, jet or circulating apparatus.
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 bei 2 bis 7, vorzugsweise bei 4 bis 7 und insbesondere bei 4 bis 6.It is convenient to operate at a temperature of e.g. 20 to 100 ° C, preferably 50 to 100 ° C and especially 60 to 100 ° C. The treatment time may e.g. 10 to 60 minutes and preferably 15 to 40 minutes. The pH of the liquor is from 2 to 7, preferably from 4 to 7 and in particular from 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.The liquor may contain, besides the fixing agent, other usual additives, e.g. Electrolytes such as e.g. 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.Dyes or prints of dyes, e.g. anionic dyes, on polyamide fiber material, which have a significant improvement in ozone fastness, without the color yield, shade or light fastness are adversely 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 illustrate the invention. The temperatures are given in degrees Centigrade, parts are parts by weight, the percentages refer by weight, unless otherwise stated. Parts by weight are in parts by volume in the ratio of kilograms to liters.
Beispiel 1: 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)
Beispiel 2: 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)
Beispiel 3: 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)
Beispiel 4: 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)
Beispiel 5: Ein Färbebad enthaltend 600 Teile Wasser,
0,0108 Teile eines Farbstoffs der Formel
0.0108 parts of a dye of the formula
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 wt .-%, based on the carpet fabric, of the polymer according to Example 1, the equivalent amount one of the polymers according to one of Examples 2 to 4, so also a polyamide carpet fabric is obtained with a gray, ozonechten coloring.
0,0108 Teile eines Farbstoffs der Formel
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.If the procedure described in Example 6, but instead of 2 wt .-%, based on the carpet fabric, of the polymer according to Example 1, the equivalent amount of one of the polymers according to one of Examples 2 to 4, so also a polyamide carpet fabric with a gray Obtained ozone fast staining.
Claims (11)
- A method of improving the stability to ozone exposure of dyes on natural or synthetic polyamide fibre materials, which comprises treating the fibre material at a pH of from 2 to 7, before, during or after dyeing, with a liquor comprising a homopolymer or copolymer having structural repeating units of formula (1)
R1 is unsubstituted or substituted C1-C4alkyl, - A method according to claim 1, wherein
R1 is C1-C4alkyl and, in particular methyl. - A method according to claim 1 or 2, wherein the homopolymer or copolymer contains from 50 to 100 mol% and preferably from 80 to 100 mol% of structural repeating units of the formula (1).
- A method according to any one of claims 1 to 3, wherein the homopolymer or copolymer has an average molecular weight of from 1000 to 1 000 000 and preferably from 5000 to 200 000.
- A method according to any one of claims 1 to 4, wherein the homopolymer or copolymer is present in the liquor in an amount of from 0.05 to 10% by weight and preferably from 0.1 to 6% by weight based on the weight of the polyamide fibre material.
- A method according to any one of claims 1 to 5, wherein the fibre material is treated during or after dyeing.
- A method according to claim 6, wherein treatment with the liquor comprising the homopolymer or copolymer is conducted at a pH of from 4 to 7.
- A method according to claim 6, wherein treatment with the liquor comprising the homopolymer or copolymer is conducted at a temperature of from 50 to 100°C.
- A method according to any one of claims 1 to 8, wherein treatment with the liquor comprising the homopolymer or copolymer takes place by the exhaust process.
- A method according to any one of claims 1 to 9, wherein the fibre material is synthetic polyamide fibre material.
- A method according to any one of claims 1 to 10, wherein the dyes are anthraquinone dyes.
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 EP0957197A1 (en) | 1999-11-17 |
EP0957197B1 true 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) |
Families Citing this family (6)
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 |
WO2003041639A2 (en) * | 2001-10-30 | 2003-05-22 | Microbiotix, Inc. | Methods and compositions for treating rotavirus-mediated disease |
JP2005511909A (en) * | 2001-12-05 | 2005-04-28 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | Process for processing natural or synthetic polyamide fiber 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 |
Family Cites Families (13)
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 |
CH642806B (en) * | 1978-07-07 | Sandoz Ag | PROCESS FOR INKING OR PRINTING CELLULOSIC TEXTILE MATERIALS WITH REACTIVE DYES. | |
DE68926042T2 (en) * | 1988-02-17 | 1996-08-14 | Dow Chemical Co | USE OF A POLYMER SALT COMPLEX FOR FIBER AND TISSUE TREATMENT |
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 |
US4937123A (en) | 1988-03-11 | 1990-06-26 | Minnesota Mining And Manufacturing Company | Process for providing polyamide materials with stain resistance |
US5464452A (en) * | 1994-05-10 | 1995-11-07 | Henkel Corporation | Process for fixing dyes in textile materials |
EP0812949A3 (en) | 1996-06-11 | 1998-07-22 | Ciba SC Holding AG | Process for the treatment of dyed fibrous cellulosic 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 |
JPH1096180A (en) | 1996-08-15 | 1998-04-14 | Clariant Internatl Ltd | Concentrated aqueous solution of polycarboxylic acid sodium salt and its 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 DE DE59913578T patent/DE59913578D1/en not_active Expired - Lifetime
- 1999-05-04 DK DK99810385T patent/DK0957197T3/en active
- 1999-05-11 JP JP12942399A patent/JP4443669B2/en not_active Expired - Fee Related
- 1999-05-11 CA CA002271873A patent/CA2271873A1/en not_active Abandoned
- 1999-05-12 AU AU28102/99A patent/AU751951B2/en not_active Ceased
- 1999-05-12 ZA ZA9903274A patent/ZA993274B/en unknown
-
2000
- 2000-07-05 US US09/609,955 patent/US6280482B1/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
DE59913578D1 (en) | 2006-08-03 |
CA2271873A1 (en) | 1999-11-13 |
DK0957197T3 (en) | 2006-10-09 |
JPH11350354A (en) | 1999-12-21 |
AU2810299A (en) | 1999-11-25 |
US6280482B1 (en) | 2001-08-28 |
EP0957197A1 (en) | 1999-11-17 |
AU751951B2 (en) | 2002-09-05 |
ZA993274B (en) | 1999-11-15 |
JP4443669B2 (en) | 2010-03-31 |
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