EP0442844A1 - Process for dyeing of wool with reactive dyes - Google Patents
Process for dyeing of wool with reactive dyes Download PDFInfo
- Publication number
- EP0442844A1 EP0442844A1 EP91810078A EP91810078A EP0442844A1 EP 0442844 A1 EP0442844 A1 EP 0442844A1 EP 91810078 A EP91810078 A EP 91810078A EP 91810078 A EP91810078 A EP 91810078A EP 0442844 A1 EP0442844 A1 EP 0442844A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- component
- formula
- hydrogen
- compound
- independently
- 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
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000004043 dyeing Methods 0.000 title claims abstract description 32
- 239000000985 reactive dye Substances 0.000 title claims abstract description 21
- 210000002268 wool Anatomy 0.000 title claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 32
- 239000001257 hydrogen Substances 0.000 claims abstract description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 17
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 15
- 239000000835 fiber Substances 0.000 claims abstract description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 12
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 10
- 150000001450 anions Chemical class 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000004040 coloring Methods 0.000 claims abstract description 4
- -1 bromoacetyl Chemical group 0.000 claims description 26
- 239000002657 fibrous material Substances 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 125000002668 chloroacetyl group Chemical group ClCC(=O)* 0.000 claims description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims 1
- 239000000975 dye Substances 0.000 description 34
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 25
- 150000001412 amines Chemical class 0.000 description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000003760 tallow Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 7
- 150000003863 ammonium salts Chemical class 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- VXIVSQZSERGHQP-UHFFFAOYSA-N chloroacetamide Chemical compound NC(=O)CCl VXIVSQZSERGHQP-UHFFFAOYSA-N 0.000 description 5
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 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 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000001007 phthalocyanine dye Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 235000015424 sodium Nutrition 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 150000003470 sulfuric acid monoesters Chemical class 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- LUYAMNYBNTVQJG-UHFFFAOYSA-N 1-chloro-2-(2-chloroethylsulfonyl)ethane Chemical group ClCCS(=O)(=O)CCCl LUYAMNYBNTVQJG-UHFFFAOYSA-N 0.000 description 1
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 description 1
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- CWBAMDVCIHSKNW-UHFFFAOYSA-N 2-iminonaphthalene-1,4-dione Chemical compound C1=CC=C2C(=O)C(=N)CC(=O)C2=C1 CWBAMDVCIHSKNW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 241001584775 Tunga penetrans Species 0.000 description 1
- PDWCVHGVTVOSIE-UHFFFAOYSA-N [nitro(diphenyl)methyl]benzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)([N+](=O)[O-])C1=CC=CC=C1 PDWCVHGVTVOSIE-UHFFFAOYSA-N 0.000 description 1
- FXXACINHVKSMDR-UHFFFAOYSA-N acetyl bromide Chemical class CC(Br)=O FXXACINHVKSMDR-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical class CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical compound O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- VPNOHCYAOXWMAR-UHFFFAOYSA-N docosan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCCCN VPNOHCYAOXWMAR-UHFFFAOYSA-N 0.000 description 1
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- BUHXFUSLEBPCEB-UHFFFAOYSA-N icosan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCN BUHXFUSLEBPCEB-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009981 jet dyeing Methods 0.000 description 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000001918 phosphonic acid ester group Chemical group 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical compound C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UFUASNAHBMBJIX-UHFFFAOYSA-N propan-1-one Chemical compound CC[C]=O UFUASNAHBMBJIX-UHFFFAOYSA-N 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 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
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/14—Wool
-
- 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
- D06P1/60—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 polyethers
- D06P1/607—Nitrogen-containing polyethers or their quaternary derivatives
- D06P1/6076—Nitrogen-containing polyethers or their quaternary derivatives addition products of amines and alkylene oxides or oxiranes
-
- 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
- D06P3/14—Wool
- D06P3/148—Wool using reactive dyes
-
- 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
- Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
- Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
- Y10S516/07—Organic amine, amide, or n-base containing
-
- 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
- Y10S8/916—Natural fiber dyeing
- Y10S8/917—Wool or silk
Definitions
- the present invention relates to a new method for fiber and flat level dyeing of wool with reactive dyes, the material dyed by the new method and a means for carrying out the method.
- the present invention thus relates to a process for fiber and area-level dyeing of wool with reactive dyes in the presence of an auxiliary mixture, which is characterized in that an aqueous liquor is used for dyeing these materials which contains at least one reactive dye and an auxiliary mixture as component ( a) at least one compound of the formula and as component (b) at least one compound of the formula contains what R1 and R2 independently of one another are an aliphatic radical having 12 to 24 carbon atoms, A ⁇ and A ′ ⁇ an anion, Z1, Z2, Z'1 and Z'2 independently of one another are hydrogen, SO3M or PO3M, where M is hydrogen, alkali metal or ammonium, t1 and t2 are 1 or 0 if t1 and t2 are 0, Z1, Z2, Z'1 and Z'2 is hydrogen or Z1, Z2, Z'1 and Z'2 which is one radical hydrogen and the other SO3M or PO3M, m1, n1, p1 and q1 are integers, the sum of
- the present method is particularly suitable for producing light to medium shades.
- auxiliary mixture as component (c) can be a nonionic compound of the formula wherein R "is an alkyl or alkenyl radical having 12 to 22 carbon atoms and x and y are integers, the sum of x and y being 80 to 140.
- auxiliaries which comprise a compound of the formula as component (a) as component (b) at least one compound of the formula and contain as component (c) a compound of formula (2), wherein R3 and R4 independently of one another are an aliphatic radical having 12 to 24 carbon atoms, Q1 and Q′1 independently of one another are C1 to C4-alkyl or -CH2-CO-NH2, Z3, Z4, Z′3 and Z′4 independently of one another are hydrogen or SO3M, M hydrogen, alkali metal or ammonium, m2, n2, p2 and q2 are integers, the sum of (m2 + n2) 5 to 12 and (p2 + q2) 25 to 100 and A1 ⁇ and A2 ⁇ represent an anion.
- R3 and R4 independently of one another are an aliphatic radical having 12 to 24 carbon atoms
- Q1 and Q′1 independently of one another are C1 to C4-alkyl or -CH2-CO-NH2
- Another preferred auxiliary mixture contains as component (a) a compound of the formula and as component (b) a compound of the formula wherein R5 and R6 independently of one another are an aliphatic radical having 12 to 24 carbon atoms, Z5 and Z6 hydrogen or of Z5 and Z6 one residue hydrogen and the other SO3M, Z′5 and Z′6 independently of one another are hydrogen or SO3M, M is hydrogen, alkali metal or ammonium and m3, n3, p3 and q3 are integers, the sum of (m3 + n3) 5 to 12 and (p3 + q3) 25 to 100.
- auxiliary mixtures which comprise a compound of the formula (3a) as component (a) and a compound of the formula (4b) as component (b) or auxiliary mixtures which comprise a compound of the formula (3b) as component (a) and as a component (b) contain a compound of formula (4a).
- M in the formulas (1), (3) and (4) denotes hydrogen, alkali metal, such as sodium, potassium and in particular ammonium.
- the radicals Q, Q ′, Q1 and Q′1 and A ⁇ , A ′ ⁇ , A1 ⁇ and A2 ⁇ in the formulas (1) and (3) are derived from quaternizing agents, Q Q1 to C4-alkyl, CH2-CO-NH2,
- quaternizing agents include Acetyl bromides, ethyl bromides, ethylene chlorohydrin, ethylene bromohydrin, epichlorohydrin, epibromohydrin, dimethyl sulfate, diethyl sulfate and especially chloroacetamide.
- R1, R2, R3, R4, R5 and R6 in the formulas (1), (3) and (4) are alkyl or alkeny radicals having 12 to 24, preferably 16 to 22 carbon atoms. Examples include: the n-dodecyl, myristyl, n-hexadecyl, n-heptadecyl, n-octadecyl, arachidyl, behenyl, dodecenyl, hexadecenyl, oleyl and octadecenyl radical.
- the compounds of component (a) corresponding to formula (1a) are prepared by adding 2 to 15 mol of ethylene oxide to aliphatic amines which have an aliphatic radical having 12 to 24 carbon atoms, and optionally the adduct converted into the acidic monoester and optionally the acidic monoester in the alkali metal or ammonium salts or reacting the adduct with one of the quaternizing agents mentioned above.
- the compounds of component (b) corresponding to formula (1b) are prepared by adding 25 to 200 moles of ethylene oxide to aliphatic amines which have an aliphatic radical having 12 to 24 carbon atoms, and optionally the adduct in the acidic ester and optionally the acidic one Converted ester into the alkali or ammonium salts or reacted the adduct with one of the quaternizing agents mentioned above.
- the compounds of formula (2) are prepared by adding 80 to 140 moles of ethylene oxide to a compound of formula wherein R ⁇ has the meaning given under formula (2).
- the amines which are required as starting materials for the preparation of the compounds of the formulas (1), (3) and (4) can have saturated or unsaturated, branched or unbranched hydrocarbon radicals having 12 to 24, preferably 16 to 22, carbon atoms.
- the amines can be chemically uniform or in the form of mixtures.
- Dodecylamine, hexadecylamine, octadecylamine, arachidylamine, behenylamine and octadecenylamine may be mentioned in particular as amines.
- Tallow fatty amine is a mixture of approx. 30% hexadecylamine, 25% octadecylamine and 45% octadecenylamine.
- Both the ethylene oxide addition and the esterification can be carried out according to methods known per se.
- sulfuric acid or its Functional derivatives such as chlorosulfonic acid and especially sulfamic acid are used.
- the esterification is generally carried out by simply mixing the reactants with heating, advantageously to a temperature between 50 and 100 ° C.
- the free acids can then be converted into the alkali metal or ammonium salts by using bases such as e.g. Ammonia, sodium or potassium hydroxide can be added.
- An auxiliary mixture comprising 10 to 80 parts, preferably 20 to 70 parts of component (a), 5 to 70 parts, preferably 5 to 50 parts of component (b) and 0 to 70, preferably 0 to 50, is used for the process according to the invention
- Parts of the compound of component (c) and ad contains 100 parts of water.
- auxiliary mixture consisting of components (a), (b) and optionally (c) are added to the dyebath range from 0.5 to 4 percent by weight, based on the fiber material to be dyed. 1 to 2 percent by weight of the auxiliary mixture, based on the fiber material, is preferably used.
- the weight ratio of components (a) and (b) is between 1: 5 and 10: 1, preferably between 1: 2 and 5: 1.
- Wool can be considered as the fiber material that can be dyed according to the invention.
- the fiber material can be in various forms. Examples include: flake, sliver, yarn, fabric, knitwear or carpets.
- the wool can be finished normally or without felt.
- reactive dyes This class of dyes is referred to in the Color Index 3rd edition 1971 as "reactive dyes". These are predominantly those dyes which have at least one reactive group with polyhydroxyl fibers (cellulose fibers) or polyamide fibers, especially wool, a precursor for this or one with polyhydroxyl fibers or polyamide fibers contain reactive substituents.
- Suitable bases for the reactive dyes are particularly those from the series of mono-, dis- or polyazo dyes including formazan dyes and anthraquinone, xanthene, nitro, triphenylmethane, naphthoquinonimine, dioxazine and phthalocyanine dyes, the azo and phthalocyanine dyes can be both metal-free and metal-containing.
- Reactive groups and precursors which form such reactive groups include, for example, epoxy groups, the ethyleneimide group, the vinyl grouping in vinylsulfone or in acrylic acid residues and the ⁇ -sulfatoethylsulfone group, the ⁇ -chloroethylsulfone group or the ⁇ -dialkylaminoethylsulfone group.
- the reactive substituents in reactive dyes are those that are easily removable and leave an electrophilic residue.
- substituents are 1 or 2 halogen atoms in an aliphatic acyl radical, e.g. in the ⁇ -position or ⁇ - and ⁇ -position of a propionyl radical or in the ⁇ - and / or ⁇ -position of an acrylic acid radical, or 1 to 3 halogen atoms on the following ring system into consideration: pyridazine, pyrimidine, pyridazone, triazine, quinoxaline or phthalazine.
- Dyes with two or more identical or different reactive groups can also be used.
- Preferred reactive dyes contain chloroacetyl, bromoacrylic or dibromopropionyl as reactive substituents.
- the reactive dyes can be acidic, salt-forming substituents such as e.g. Contain carboxylic acid groups, sulfuric acid and phosphonic acid ester groups, phosphonic acid groups or preferably sulfonic acid groups.
- Reactive dyes with at least one sulfonic acid group are preferred, in particular reactive dyes with an azo or anthraquinone base body which preferably has two to three sulfonic acid groups.
- Mixtures of reactive dyes can also be used, it being possible to produce bichromatic or trichromatic stains.
- the coloring takes place after the pull-out procedure.
- the amount of dyes added to the dye liquor depends on the desired color strength. In general, amounts of 0.01 to 10 percent by weight, preferably 0.01 to 2 percent by weight, based on the fiber material used, have proven successful.
- the liquor ratio can be chosen within a wide range e.g. 1: 3 to 1: 100, preferably 1: 8 to 1:30.
- the dye baths can contain mineral acids, e.g. Sulfuric acid or phosphoric acid, organic acids, advantageously contain aliphatic carboxylic acids such as formic acid, acetic acid, oxalic acid or citric acid and / or salts such as ammonium acetate, ammonium sulfate or sodium acetate.
- the acids are used primarily to adjust the pH of the liquors used according to the invention, which is between 4 and 5.
- the dye liquors can also contain other additives, e.g. Wool protection, dispersing and wetting agents as well as defoamers included.
- the customary dyeing apparatus such as, for example, open baths, combed, strand yarn or packing apparatus, jigger, paddle apparatus, tree dyeing apparatus, circulation or jet dyeing apparatus or reel runners can be used.
- the dyeing is advantageously carried out at a temperature in the range from 60 to 120 ° C., preferably 70 to 105 ° C.
- the dyeing time is within the usual range and is usually 20 to 120 minutes.
- the dyeing process can be followed by an alkaline after-treatment, e.g. with aqueous ammonia, alkali metal hydroxides, alkali metal carbonates, bicarbonates or hexamethylenetetraamine.
- the pH of the dye baths containing alkali is expediently 7.5 to 9, preferably 8 to 8.5.
- the dyeing of the fiber material is expediently carried out in such a way that the material to be dyed treated briefly with an aqueous liquor which contains the acid, the auxiliary mixture of components (a) and (b) and optionally component (c) and has a temperature of 30 to 60 ° C. and adds the reactive dye to the same bath.
- the temperature is then slowly increased in order to dye in a range from 80 to 100 ° C. and for 20 to 90 minutes, preferably 30 to 60 minutes.
- the material to be dyed is then treated for 10 to 20 minutes at 70 to 90 ° C. after addition of alkalis, preferably sodium hydrogen carbonate or sodium carbonate. Finally, the colored material is pulled out and rinsed, acidified and dried as usual.
- the present invention furthermore relates to the auxiliary dyeing mixture which, as component (a), comprises 10 to 80 parts of the compound of the formula as component (b) 5 to 70 parts of the compound of the formula contains what R1 and R2 independently of one another are an aliphatic radical having 12 to 24 carbon atoms, A ⁇ and A ′ ⁇ an anion, Z1, Z2, Z'1 and Z'2 independently of one another are hydrogen, SO3M or PO3M, where M is hydrogen, alkali metal or ammonium, t1 and t2 are 0 or 1 if t1 and t2 are 0, Z1, Z'1, Z2 and Z'2 is hydrogen or of Z1, Z2, Z'1 and Z'2 the one rest Is hydrogen and the other SO3M or PO3M, m1, n1, p1 and q1 are integers, the sum of (m1 + n1) 2 to 15 and (p1 + q1) 25 to 200, and as component (c) 0 up to 70 parts of the compound of the formula (2)
- the dyeing process according to the invention gives fiber and flat dyeings, especially in light to medium shades with good light and wet fastness properties.
- the pH of the liquor is 4.5.
- the 12 mg of the dye of the formula 24 mg of the dye of the formula and 44 mg of the dye of the formula contains, the dye liquor is kept at 40 ° for about 5 minutes and then with a Heating rate increased from 1 ° / min to 60 ° and held at 60 ° for 20 minutes. The mixture is then heated to 98 ° at 1 ° / min and dyed for 30 minutes. After the liquor has cooled to 70 °, rinsing is carried out as usual. A fiber- and flat-level dyeing with good fastness properties is obtained.
- Example 3 The procedure is as described in Example 1, with the difference that, instead of the auxiliary B2, 0.2 g of the adduct of 34 moles of ethylene oxide and 1 mole of a C20-C22 fatty amine is used. A fiber- and flat-level dyeing with good fastness properties is obtained.
- Example 4 The procedure is as described in Example 1, with the difference that, instead of the auxiliary B2, 0.2 g of the quaternized adduct of 34 moles of ethylene oxide and 1 mole of a C20-C22 fatty amine is used. A fiber- and flat-level dyeing with good fastness properties is obtained.
- Example 5 The procedure is as described in Example 1, with the difference that 0.2 g of the adduct of 30 moles of ethylene oxide and 1 mole of tallow fatty amine is used instead of B2. A fiber- and flat-level dyeing with good fastness properties is obtained.
- Example 6 1 kg of woolen worsted in the form of a cross-wound bobbin is circulated with 9 l of water at 40 °, 100 g sodium sulfate 9 g ammonium acetate 37 ml 80% acetic acid 9 g of a non-ionic wetting agent based on 2-ethylhexanol 10 g of the auxiliary mixture A1 10 g of the auxiliary mixture B1 Pretreated for 15 minutes. The pH of the moth is 4.65.
- the rate of heating is 1 ° / min heated to 60 ° and held at 60 ° for 20 minutes.
- the mixture is then heated at 1 ° / min and stained for 30 minutes.
- rinsing is carried out as usual.
- an alkaline aftertreatment for example with ammonia, sodium carbonate or sodium hydrogen carbonate, can be added to improve the fastness properties. This gives fiber and flat level dyeings with excellent fastness properties.
- Example 7 The procedure is as in Example 7, with the difference that a dye solution consisting of 4 g of the dye of the formula (101) 6 g of the dye of the formula (102) and 4 g of the dye of the formula (103) starts.
- EXAMPLE 9 The procedure is as described in Example 2, with the difference that, instead of the dye mixture, 80 mg of the dye of the formula is used.
- EXAMPLE 10 The procedure is as described in Example 9, with the difference that instead of 80 mg of the dye of the formula (105), 80 mg of the dye of the formula starts.
- EXAMPLE 11 The procedure is as described in Example 9, with the difference that instead of 80 mg of the dye of the formula (105), 200 mg of the dye of the formula used.
- EXAMPLE 12 The procedure is as described in Example 9, with the difference that instead of 80 mg of the dye of the formula (105), 320 mg of the dye of the formula used.
- EXAMPLE 13 The procedure is as described in Example 9, with the difference that instead of 80 mg of the dye of the formula (105), 100 mg of the dye of the formula used.
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Abstract
Beschrieben wird ein Verfahren zum faser- und flächenegalen Färben von Wolle mit Reaktivfarbstoffen in Gegenwart eines Hilfsmittelgemisches, das dadurch gekennzeichnet ist, dass man zum Färben dieser Materialien in hellen und mittleren Farbtönen eine wässrige Flotte verwendet, welche mindestens einen Reaktivfarbstoff und ein Hilfsmittelgemisch enthaltend als Komponente (a) mindestens eine Verbindung der Formel <IMAGE> und als Komponente (b) mindestens eine Verbindung der Formel <IMAGE> enthält, worin R1 und R2 unabhängig voneinander einen aliphatischen Rest mit 12 bis 24 C-Atomen, <IMAGE> A<⊖> und A'<⊖> ein Anion, Z1 und Z2 unabhängig voneinander Wasserstoff, SO3M oder PO3M, wobei M Wasserstoff, Alkalimetall oder Ammonium, wenn t1 und t2 0 bedeuten, Z1, Z2, Z'1 und Z'2 Wasserstoff oder von Z1, Z2, Z'1 und Z'2 der eine Rest Wasserstoff und der andere SO3M oder PO3M bedeutet, m1, n1, p1 und q1 ganze Zahlen bedeuten, wobei die Summe von (m1+n1) 2 bis 15 und (p1+q1) 25 bis 200 ist, und die Färbung unabhängig von der Farbtiefe bei einem pH-Wert von 4,0 bis 5,0 fertigstellt. Man erhält nach dem erfindungsgemässen Färbeverfahren faser- und flächenegale Färbungen, besonders in hellen bis mittleren Farbtönen mit guten Licht- und Nassechtheiten.A process is described for fiber and area-level dyeing of wool with reactive dyes in the presence of an auxiliary mixture, which is characterized in that an aqueous liquor is used for dyeing these materials in light and medium shades, which contains at least one reactive dye and an auxiliary mixture as a component (a) contains at least one compound of the formula <IMAGE> and as component (b) at least one compound of the formula <IMAGE>, in which R1 and R2 independently of one another are an aliphatic radical having 12 to 24 C atoms, <IMAGE> A <⊖ > and A '<⊖> an anion, Z1 and Z2 independently of one another hydrogen, SO3M or PO3M, where M is hydrogen, alkali metal or ammonium, if t1 and t2 are 0, Z1, Z2, Z'1 and Z'2 are hydrogen or of Z1, Z2, Z'1 and Z'2, one radical being hydrogen and the other being SO3M or PO3M, m1, n1, p1 and q1 being integers, the sum of (m1 + n1) 2 to 15 and (p1 + q1) 25 to 200 and the coloring is completed regardless of the color depth at a pH of 4.0 to 5.0. The dyeing process according to the invention gives fiber and flat dyeings, especially in light to medium shades with good light and wet fastness properties.
Description
Die vorliegende Erfindung betrifft ein neues Verfahren zum faser- und flächenegalen Färben von Wolle mit Reaktivfarbstoffen, das nach dem neuen Verfahren gefärbte Material und ein Mittel zur Ausführung des Verfahrens.The present invention relates to a new method for fiber and flat level dyeing of wool with reactive dyes, the material dyed by the new method and a means for carrying out the method.
Aus der US-A-4 444 564 ist es bekannt, Fasern aus natürlichen Polyamiden im faserschonenden pH-Bereich zu färben. Allerdings können mit diesem Verfahren mit Reaktivfarbstoffen nur dunkle Farbtöne zufriedenstellend hergestellt werden.From US-A-4 444 564 it is known to dye fibers from natural polyamides in the fiber-protecting pH range. However, only dark shades can be satisfactorily produced with this process using reactive dyes.
Ueberraschenderweise wurde nun ein neues Verfahren gefunden, das es ermöglicht, auch Wolle mit Reaktivfarbstoffen im faserschonenden pH-Bereich faser- und flächenegal besonders in hellen bis mittleren Farbtönen herzustellen.Surprisingly, a new process has now been found which makes it possible to also produce wool with reactive dyestuffs in the pH-friendly pH range, regardless of fiber and area, especially in light to medium shades.
Gegenstand der vorliegenden Erfindung ist somit ein Verfahren zum faser- und flächenegalen Färben von Wolle mit Reaktivfarbstoffen in Gegenwart eines Hilfsmittelgemisches, das dadurch gekennzeichnet ist, dass man zum Färben dieser Materialien eine wässrige Flotte verwendet, welche mindestens einen Reaktivfarbstoff und ein Hilfsmittelgemisch enthaltend als Komponente (a) mindestens eine Verbindung der Formel
und als Komponente (b) mindestens eine Verbindung der Formel
enthält, worin
R₁ und R₂ unabhängig voneinander einen aliphatischen Rest mit 12 bis 24 C-Atomen,
A⊖ und A′⊖ ein Anion,
Z₁, Z₂, Z′₁ und Z′₂ unabhängig voneinander Wasserstoff, SO₃M oder PO₃M, wobei M Wasserstoff, Alkalimetall oder Ammonium, t₁ und t₂ 1 oder 0 bedeuten, wenn t₁ und t₂ 0 bedeuten, Z₁, Z₂, Z′₁ und Z′₂ Wasserstoff oder von Z₁, Z₂, Z′₁ und Z′₂ der eine Rest Wasserstoff und der andere SO₃M oder PO₃M bedeutet, m₁, n₁, p₁ und q₁ ganze Zahlen bedeuten, wobei die Summe von (m₁+n₁) 2 bis 15 und (p₁+q₁) 25 bis 200 ist, und die Färbung unabhängig von der Farbtiefe bei einem pH-Wert von 4,0 bis 5,0 fertigstellt.The present invention thus relates to a process for fiber and area-level dyeing of wool with reactive dyes in the presence of an auxiliary mixture, which is characterized in that an aqueous liquor is used for dyeing these materials which contains at least one reactive dye and an auxiliary mixture as component ( a) at least one compound of the formula
and as component (b) at least one compound of the formula
contains what
R₁ and R₂ independently of one another are an aliphatic radical having 12 to 24 carbon atoms,
A ⊖ and A ′ ⊖ an anion,
Z₁, Z₂, Z'₁ and Z'₂ independently of one another are hydrogen, SO₃M or PO₃M, where M is hydrogen, alkali metal or ammonium, t₁ and t₂ are 1 or 0 if t₁ and t₂ are 0, Z₁, Z₂, Z'₁ and Z'₂ is hydrogen or Z₁, Z₂, Z'₁ and Z'₂ which is one radical hydrogen and the other SO₃M or PO₃M, m₁, n₁, p₁ and q₁ are integers, the sum of (m₁ + n₁) 2 to 15 and (p₁ + q₁) 25 to 200, and the coloring is completed regardless of the depth of color at a pH of 4.0 to 5.0.
Das vorliegende Verfahren eignet sich besonders zur Herstellung von hellen bis mittleren Farbtönen.The present method is particularly suitable for producing light to medium shades.
Bevorzugt sind Hilfsmittelgemisch-Komponenten der Formeln (1a) und (1b), bei denen die Summe (m₁+n₁) 5 bis 12 und (p₁+q₁) 25 bis 100 bedeuten.Auxiliary mixture components of the formulas (1a) and (1b) are preferred, in which the sum (m 1 + n 1) 5 to 12 and (p 1 + q 1) 25 to 100.
Zusätzlich kann das Hilfsmittelgemisch als Komponente (c) eine nichtionogene Verbindung der Formel
worin R" einen Alkyl- oder Alkenylrest mit 12 bis 22 Kohlenstoffatomen und x und y ganze Zahlen bedeuten, wobei die Summe von x und y 80 bis 140 ist, enthalten.In addition, the auxiliary mixture as component (c) can be a nonionic compound of the formula
wherein R "is an alkyl or alkenyl radical having 12 to 22 carbon atoms and x and y are integers, the sum of x and y being 80 to 140.
Bevorzugt kommen Hilfsmittelgemische zum Einsatz, die als Komponente (a) eine Verbindung der Formel
als Komponente (b) mindestens eine Verbindung der Formel
und als Komponente (c) eine Verbindung der Formel (2) enthalten, worin
R₃ und R₄ unabhängig voneinander einen aliphatischen Rest mit 12 bis 24 C-Atomen,
Q₁ und Q′₁ unabhängig voneinander C₁ bis C₄-Alkyl oder -CH₂-CO-NH₂,
Z₃, Z₄, Z′₃ und Z′₄ unabhängig voneinander Wasserstoff oder SO₃M,
M Wasserstoff, Alkalimetall oder Ammonium,
m₂, n₂, p₂ und q₂ ganze Zahlen bedeuten, wobei die Summe von (m₂+n₂) 5 bis 12 und (p₂+q₂) 25 bis 100 ist und
A₁⊖ und A₂⊖ ein Anion bedeuten.Mixtures of auxiliaries are preferably used which comprise a compound of the formula as component (a)
as component (b) at least one compound of the formula
and contain as component (c) a compound of formula (2), wherein
R₃ and R₄ independently of one another are an aliphatic radical having 12 to 24 carbon atoms,
Q₁ and Q′₁ independently of one another are C₁ to C₄-alkyl or -CH₂-CO-NH₂,
Z₃, Z₄, Z′₃ and Z′₄ independently of one another are hydrogen or SO₃M,
M hydrogen, alkali metal or ammonium,
m₂, n₂, p₂ and q₂ are integers, the sum of (m₂ + n₂) 5 to 12 and (p₂ + q₂) 25 to 100 and
A₁ ⊖ and A₂ ⊖ represent an anion.
Ein weiteres bevorzugtes Hilfsmittelgemisch enthält als Komponente (a) eine Verbindung der Formel
und als Komponente (b) eine Verbindung der Formel
worin
R₅ und R₆ unabhängig voneinander einen aliphatischen Rest mit 12 bis 24 C-Atomen,
Z₅ und Z₆ Wasserstoff oder von Z₅ und Z₆ der eine Rest Wasserstoff und der andere SO₃M,
Z′₅ und Z′₆ unabhängig voneinander Wasserstoff oder SO₃M,
M Wasserstoff, Alkalimetall oder Ammonium und
m₃, n₃, p₃ und q₃ ganze Zahlen bedeuten, wobei die Summe von (m₃+n₃) 5 bis 12 und (p₃+q₃) 25 bis 100 ist.Another preferred auxiliary mixture contains as component (a) a compound of the formula
and as component (b) a compound of the formula
wherein
R₅ and R₆ independently of one another are an aliphatic radical having 12 to 24 carbon atoms,
Z₅ and Z₆ hydrogen or of Z₅ and Z₆ one residue hydrogen and the other SO₃M,
Z′₅ and Z′₆ independently of one another are hydrogen or SO₃M,
M is hydrogen, alkali metal or ammonium and
m₃, n₃, p₃ and q₃ are integers, the sum of (m₃ + n₃) 5 to 12 and (p₃ + q₃) 25 to 100.
Weiterhin bevorzugt sind Hilfsmittelgemische, die als Komponente (a) eine Verbindung der Formel (3a) und als Komponente (b) eine Verbindung der Formel (4b) oder Hilfsmittelgemische, die als Komponente (a) eine Verbindung der Formel (3b) und als Komponente (b) eine Verbindung der Formel (4a) enthalten.Preference is further given to auxiliary mixtures which comprise a compound of the formula (3a) as component (a) and a compound of the formula (4b) as component (b) or auxiliary mixtures which comprise a compound of the formula (3b) as component (a) and as a component (b) contain a compound of formula (4a).
M in den Formeln (1), (3) und (4) bedeutet Wasserstoff, Alkalimetall, wie z.B. Natrium, Kalium und insbesondere Ammonium. Die Reste Q, Q′, Q₁ und Q′₁ sowie A⊖, A′⊖, A₁⊖ und A₂⊖ in den Formeln (1) und (3) leiten sich von Quaternierungsmitteln ab, wobei Q C₁ bis C₄-Alkyl, -CH₂-CO-NH₂,
Als Beispiele solcher Quaternierungsmittel kommen z.B. Acetylbromide, Ethylbromide, Ethylenchlorhydrin, Ethylenbromhydrin, Epichlorhydrin, Epibromhydrin, Dimethylsulfat, Diethylsulfat und insbesondere Chloracetamid in Betracht.Examples of such quaternizing agents include Acetyl bromides, ethyl bromides, ethylene chlorohydrin, ethylene bromohydrin, epichlorohydrin, epibromohydrin, dimethyl sulfate, diethyl sulfate and especially chloroacetamide.
Als aliphatische Reste R₁, R₂, R₃, R₄, R₅ und R₆ in den Formeln (1), (3) und (4) kommen Alkyl- oder Alkenyreste mit 12 bis 24, vorzugsweise 16 bis 22 Kohlenstoffatomen in Betracht. Als Beispiele seien genannt: der n-Dodecyl-, Myristyl-, n-Hexadecyl-, n-Heptadecyl-, n-Octadecyl-, Arachidyl-, Behenyl-, Dodecenyl-, Hexadecenyl-, Oleyl- und Octadecenylrest.As aliphatic radicals R₁, R₂, R₃, R₄, R₅ and R₆ in the formulas (1), (3) and (4) are alkyl or alkeny radicals having 12 to 24, preferably 16 to 22 carbon atoms. Examples include: the n-dodecyl, myristyl, n-hexadecyl, n-heptadecyl, n-octadecyl, arachidyl, behenyl, dodecenyl, hexadecenyl, oleyl and octadecenyl radical.
Die Verbindungen der Komponenten (a), (b) und (c) sind z.B. aus der US-A-4 444 564 bekannt.The compounds of components (a), (b) and (c) are e.g. known from US-A-4 444 564.
Die Verbindungen der Komponente (a) entsprechend Formel (1a) werden hergestellt, indem man 2 bis 15 Mol Ethylenoxid an aliphatische Amine, die einen aliphatischen Rest mit 12 bis 24 Kohlenstoffatomen aufweisen, anlagert und gegebenenfalls das Anlagerungsprodukt in den sauren Monoester und gegebenenfalls den sauren Monoester in die Alkali- oder Ammoniumsalze überführt oder das Anlagerungsprodukt mit einem der oben genannten Quaternierungsmittel umsetzt. Die Verbindungen der Komponente (b) entsprechend Formel (1b) werden hergestellt, indem man 25 bis 200 Mol Ethylenoxid an aliphatische Amine, die einen aliphatischen Rest mit 12 bis 24 Kohlenstoffatomen aufweisen, anlagert und gegebenenfalls das Anlagerungsprodukt in den sauren Ester und gegebenenfalls den sauren Ester in die Alkali- oder Ammoniumsalze überführt oder das Anlagerungsprodukt mit einem der oben genannten Quaternierungsmittel umsetzt.The compounds of component (a) corresponding to formula (1a) are prepared by adding 2 to 15 mol of ethylene oxide to aliphatic amines which have an aliphatic radical having 12 to 24 carbon atoms, and optionally the adduct converted into the acidic monoester and optionally the acidic monoester in the alkali metal or ammonium salts or reacting the adduct with one of the quaternizing agents mentioned above. The compounds of component (b) corresponding to formula (1b) are prepared by adding 25 to 200 moles of ethylene oxide to aliphatic amines which have an aliphatic radical having 12 to 24 carbon atoms, and optionally the adduct in the acidic ester and optionally the acidic one Converted ester into the alkali or ammonium salts or reacted the adduct with one of the quaternizing agents mentioned above.
Die Verbindungen der Formel (2) werden hergestellt, indem man 80 bis 140 Mol Ethylenoxid an eine Verbindung der Formel
worin R˝ die unter Formel (2) angegebene Bedeutung hat, anlagert.The compounds of formula (2) are prepared by adding 80 to 140 moles of ethylene oxide to a compound of formula
wherein R˝ has the meaning given under formula (2).
Die Amine, die als Ausgangsstoffe für die Herstellung der Verbindungen der Formeln (1), (3) und (4) benötigt werden, können gesättigte oder ungesättigte, verzweigte oder unverzweigte Kohlenwasserstoffreste mit 12 bis 24, vorzugsweise 16 bis 22 Kohlenstoffatomen aufweisen. Die Amine können chemisch einheitlich sein oder in Form von Gemischen vorliegen. Als Amingemische werden vorzugsweise solche herangezogen, wie sie bei der Ueberführung von natürlichen Fetten oder Oelen wie z.B. Talgfett, Soja- oder Kokosöl in die entsprechenden Amine entstehen. Als Amine seien im einzelnen Dodecylamin, Hexadecylamin, Octadecylamin, Arachidylamin, Behenylamin und Octadecenylamin genannt. Bevorzugt ist ein Gemisch aus C₁₈ bis C₂₂-Fettaminen und Talgfettamin. Talgfettamin ist ein Gemisch aus ca. 30 % Hexadecylamin, 25 % Octadecylamin und 45 % Octadecenylamin.The amines which are required as starting materials for the preparation of the compounds of the formulas (1), (3) and (4) can have saturated or unsaturated, branched or unbranched hydrocarbon radicals having 12 to 24, preferably 16 to 22, carbon atoms. The amines can be chemically uniform or in the form of mixtures. As amine mixtures, preference is given to those used in the transfer of natural fats or oils such as e.g. Tallow fat, soybean or coconut oil are formed in the corresponding amines. Dodecylamine, hexadecylamine, octadecylamine, arachidylamine, behenylamine and octadecenylamine may be mentioned in particular as amines. A mixture of C₁₈ to C₂₂ fatty amines and tallow fatty amine is preferred. Tallow fatty amine is a mixture of approx. 30% hexadecylamine, 25% octadecylamine and 45% octadecenylamine.
Sowohl die Ethylenoxidanlagerung als auch die Veresterung können nach an sich bekannten Methoden durchgeführt werden. Zur Veresterung können Schwefelsäure oder deren funktionelle Derivate wie z.B. Chlorsulfonsäure und insbesondere Sulfaminsäure dienen.Both the ethylene oxide addition and the esterification can be carried out according to methods known per se. For the esterification, sulfuric acid or its Functional derivatives such as chlorosulfonic acid and especially sulfamic acid are used.
Die Veresterung wird in der Regel durch einfaches Vermischen der Reaktionspartner unter Erwärmen, zweckmässig auf eine Temperatur zwischen 50 und 100°C, durchgeführt. Die freien Säuren können anschliessend in die Alkalimetall- oder Ammoniumsalze übergeführt werden, indem auf übliche Weise Basen wie z.B. Ammoniak, Natrium- oder Kaliumhydroxid zugegeben werden.The esterification is generally carried out by simply mixing the reactants with heating, advantageously to a temperature between 50 and 100 ° C. The free acids can then be converted into the alkali metal or ammonium salts by using bases such as e.g. Ammonia, sodium or potassium hydroxide can be added.
Für das erfindungsgemässe Verfahren verwendet man ein Hilfsmittelgemisch, das 10 bis 80 Teile, vorzugsweise 20 bis 70 Teile der Komponente (a), 5 bis 70 Teile, vorzugsweise 5 bis 50 Teile der Komponente (b) und 0 bis 70, vorzugsweise 0 bis 50 Teile der Verbindung der Komponente (c) und ad 100 Teile Wasser enthält.An auxiliary mixture comprising 10 to 80 parts, preferably 20 to 70 parts of component (a), 5 to 70 parts, preferably 5 to 50 parts of component (b) and 0 to 70, preferably 0 to 50, is used for the process according to the invention Parts of the compound of component (c) and ad contains 100 parts of water.
Die Einsatzmengen, in denen das Hilfsmittelgemisch bestehend aus den Komponenten (a), (b) und gegebenenfalls (c) dem Färbebad zugesetzt wird, bewegen sich zwischen 0,5 und 4 Gewichtsprozent, bezogen auf das zu färbende Fasermaterial. Vorzugsweise verwendet man 1 bis 2 Gewichtsprozent des Hilfsmittelgemisches, bezogen auf das Fasermaterial.The amounts used in which the auxiliary mixture consisting of components (a), (b) and optionally (c) are added to the dyebath range from 0.5 to 4 percent by weight, based on the fiber material to be dyed. 1 to 2 percent by weight of the auxiliary mixture, based on the fiber material, is preferably used.
Das Gewichtsverhältnis der Komponenten (a) und (b) liegt zwischen 1:5 und 10:1, vorzugsweise zwischen 1:2 und 5:1.The weight ratio of components (a) and (b) is between 1: 5 and 10: 1, preferably between 1: 2 and 5: 1.
Als Fasermaterial, das erfindungsgemäss gefärbt werden kann, kommt Wolle in Betracht. Das Fasermaterial kann dabei in den verschiedenen Aufmachungen vorliegen. Beispielsweise kommen in Betracht: Flocke, Kammzug, Garn, Gewebe, Maschenware oder Teppiche. Die Wolle kann normal oder filzfrei ausgerüstet sein.Wool can be considered as the fiber material that can be dyed according to the invention. The fiber material can be in various forms. Examples include: flake, sliver, yarn, fabric, knitwear or carpets. The wool can be finished normally or without felt.
Für das Färben von normaler Wolle bzw. von filzfrei ausgerüsteter Wolle nach dem vorliegenden Verfahren kommen als Reaktivfarbstoffe die unter diesem Begriff bekannten organischen Farbstoffe - unabhängig von der Art ihrer reaktiven Gruppe - in Betracht.For the dyeing of normal wool or of felt-free finished wool according to the present method, the organic dyes known under this term - regardless of the type of their reactive group - come into consideration as reactive dyes.
Diese Farbstoffklasse wird im Colour Index 3. Auflage 1971 als "Reaktive Dyes" bezeichnet. Es handelt sich dabei vorwiegend um solche Farbstoffe, die mindestens eine mit Polyhydroxylfasem (Cellulosefasern) oder Polyamidfasern, besonders Wolle, reaktionsfähige Gruppe, eine Vorstufe hierfür oder einen mit Polyhydroxylfasern oder Polyamidfasern reaktionsfähigen Substituenten enthalten.This class of dyes is referred to in the Color Index 3rd edition 1971 as "reactive dyes". These are predominantly those dyes which have at least one reactive group with polyhydroxyl fibers (cellulose fibers) or polyamide fibers, especially wool, a precursor for this or one with polyhydroxyl fibers or polyamide fibers contain reactive substituents.
Als Grundkörper der Reaktivfarbstoffe eignen sich besonders solche aus der Reihe der Mono-, Dis- oder Polyazofarbstoffe einschliesslich der Formazanfarbstoffe sowie der Anthrachinon-, Xanthen-, Nitro-, Triphenylmethan-, Naphthochinonimin-, Dioxazin- und Phthalocyaninfarbstoffe, wobei die Azo- und Phthalocyaninfarbstoffe sowohl metallfrei als auch metallhaltig sein können.Suitable bases for the reactive dyes are particularly those from the series of mono-, dis- or polyazo dyes including formazan dyes and anthraquinone, xanthene, nitro, triphenylmethane, naphthoquinonimine, dioxazine and phthalocyanine dyes, the azo and phthalocyanine dyes can be both metal-free and metal-containing.
Als reaktionsfähige Gruppen und Vorstufen, die solche reaktionsfähige Gruppen bilden, seien beispielsweise Epoxygruppen, die Ethylenimidgruppe, die Vinylgruppierung in Vinylsulfon- oder im Acrylsäurerest sowie die β-Sulfatoethylsulfongruppe, die β-Chlorethylsulfongruppe oder die β-Dialkylaminoethylsulfongruppe genannt.Reactive groups and precursors which form such reactive groups include, for example, epoxy groups, the ethyleneimide group, the vinyl grouping in vinylsulfone or in acrylic acid residues and the β-sulfatoethylsulfone group, the β-chloroethylsulfone group or the β-dialkylaminoethylsulfone group.
Als reaktionsfähige Substituenten in Reaktivfarbstoffen dienen solche, die leicht abspaltbar sind und einen elektrophilen Rest hinterlassen.The reactive substituents in reactive dyes are those that are easily removable and leave an electrophilic residue.
Als solche Substituenten kommen beispielsweise 1 oder 2 Halogenatome in einem aliphatischen Acylrest z.B. in β-Stellung oder α- und β-Stellung eines Propionylrestes oder in α- und/oder β-Stellung eines Acrylsäurerestes, oder 1 bis 3 Halogenatome an folgenden Ringsystem in Betracht: Pyridazin, Pyrimidin, Pyridazon, Triazin, Chinoxalin oder Phthalazin.Examples of such substituents are 1 or 2 halogen atoms in an aliphatic acyl radical, e.g. in the β-position or α- and β-position of a propionyl radical or in the α- and / or β-position of an acrylic acid radical, or 1 to 3 halogen atoms on the following ring system into consideration: pyridazine, pyrimidine, pyridazone, triazine, quinoxaline or phthalazine.
Es können auch Farbstoffe mit zwei oder mehreren gleich- oder verschiedenartigen Reaktivgruppen verwendet werden.Dyes with two or more identical or different reactive groups can also be used.
Bevorzugte Reaktivfarbstoffe enthalten als reaktionsfähige Substituenten Chloracetyl, Bromacryl oder Dibrompropionyl.Preferred reactive dyes contain chloroacetyl, bromoacrylic or dibromopropionyl as reactive substituents.
Die Reaktivfarbstoffe können saure, salzbildende Substituenten, wie z.B. Carbonsäuregruppen, Schwefelsäure- und Phosphonsäureestergruppen, Phosphonsäuregruppen oder vorzugsweise Sulfonsäuregruppen enthalten.The reactive dyes can be acidic, salt-forming substituents such as e.g. Contain carboxylic acid groups, sulfuric acid and phosphonic acid ester groups, phosphonic acid groups or preferably sulfonic acid groups.
Bevorzugt sind Reaktivfarbstoffe mit mindestens einer Sulfonsäuregruppe, insbesondere Reaktivfarbstoffe mit einem Azo- oder Anthrachinongrundkörper, welcher vorzugsweise zwei bis drei Sulfonsäuregruppen aufweist.Reactive dyes with at least one sulfonic acid group are preferred, in particular reactive dyes with an azo or anthraquinone base body which preferably has two to three sulfonic acid groups.
Es können auch Mischungen von Reaktivfarbstoffen eingesetzt werden, wobei Bichromie- oder Trichromiefärbungen erzeugt werden können.Mixtures of reactive dyes can also be used, it being possible to produce bichromatic or trichromatic stains.
Die Färbung erfolgt nach dem Ausziehverfahren. Die Menge der der Färbeflotte zugesetzten Farbstoffe richtet sich nach der gewünschten Farbstärke. Im allgemeinen haben sich Mengen von 0,01 bis 10 Gewichtsprozent, vorzugsweise 0,01 bis 2 Gewichtsprozent, bezogen auf das eingesetzte Fasermaterial, bewährt.The coloring takes place after the pull-out procedure. The amount of dyes added to the dye liquor depends on the desired color strength. In general, amounts of 0.01 to 10 percent by weight, preferably 0.01 to 2 percent by weight, based on the fiber material used, have proven successful.
Das Flottenverhältnis kann innerhalb eines weiten Bereiches gewählt werden z.B. 1:3 bis 1:100, vorzugsweise 1:8 bis 1:30.The liquor ratio can be chosen within a wide range e.g. 1: 3 to 1: 100, preferably 1: 8 to 1:30.
Die Färbebäder können Mineralsäuren, wie z.B. Schwefelsäure oder Phosphorsäure, organische Säuren, zweckmässig aliphatische Carbonsäuren wie Ameisensäure, Essigsäure, Oxalsäure oder Zitronensäure und/oder Salze wie Ammoniumacetat, Ammoniumsulfat oder Natriumacetat enthalten. Die Säuren dienen vor allem der Einstellung des pH-Wertes der erfindungsgemäss verwendeten Flotten, der zwischen 4 und 5 liegt.The dye baths can contain mineral acids, e.g. Sulfuric acid or phosphoric acid, organic acids, advantageously contain aliphatic carboxylic acids such as formic acid, acetic acid, oxalic acid or citric acid and / or salts such as ammonium acetate, ammonium sulfate or sodium acetate. The acids are used primarily to adjust the pH of the liquors used according to the invention, which is between 4 and 5.
Die Färbeflotten können auch weitere Zusätze, wie z.B. Wollschutz-, Dispergier- und Netzmittel sowie auch Entschäumer enthalten.The dye liquors can also contain other additives, e.g. Wool protection, dispersing and wetting agents as well as defoamers included.
Besondere Vorrichtungen sind beim erfindungsgemässen Verfahren nicht erforderlich. Es können die üblichen Färbeapparaturen, wie beispielsweise offene Bäder, Kammzug-, Stranggarn- oder Packapparate, Jigger-, Paddelapparate, Baumfärbeapparate, Zirkulations- oder Düsenfärbeapparate oder Haspelkufen verwendet werden.Special devices are not required in the method according to the invention. The customary dyeing apparatus, such as, for example, open baths, combed, strand yarn or packing apparatus, jigger, paddle apparatus, tree dyeing apparatus, circulation or jet dyeing apparatus or reel runners can be used.
Das Färben erfolgt mit Vorteil bei einer Temperatur im Bereich von 60 bis 120°C, vorzugsweise 70 bis 105°C. Die Färbedauer hält sich im üblichen Rahmen und beträgt in der Regel 20 bis 120 Minuten.The dyeing is advantageously carried out at a temperature in the range from 60 to 120 ° C., preferably 70 to 105 ° C. The dyeing time is within the usual range and is usually 20 to 120 minutes.
Nach Beendigung der Färbung kann dem Färbeprozess eine alkalische Nachbehandlung, wie z.B. mit wässerigem Ammoniak, Alkalimetallhydroxiden, Alkalimetallcarbonaten, -hydrogencarbonaten oder Hexamethylentetraamin angeschlossen werden. Der pH-Wert der Alkali enthaltenden Färbebäder beträgt zweckmässigerweise 7,5 bis 9, vorzugsweise 8 bis 8,5.After the dyeing process, the dyeing process can be followed by an alkaline after-treatment, e.g. with aqueous ammonia, alkali metal hydroxides, alkali metal carbonates, bicarbonates or hexamethylenetetraamine. The pH of the dye baths containing alkali is expediently 7.5 to 9, preferably 8 to 8.5.
Das Färben des Fasermaterials wird zweckmässig so durchgeführt, dass man das Färbegut mit einer wässerigen Flotte, die die Säure, das Hilfsmittelgemisch aus den Komponenten (a) und (b) und gegebenenfalls der Komponente (c) enthält und eine Temperatur von 30 bis 60°C aufweist, kurz behandelt und dem gleichen Bade den Reaktivfarbstoff zusetzt. Hierauf steigert man die Temperatur langsam, um in einem Bereich von 80 bis 100°C und während 20 bis 90 Minuten, vorzugsweise 30 bis 60 Minuten zu färben. Anschliessend wird das Färbegut bei Bedarf nach Zusatz von Alkalien, vorzugsweise Natriumhydrogencarbonat oder Natriumcarbonat noch 10 bis 20 Minuten bei 70 bis 90°C behandelt. Am Schluss wird das gefärbte Material herausgezogen und wie üblich gespült, abgesäuert und getrocknet.The dyeing of the fiber material is expediently carried out in such a way that the material to be dyed treated briefly with an aqueous liquor which contains the acid, the auxiliary mixture of components (a) and (b) and optionally component (c) and has a temperature of 30 to 60 ° C. and adds the reactive dye to the same bath. The temperature is then slowly increased in order to dye in a range from 80 to 100 ° C. and for 20 to 90 minutes, preferably 30 to 60 minutes. The material to be dyed is then treated for 10 to 20 minutes at 70 to 90 ° C. after addition of alkalis, preferably sodium hydrogen carbonate or sodium carbonate. Finally, the colored material is pulled out and rinsed, acidified and dried as usual.
Gegenstand der vorliegenden Erfindung ist ferner das Färbereihilfsgemisch, welches als Komponente (a) 10 bis 80 Teile der Verbindung der Formel
als Komponente (b) 5 bis 70 Teile der Verbindung der Formel
enthält, worin
R₁ und R₂ unabhängig voneinander einen aliphatischen Rest mit 12 bis 24 C-Atomen,
A⊖ und A′⊖ ein Anion,
Z₁, Z₂, Z′₁ und Z′₂ unabhängig voneinander Wasserstoff, SO₃M oder PO₃M, wobei M Wasserstoff, Alkalimetall oder Ammonium, t₁ und t₂ 0 oder 1 bedeuten, wenn t₁ und t₂ 0 bedeuten, Z₁, Z′₁, Z₂ und Z′₂ Wasserstoff oder von Z₁, Z₂, Z′₁ und Z′₂ der eine Rest Wasserstoff und der andere SO₃M oder PO₃M bedeutet, m₁, n₁, p₁ und q₁ ganze Zahlen bedeuten, wobei die Summe von (m₁+n₁) 2 bis 15 und (p₁+q₁) 25 bis 200 ist, und als Komponente (c) 0 bis 70 Teile der Verbindung der Formel (2)
worin R˝ einen Alkyl- oder Alkenylrest mit 12 bis 22 Kohlenstoffatomen und x und y ganze Zahlen bedeuten, wobei die Summe von x und y 80 bis 140 ist, enthält.The present invention furthermore relates to the auxiliary dyeing mixture which, as component (a), comprises 10 to 80 parts of the compound of the formula
as component (b) 5 to 70 parts of the compound of the formula
contains what
R₁ and R₂ independently of one another are an aliphatic radical having 12 to 24 carbon atoms,
A ⊖ and A ′ ⊖ an anion,
Z₁, Z₂, Z'₁ and Z'₂ independently of one another are hydrogen, SO₃M or PO₃M, where M is hydrogen, alkali metal or ammonium, t₁ and t₂ are 0 or 1 if t₁ and t₂ are 0, Z₁, Z'₁, Z₂ and Z'₂ is hydrogen or of Z₁, Z₂, Z'₁ and Z'₂ the one rest Is hydrogen and the other SO₃M or PO₃M, m₁, n₁, p₁ and q₁ are integers, the sum of (m₁ + n₁) 2 to 15 and (p₁ + q₁) 25 to 200, and as component (c) 0 up to 70 parts of the compound of the formula (2)
wherein R˝ is an alkyl or alkenyl radical having 12 to 22 carbon atoms and x and y are integers, the sum of x and y being 80 to 140.
Man erhält nach dem erfindungsgemässen Färbeverfahren faser- und flächenegale Färbungen, besonders in hellen bis mittleren Farbtönen mit guten Licht- und Nassechtheiten.The dyeing process according to the invention gives fiber and flat dyeings, especially in light to medium shades with good light and wet fastness properties.
Die nachfolgenden Beispiele veranschaulichen die Erfindung. Darin sind die Teile Gewichtsteile und Prozente Gewichtsprozente. Die Temperaturen sind in °C angegeben.The following examples illustrate the invention. The parts are parts by weight and percentages by weight. The temperatures are given in ° C.
Beispiel 1: 40 g Wollgewebe werden in einem Zirkulationsapparat nach der Baumfärbemethode während 10 Minuten bei 40° vorbehandelt. Die Flotte besteht aus
4 g Natriumsulfat sicc.
0, 8 g Natriumacetat
2 g 80%-ige Essigsäure
800 ml Wasser
0,4 g des Hilfsmittelgemisches A₁ bestehend aus
- a) 50 Teilen des mit Chloracetamid quaternisiertes Anlagerungsproduktes von 7 Mol Ethylenoxid an 1 Mol Talgfettamin und
- b) 50 Teilen des Ammoniumsalzes des sauren Schwefelsäuremonoesters des Anlagerungsproduktes von 7 Mol Ethylenoxid an 1 Mol Talgfettamin und
4 g of sodium sulfate sicc.
0.8 g of sodium acetate
2 g 80% acetic acid
800 ml of water
0.4 g of the auxiliary mixture A₁ consisting of
- a) 50 parts of the addition product quaternized with chloroacetamide of 7 moles of ethylene oxide with 1 mole of tallow fatty amine and
- b) 50 parts of the ammonium salt of the acidic sulfuric acid monoester of the adduct of 7 moles of ethylene oxide with 1 mole of tallow fatty amine and
Der pH-Wert der Flotte beträgt 4,5.The pH of the liquor is 4.5.
Nach Zugabe einer Lösung, die 12 mg des Farbstoffes der Formel
24 mg des Farbstoffes der Formel
und 44 mg des Farbstoffes der Formel
enthält, wird die Färbeflotte noch ca. 5 Minuten bei 40° gehalten und dann mit einer Aufheizrate von 1°/min auf 60° erwärmt und 20 Minuten bei 60° gehalten. Anschliessend wird mit 1°/min auf 98° erwärmt und 30 Minuten gefärbt. Nach Abkühlen der Flotte auf 70° wird wie üblich gespült. Man erhält eine faser- und flächenegale Färbung mit guten Echtheitseigenschaften.After adding a solution, the 12 mg of the dye of the formula
24 mg of the dye of the formula
and 44 mg of the dye of the formula
contains, the dye liquor is kept at 40 ° for about 5 minutes and then with a Heating rate increased from 1 ° / min to 60 ° and held at 60 ° for 20 minutes. The mixture is then heated to 98 ° at 1 ° / min and dyed for 30 minutes. After the liquor has cooled to 70 °, rinsing is carried out as usual. A fiber- and flat-level dyeing with good fastness properties is obtained.
Beispiel 2: Man verfährt wie in Beispiel 1 beschrieben mit dem Unterschied, dass anstelle des Hilfsmittels B₂
0,4 g des Hilfsmittelgemisches B₁, bestehend aus
- a) 25,2 Teilen des Ammoniumsalzes des sauren Schwefelsäureesters des Anlagerungsproduktes von 8 Mol Ethylenoxid an 1 Mol Talgfettamin
- b) 21,3 Teilen des mit Dimethylsulfat quaterniertem Anlagerungsproduktes von 34 Mol Ethylenoxid an ein Mol eines C₂₀₋₂₂-Fettamins und
- c) 7,0 Teilen der Verbindung der Formel
0.4 g of the auxiliary mixture B₁, consisting of
- a) 25.2 parts of the ammonium salt of the acid sulfuric acid ester of the adduct of 8 moles of ethylene oxide and 1 mole of tallow fatty amine
- b) 21.3 parts of the adduct quaternized with dimethyl sulfate of 34 moles of ethylene oxide to one mole of a C₂₀₋₂₂ fatty amine and
- c) 7.0 parts of the compound of the formula
Beispiel 3: Man verfährt wie in Beispiel 1 beschrieben mit dem Unterschied, dass anstelle des Hilfsmittels B₂ 0,2 g des Anlagerungsproduktes von 34 Mol Ethylenoxid an 1 Mol eines C₂₀-C₂₂-Fettamins eingesetzt wird. Man erhält eine faser- und flächenegale Färbung mit guten Echtheitseigenschaften. Example 3: The procedure is as described in Example 1, with the difference that, instead of the auxiliary B₂, 0.2 g of the adduct of 34 moles of ethylene oxide and 1 mole of a C₂₀-C₂₂ fatty amine is used. A fiber- and flat-level dyeing with good fastness properties is obtained.
Beispiel 4: Man verfährt wie in Beispiel 1 beschrieben mit dem Unterschied, dass anstelle des Hilfsmittels B₂ 0,2 g des quaternierten Anlagerungsproduktes von 34 Mol Ethylenoxid an 1 Mol eines C₂₀-C₂₂-Fettamins eingesetzt wird. Man erhält eine faser- und flächenegale Färbung mit guten Echtheitseigenschaften. Example 4: The procedure is as described in Example 1, with the difference that, instead of the auxiliary B₂, 0.2 g of the quaternized adduct of 34 moles of ethylene oxide and 1 mole of a C₂₀-C₂₂ fatty amine is used. A fiber- and flat-level dyeing with good fastness properties is obtained.
Beispiel 5: Man verfährt wie in Beispiel 1 beschrieben mit dem Unterschied, dass anstelle von B₂ 0,2 g des Anlagerungsproduktes von 30 Mol Ethylenoxid an 1 Mol Talgfettamin eingesetzt wird. Man erhält eine faser- und flächenegale Färbung mit guten Echtheitseigenschaften. Example 5: The procedure is as described in Example 1, with the difference that 0.2 g of the adduct of 30 moles of ethylene oxide and 1 mole of tallow fatty amine is used instead of B₂. A fiber- and flat-level dyeing with good fastness properties is obtained.
Beispiel 6: 1 kg Wollkammgarn in Form einer Kreuzspule wird in einem Zirkulationsapparat mit 9 1 Wasser von 40°,
100 g Natriumsulfat
9 g Ammoniumacetat
37 ml 80%-ige Essigsäure
9 g eines nichtionogenen Netzmittels auf der Basis von 2-Ethylhexanol
10 g des Hilfsmittelgemisches A₁
10 g des Hilfsmittelgemisches B₁
15 Minuten vorbehandelt. Der pH-Wert der Motte beträgt 4,65. Nach Zugabe einer Lösung, die 0,3 g des Farbstoffes der Formel (101), 0,6 g des Farbstoffes der Formel (102) und 1,1 g des Farbstoffes der Formel (103) enthält, wird mit einer Aufheizrate von 1°/min auf 60° erwärmt und 20 Minuten bei 60° gehalten. Anschliessend wird mit 1°/min erwärmt und 30 Minuten gefärbt. Nach Abkühlen der Flotte auf 70° wird wie üblich gespült. Bei Bedarf kann zur Verbesserung der Echtheitseigenschaften eine alkalische Nachbehandlung beispielsweise mit Ammoniak, Natriumcarbonat oder Natriumhydrogencarbonat angeschlossen werden. Man erhält faser- und flächenegale Färbungen mit ausgezeichneten Echtheitseigenschaften. Example 6: 1 kg of woolen worsted in the form of a cross-wound bobbin is circulated with 9 l of water at 40 °,
100 g sodium sulfate
9 g ammonium acetate
37 ml 80% acetic acid
9 g of a non-ionic wetting agent based on 2-ethylhexanol
10 g of the auxiliary mixture A₁
10 g of the auxiliary mixture B₁
Pretreated for 15 minutes. The pH of the moth is 4.65. After adding a solution containing 0.3 g of the dye of the formula (101), 0.6 g of the dye of the formula (102) and 1.1 g of the dye of the formula (103), the rate of heating is 1 ° / min heated to 60 ° and held at 60 ° for 20 minutes. The mixture is then heated at 1 ° / min and stained for 30 minutes. After the liquor has cooled to 70 °, rinsing is carried out as usual. If necessary, an alkaline aftertreatment, for example with ammonia, sodium carbonate or sodium hydrogen carbonate, can be added to improve the fastness properties. This gives fiber and flat level dyeings with excellent fastness properties.
Beispiel 7: Man verfährt wie in Beispiel 7, mit dem Unterschied, dass man eine Farbstofflösung, bestehend aus
4 g des Farbstoffes der Formel (101)
6 g des Farbstoffes der Formel ( 102) und
4 g des Farbstoffes der Formel (103)
einsetzt. Example 7: The procedure is as in Example 7, with the difference that a dye solution consisting of
4 g of the dye of the formula (101)
6 g of the dye of the formula (102) and
4 g of the dye of the formula (103)
starts.
Beispiel 8: Man verfährt wie in Beispiel 6 mit dem Unterschied, dass man anstelle der Hilfsmittelgemischkombinationen aus A₁ und B₁ 30 g des Hilfsmittelgemisches C₁ verwendet, das folgende Zusammensetzung aufweist:
- a) 5 Teile des mit Dimethylsulfat quaternierten Anlagerungsproduktes von 34 Mol Ethylenoxid an 1 Mol eines C₂₀₋₂₂-Fettamins
- b) 2 Teile der Verbindung der Formel (104)
- c) 20 Teile des mit Chloracetamid quaternierten Anlagerungsproduktes von 7 Mol Ethylenoxid an 1 Mol Talgfettamin
- d) 20 Teile des Ammoniumsalzes des sauren Schwefelsäuremonoesters des Anlagerungsproduktes von 7 Mol Ethylenoxid an 1 Mol Talgfettamin und
- e) 2 Teile des Anlagerungsproduktes von 80 Mol Ethylenoxid an 1 Mol Oleylalkohol.
- a) 5 parts of the quaternized with dimethyl sulfate adduct of 34 moles of ethylene oxide to 1 mole of a C₂₀₋₂₂ fatty amine
- b) 2 parts of the compound of the formula (104)
- c) 20 parts of the addition product quaternized with chloroacetamide from 7 mol of ethylene oxide to 1 mol of tallow fatty amine
- d) 20 parts of the ammonium salt of the acidic sulfuric acid monoester of the adduct of 7 moles of ethylene oxide and 1 mole of tallow fatty amine and
- e) 2 parts of the adduct of 80 moles of ethylene oxide and 1 mole of oleyl alcohol.
Beispiel 9: Man verfährt wie in Beispiel 2 beschrieben mit dem Unterschied, dass an Stelle der Farbstoffmischung 80 mg des Farbstoffes der Formel
verwendet wird. EXAMPLE 9 The procedure is as described in Example 2, with the difference that, instead of the dye mixture, 80 mg of the dye of the formula
is used.
Beispiel 10: Man verfährt wie in Beispiel 9 beschrieben mit dem Unterschied, dass man anstelle von 80 mg des Farbstoffs der Formel (105) 80 mg des Farbstoffes der Formel
einsetzt. EXAMPLE 10 The procedure is as described in Example 9, with the difference that instead of 80 mg of the dye of the formula (105), 80 mg of the dye of the formula
starts.
Beispiel 11: Man verfährt wie in Beispiel 9 beschrieben mit dem Unterschied, dass man anstelle von 80 mg des Farbstoffs der Formel (105) 200 mg des Farbstoffes der Formel
verwendet. EXAMPLE 11 The procedure is as described in Example 9, with the difference that instead of 80 mg of the dye of the formula (105), 200 mg of the dye of the formula
used.
Beispiel 12: Man verfährt wie in Beispiel 9 beschrieben mit dem Unterschied, dass man anstelle von 80 mg des Farbstoffs der Formel (105) 320 mg des Farbstoffs der Formel
verwendet. EXAMPLE 12 The procedure is as described in Example 9, with the difference that instead of 80 mg of the dye of the formula (105), 320 mg of the dye of the formula
used.
Beispiel 13: Man verfährt wie in Beispiel 9 beschrieben mit dem Unterschied, dass man anstelle von 80 mg des Farbstoffs der Formel (105) 100 mg des Farbstoffes der Formel
verwendet. EXAMPLE 13 The procedure is as described in Example 9, with the difference that instead of 80 mg of the dye of the formula (105), 100 mg of the dye of the formula
used.
Claims (16)
R₁ und R₂ unabhängig voneinander einen aliphatischen Rest mit 12 bis 24 C-Atomen,
Z₁, Z₂, Z′₁ und Z′₂ unabhängig voneinander Wasserstoff, SO₃M oder PO₃M, wobei M Wasserstoff, Alkalimetall oder Ammonium, t₁ und t₂ 0 oder 1 bedeuten, wenn t₁ und t₂ 0 bedeuten, Z₁, Z₂, Z′₁ und Z′₂ Wasserstoff oder von Z₁, Z₂, Z′₁ und Z′₂ der eine Rest Wasserstoff und der andere SO₃M oder PO₃M bedeutet, m₁, n₁, p₁ und q₁ ganze Zahlen bedeuten, wobei die Summe von (m₁+n₁) 2 bis 15 und (p₁+q₁) 25 bis 200 ist, und die Färbung unabhängig von der Farbtiefe bei einem pH-Wert von 4,0 bis 5,0 fertigstellt.Process for fiber and flat level dyeing of wool with reactive dyes in the presence of an auxiliary mixture, characterized in that an aqueous liquor is used for dyeing these materials, which contains at least one reactive dye and an auxiliary mixture as component (a) at least one compound of the formula
R₁ and R₂ independently of one another are an aliphatic radical having 12 to 24 carbon atoms,
Z₁, Z₂, Z'₁ and Z'₂ independently of one another are hydrogen, SO₃M or PO₃M, where M is hydrogen, alkali metal or ammonium, t₁ and t₂ are 0 or 1 if t₁ and t₂ are 0, Z₁, Z₂, Z'₁ and Z'₂ is hydrogen or Z₁, Z₂, Z'₁ and Z'₂ which is one radical hydrogen and the other SO₃M or PO₃M, m₁, n₁, p₁ and q₁ are integers, the sum of (m₁ + n₁) 2 to 15 and (p₁ + q₁) 25 to 200, and the coloring is completed regardless of the depth of color at a pH of 4.0 to 5.0.
R₃ und R₄ unabhängig voneinander einen aliphatischen Rest mit 12 bis 24 C-Atomen,
Q₁ und Q′₁ unabhängig voneinander C₁ bis C₄-Alkyl oder -CH₂-CO-NH₂,
Z₃, Z₄, Z′₃ und Z′₄ unabhängig voneinander Wasserstoff oder SO₃M,
M Wasserstoff, Alkalimetall oder Ammonium,
m₂, n₂, p₂ und q₂ ganze Zahlen bedeuten, wobei die Summe von (m₂+n₂) 2 bis 15 und (p₂+q₂) 25 bis 100 ist und
A₁⊖ und A₂⊖ ein Anion bedeuten.Method according to one of claims 1 to 4, characterized in that an auxiliary mixture containing as component (a) a compound of the formula
R₃ and R₄ independently of one another are an aliphatic radical having 12 to 24 carbon atoms,
Q₁ and Q′₁ independently of one another are C₁ to C₄-alkyl or -CH₂-CO-NH₂,
Z₃, Z₄, Z′₃ and Z′₄ independently of one another are hydrogen or SO₃M,
M hydrogen, alkali metal or ammonium,
m₂, n₂, p₂ and q₂ mean integers, the sum of (m₂ + n₂) 2 to 15 and (p₂ + q₂) is 25 to 100 and
A₁ ⊖ and A₂ ⊖ represent an anion.
R₅ und R₆ unabhängig voneinander einen aliphatischen Rest mit 12 bis 24 C-Atomen,
Z₅ und Z₆ Wasserstoff oder SO₃M,
Z′₅ und Z′₆ unabhängig voneinander Wasserstoff oder SO₃M,
M Wasserstoff, Alkalimetall oder Ammonium und
m₃, n₃, p₃ und q₃ ganze Zahlen bedeuten, wobei die Summe von (m₃+n₃) 5 bis 12 und (p₃+q₃) 25 bis 100 ist, verwendet wird.Method according to one of claims 1 to 4, characterized in that an auxiliary mixture containing as component (a) a compound of the formula
R₅ and R₆ independently of one another are an aliphatic radical having 12 to 24 carbon atoms,
Z₅ and Z₆ are hydrogen or SO₃M,
Z′₅ and Z′₆ independently of one another are hydrogen or SO₃M,
M is hydrogen, alkali metal or ammonium and
m₃, n₃, p₃ and q₃ are integers, the sum of (m₃ + n₃) 5 to 12 and (p₃ + q₃) 25 to 100 is used.
10 bis 80 Teile der Komponente (a)
5 bis 70 Teile der Komponente (b) und
0 bis 70 Teile der Komponente (c)
und ad 100 Teile Wasser
verwendet.Method according to one of claims 1 to 8, characterized in that containing an auxiliary mixture
10 to 80 parts of component (a)
5 to 70 parts of component (b) and
0 to 70 parts of component (c)
and ad 100 parts of water
used.
R₁ und R₂ unabhängig voneinander einen aliphatischen Rest mit 12 bis 24 C-Atomen,
Z₁, Z₂, Z′₁ und Z′₂ unabhängig voneinander Wasserstoff, SO₃M oder PO₃M, wobei M Wasserstoff, Alkalimetall oder Ammonium, t₁ und t₂ 0 oder 1 bedeuten, wenn t₁ und t₂ 0 bedeuten, Z₁, Z′₁, Z₂ und Z′₂ Wasserstoff oder von Z₁, Z₂, Z′₁ und Z′₂ der eine Rest Wasserstoff und der andere SO₃M oder PO₃M bedeutet, m₁, n₁, p₁ und q₁ ganze Zahlen bedeuten, wobei die Summe von (m₁+n₁) 2 bis 15 und (p₁+q₁) 25 bis 200 ist, und als Komponente (c) 0 bis 70 Teile der Verbindung der Formel (2)
R₁ and R₂ independently of one another are an aliphatic radical having 12 to 24 carbon atoms,
Z₁, Z₂, Z'₁ and Z'₂ independently of one another are hydrogen, SO₃M or PO₃M, where M is hydrogen, alkali metal or ammonium, t₁ and t₂ are 0 or 1 if t₁ and t₂ are 0, Z₁, Z'₁, Z₂ and Z'₂ is hydrogen or Z₁, Z₂, Z'₁ and Z'₂ which is one radical hydrogen and the other SO₃M or PO₃M, m₁, n₁, p₁ and q₁ are integers, the sum of (m₁ + n₁) 2 to 15 and (p₁ + q₁) 25 to 200, and as component (c) 0 to 70 parts of the compound of formula (2)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH477/90 | 1990-02-14 | ||
| CH47790 | 1990-02-14 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0442844A1 true EP0442844A1 (en) | 1991-08-21 |
| EP0442844B1 EP0442844B1 (en) | 1995-02-01 |
| EP0442844B2 EP0442844B2 (en) | 1998-01-21 |
Family
ID=4187901
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP91810078A Expired - Lifetime EP0442844B2 (en) | 1990-02-14 | 1991-02-05 | Process for dyeing of wool with reactive dyes |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5145486A (en) |
| EP (1) | EP0442844B2 (en) |
| JP (1) | JPH04214476A (en) |
| KR (1) | KR910015749A (en) |
| AU (1) | AU638793B2 (en) |
| CA (1) | CA2036224A1 (en) |
| DE (1) | DE59104446D1 (en) |
| ES (1) | ES2067902T5 (en) |
| NZ (1) | NZ237087A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0548013A1 (en) * | 1991-12-16 | 1993-06-23 | Ciba-Geigy Ag | Process for dyeing of wool with help of low-temperature plasma or Corona-pretreatment |
| WO2000024749A1 (en) * | 1998-10-23 | 2000-05-04 | Bayer Aktiengesellschaft | Phosphoric acid esters |
| EP2246099A3 (en) * | 2008-11-25 | 2014-04-16 | Henkel AG & Co. KGaA | New colouring agent |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1261839B (en) * | 1992-08-03 | 1996-06-03 | Sandoz Ag | PROCEDURE FOR THE PRODUCTION OF SPECIAL COLORING EFFECTS ON TEXTILE PRODUCTS AND MIXTURES OF DYES USED. |
| DE59409028D1 (en) * | 1993-07-28 | 2000-02-03 | Ciba Sc Holding Ag | Process for dyeing wool-containing fiber materials |
| US20060138380A1 (en) * | 2003-06-26 | 2006-06-29 | Torsten Kulke | Aqueous liquid compositions of cyclodextrine or cyclodextrine derivatives and a process using the said composition |
| EP1777337A1 (en) * | 2005-10-07 | 2007-04-25 | Clariant International Ltd. | Method of dyeing polyamide fibres |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3919283A (en) * | 1965-03-18 | 1975-11-11 | Ciba Geigy Ag | Sulfate derivatives of polyglycol compounds |
| EP0089004A1 (en) * | 1982-03-12 | 1983-09-21 | Ciba-Geigy Ag | Process for dyeing fibrous material from natural polyamides |
| GB2168364A (en) * | 1984-12-14 | 1986-06-18 | Sandoz Ltd | Sulphates of oxyalkylated amines and their use as dyeing assistants |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2847913B1 (en) * | 1978-11-04 | 1980-02-07 | Hoechst Ag | Process for dyeing wool with reactive dyes |
| EP0312493B1 (en) * | 1987-10-14 | 1992-07-15 | Ciba-Geigy Ag | Process for dyeing natural polyamide fibres with reactive dyes |
| EP0414631A1 (en) * | 1989-02-22 | 1991-02-27 | Ciba-Geigy Ag | Auxiliary agent mixture and its use in dyeing polyester fibre materials |
| EP0417040A1 (en) * | 1989-09-06 | 1991-03-13 | Ciba-Geigy Ag | Dyeing process for wool |
-
1991
- 1991-02-05 EP EP91810078A patent/EP0442844B2/en not_active Expired - Lifetime
- 1991-02-05 DE DE59104446T patent/DE59104446D1/en not_active Expired - Fee Related
- 1991-02-05 ES ES91810078T patent/ES2067902T5/en not_active Expired - Lifetime
- 1991-02-11 US US07/654,139 patent/US5145486A/en not_active Expired - Fee Related
- 1991-02-12 CA CA002036224A patent/CA2036224A1/en not_active Abandoned
- 1991-02-12 KR KR1019910002313A patent/KR910015749A/en not_active Application Discontinuation
- 1991-02-12 AU AU70994/91A patent/AU638793B2/en not_active Ceased
- 1991-02-12 NZ NZ237087A patent/NZ237087A/en unknown
- 1991-02-14 JP JP3020240A patent/JPH04214476A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3919283A (en) * | 1965-03-18 | 1975-11-11 | Ciba Geigy Ag | Sulfate derivatives of polyglycol compounds |
| EP0089004A1 (en) * | 1982-03-12 | 1983-09-21 | Ciba-Geigy Ag | Process for dyeing fibrous material from natural polyamides |
| GB2168364A (en) * | 1984-12-14 | 1986-06-18 | Sandoz Ltd | Sulphates of oxyalkylated amines and their use as dyeing assistants |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0548013A1 (en) * | 1991-12-16 | 1993-06-23 | Ciba-Geigy Ag | Process for dyeing of wool with help of low-temperature plasma or Corona-pretreatment |
| WO2000024749A1 (en) * | 1998-10-23 | 2000-05-04 | Bayer Aktiengesellschaft | Phosphoric acid esters |
| EP2246099A3 (en) * | 2008-11-25 | 2014-04-16 | Henkel AG & Co. KGaA | New colouring agent |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2067902T5 (en) | 1998-04-16 |
| JPH04214476A (en) | 1992-08-05 |
| US5145486A (en) | 1992-09-08 |
| EP0442844B2 (en) | 1998-01-21 |
| DE59104446D1 (en) | 1995-03-16 |
| AU7099491A (en) | 1991-08-15 |
| ES2067902T3 (en) | 1995-04-01 |
| AU638793B2 (en) | 1993-07-08 |
| NZ237087A (en) | 1993-04-28 |
| CA2036224A1 (en) | 1991-08-15 |
| KR910015749A (en) | 1991-09-30 |
| EP0442844B1 (en) | 1995-02-01 |
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