US3401004A - Process for the dyeing of synthetic polyamide fibers - Google Patents
Process for the dyeing of synthetic polyamide fibers Download PDFInfo
- Publication number
- US3401004A US3401004A US373536A US37353664A US3401004A US 3401004 A US3401004 A US 3401004A US 373536 A US373536 A US 373536A US 37353664 A US37353664 A US 37353664A US 3401004 A US3401004 A US 3401004A
- Authority
- US
- United States
- Prior art keywords
- acid
- dyeing
- dyestuffs
- groups
- mols
- 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
- 238000004043 dyeing Methods 0.000 title description 57
- 239000004952 Polyamide Substances 0.000 title description 27
- 239000000835 fiber Substances 0.000 title description 27
- 238000000034 method Methods 0.000 title description 27
- 229920002647 polyamide Polymers 0.000 title description 27
- 230000008569 process Effects 0.000 title description 22
- -1 ether radical Chemical class 0.000 description 50
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 47
- 239000000975 dye Substances 0.000 description 39
- 239000002253 acid Substances 0.000 description 38
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 32
- 229920000151 polyglycol Polymers 0.000 description 28
- 239000010695 polyglycol Substances 0.000 description 28
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 26
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 239000000203 mixture Substances 0.000 description 22
- 239000004753 textile Substances 0.000 description 18
- 239000004312 hexamethylene tetramine Substances 0.000 description 16
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 16
- 229960004011 methenamine Drugs 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 13
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 13
- 229910052804 chromium Inorganic materials 0.000 description 13
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 239000011651 chromium Substances 0.000 description 11
- 239000007859 condensation product Substances 0.000 description 11
- 239000004744 fabric Substances 0.000 description 11
- 229920000768 polyamine Polymers 0.000 description 11
- 229910001385 heavy metal Inorganic materials 0.000 description 10
- 125000001424 substituent group Chemical group 0.000 description 10
- 210000002268 wool Anatomy 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 9
- 150000002170 ethers Chemical class 0.000 description 9
- 125000000542 sulfonic acid group Chemical group 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 229920002292 Nylon 6 Polymers 0.000 description 8
- 125000004429 atom Chemical group 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 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 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000155 melt Substances 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 125000000129 anionic group Chemical group 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 6
- 230000001737 promoting effect Effects 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 238000009976 warp beam dyeing Methods 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 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 5
- DBNYMXPUYZOHQN-UHFFFAOYSA-N n'-[2-(octadecylamino)ethyl]ethane-1,2-diamine Chemical compound CCCCCCCCCCCCCCCCCCNCCNCCN DBNYMXPUYZOHQN-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 125000001033 ether group Chemical group 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- IHZXTIBMKNSJCJ-UHFFFAOYSA-N 3-{[(4-{[4-(dimethylamino)phenyl](4-{ethyl[(3-sulfophenyl)methyl]amino}phenyl)methylidene}cyclohexa-2,5-dien-1-ylidene)(ethyl)azaniumyl]methyl}benzene-1-sulfonate Chemical compound C=1C=C(C(=C2C=CC(C=C2)=[N+](C)C)C=2C=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S(O)(=O)=O)=C1 IHZXTIBMKNSJCJ-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DGOBMKYRQHEFGQ-UHFFFAOYSA-L acid green 5 Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C=CC(=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 DGOBMKYRQHEFGQ-UHFFFAOYSA-L 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 150000001879 copper Chemical class 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- FPVGTPBMTFTMRT-UHFFFAOYSA-L disodium;2-amino-5-[(4-sulfonatophenyl)diazenyl]benzenesulfonate Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C(N)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 FPVGTPBMTFTMRT-UHFFFAOYSA-L 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 235000019233 fast yellow AB Nutrition 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- YUEUWFLCOBXUIS-UHFFFAOYSA-N n'-(2-aminoethyl)-n'-octadecylethane-1,2-diamine Chemical compound CCCCCCCCCCCCCCCCCCN(CCN)CCN YUEUWFLCOBXUIS-UHFFFAOYSA-N 0.000 description 3
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 3
- 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 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 150000001408 amides Chemical class 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
- 239000002585 base Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- NOXPGSDFQWSNSW-UHFFFAOYSA-N (sulfamoylamino)methane Chemical compound CNS(N)(=O)=O NOXPGSDFQWSNSW-UHFFFAOYSA-N 0.000 description 1
- BQUKEGNGEPWGHK-UHFFFAOYSA-N 1-[(2-hydroxy-5-phenyldiazenylphenyl)diazenyl]naphthalen-2-ol Chemical compound OC1=C(C=C(C=C1)N=NC1=CC=CC=C1)N=NC1=C(C=CC2=CC=CC=C12)O BQUKEGNGEPWGHK-UHFFFAOYSA-N 0.000 description 1
- FBWDWHONCBKETG-UHFFFAOYSA-N 1-chloro-2-(sulfamoylamino)ethane Chemical compound NS(=O)(=O)NCCCl FBWDWHONCBKETG-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- IRBQXLPYJHWQTM-UHFFFAOYSA-N 2-benzhydryl-1h-indole Chemical class N1C2=CC=CC=C2C=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 IRBQXLPYJHWQTM-UHFFFAOYSA-N 0.000 description 1
- FCBZRGXJOWSOFP-UHFFFAOYSA-N 2-hydroxy-3-methyl-4-sulfobenzoic acid Chemical class CC1=C(O)C(C(O)=O)=CC=C1S(O)(=O)=O FCBZRGXJOWSOFP-UHFFFAOYSA-N 0.000 description 1
- JTNCEQNHURODLX-UHFFFAOYSA-N 2-phenylethanimidamide Chemical compound NC(=N)CC1=CC=CC=C1 JTNCEQNHURODLX-UHFFFAOYSA-N 0.000 description 1
- LVSMGNXVKQOJGO-UHFFFAOYSA-N 3-(5-amino-3-methylpyrazol-1-yl)-4-chlorobenzenesulfonic acid Chemical compound N1=C(C)C=C(N)N1C1=CC(S(O)(=O)=O)=CC=C1Cl LVSMGNXVKQOJGO-UHFFFAOYSA-N 0.000 description 1
- YCPXWRQRBFJBPZ-UHFFFAOYSA-N 5-sulfosalicylic acid Chemical compound OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O YCPXWRQRBFJBPZ-UHFFFAOYSA-N 0.000 description 1
- RREANTFLPGEWEN-MBLPBCRHSA-N 7-[4-[[(3z)-3-[4-amino-5-[(3,4,5-trimethoxyphenyl)methyl]pyrimidin-2-yl]imino-5-fluoro-2-oxoindol-1-yl]methyl]piperazin-1-yl]-1-cyclopropyl-6-fluoro-4-oxoquinoline-3-carboxylic acid Chemical compound COC1=C(OC)C(OC)=CC(CC=2C(=NC(\N=C/3C4=CC(F)=CC=C4N(CN4CCN(CC4)C=4C(=CC=5C(=O)C(C(O)=O)=CN(C=5C=4)C4CC4)F)C\3=O)=NC=2)N)=C1 RREANTFLPGEWEN-MBLPBCRHSA-N 0.000 description 1
- FDXOYIGOUGEQBC-UHFFFAOYSA-N 8-(4-methylanilino)naphthalene-1-sulfonic acid Chemical compound C1=CC(C)=CC=C1NC1=CC=CC2=CC=CC(S(O)(=O)=O)=C12 FDXOYIGOUGEQBC-UHFFFAOYSA-N 0.000 description 1
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 1
- ZTBCHFSLHNOUNE-UHFFFAOYSA-K 8-acetamido-1-[(2-oxido-5-sulfamoylphenyl)diazenyl]naphthalen-2-olate cobalt(3+) hydron Chemical compound [H+].[Co+3].CC(=O)NC1=CC=CC2=CC=C([O-])C(N=NC3=CC(=CC=C3[O-])S(N)(=O)=O)=C12.CC(=O)NC1=CC=CC2=CC=C([O-])C(N=NC3=CC(=CC=C3[O-])S(N)(=O)=O)=C12 ZTBCHFSLHNOUNE-UHFFFAOYSA-K 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical class NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241000183024 Populus tremula Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- YNOSXQQLBPOTLB-UHFFFAOYSA-J [Na+].[Cr+3].Cc1[n-]n(-c2ccccc2)c(=O)c1\N=N\c1ccccc1C([O-])=O.Cc1[n-]n(-c2ccccc2)c(=O)c1\N=N/c1ccccc1C([O-])=O Chemical compound [Na+].[Cr+3].Cc1[n-]n(-c2ccccc2)c(=O)c1\N=N\c1ccccc1C([O-])=O.Cc1[n-]n(-c2ccccc2)c(=O)c1\N=N/c1ccccc1C([O-])=O YNOSXQQLBPOTLB-UHFFFAOYSA-J 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000004945 acylaminoalkyl group Chemical group 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000006177 alkyl benzyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 150000001649 bromium compounds Chemical class 0.000 description 1
- CYHOWEBNQPOWEI-UHFFFAOYSA-L calcium 3-carboxy-1-phenyldiazenylnaphthalen-2-olate Chemical compound OC=1C(=CC2=CC=CC=C2C1N=NC1=CC=CC=C1)C(=O)[O-].OC=1C(=CC2=CC=CC=C2C1N=NC1=CC=CC=C1)C(=O)[O-].[Ca+2] CYHOWEBNQPOWEI-UHFFFAOYSA-L 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- CFVDMKBMHNEJOD-UHFFFAOYSA-N chloro-(sulfamoylamino)methane Chemical compound ClCNS(=O)(=O)N CFVDMKBMHNEJOD-UHFFFAOYSA-N 0.000 description 1
- VXIVSQZSERGHQP-UHFFFAOYSA-N chloroacetamide Chemical compound NC(=O)CCl VXIVSQZSERGHQP-UHFFFAOYSA-N 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- GYGVRMLIQVFLPE-UHFFFAOYSA-L disodium;3-[[n-ethyl-4-[[4-[(3-sulfonatophenyl)diazenyl]naphthalen-1-yl]diazenyl]anilino]methyl]benzenesulfonate Chemical compound [Na+].[Na+].C=1C=C(N=NC=2C3=CC=CC=C3C(N=NC=3C=C(C=CC=3)S([O-])(=O)=O)=CC=2)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 GYGVRMLIQVFLPE-UHFFFAOYSA-L 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000006125 ethylsulfonyl group Chemical group 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- LMTSQIZQTFBYRL-UHFFFAOYSA-N n'-octadecylethane-1,2-diamine Chemical compound CCCCCCCCCCCCCCCCCCNCCN LMTSQIZQTFBYRL-UHFFFAOYSA-N 0.000 description 1
- 125000006126 n-butyl sulfonyl group Chemical group 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N n-hexadecyl alcohol Natural products CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 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
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229960003540 oxyquinoline Drugs 0.000 description 1
- 125000000913 palmityl 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])[H] 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- WSDQIHATCCOMLH-UHFFFAOYSA-N phenyl n-(3,5-dichlorophenyl)carbamate Chemical compound ClC1=CC(Cl)=CC(NC(=O)OC=2C=CC=CC=2)=C1 WSDQIHATCCOMLH-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 150000003220 pyrenes Chemical class 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical class [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- ORFSSYGWXNGVFB-UHFFFAOYSA-N sodium 4-amino-6-[[4-[4-[(8-amino-1-hydroxy-5,7-disulfonaphthalen-2-yl)diazenyl]-3-methoxyphenyl]-2-methoxyphenyl]diazenyl]-5-hydroxynaphthalene-1,3-disulfonic acid Chemical compound COC1=C(C=CC(=C1)C2=CC(=C(C=C2)N=NC3=C(C4=C(C=C3)C(=CC(=C4N)S(=O)(=O)O)S(=O)(=O)O)O)OC)N=NC5=C(C6=C(C=C5)C(=CC(=C6N)S(=O)(=O)O)S(=O)(=O)O)O.[Na+] ORFSSYGWXNGVFB-UHFFFAOYSA-N 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- IHRQVOBHLWHVSE-UHFFFAOYSA-N sulfamide;toluene Chemical compound NS(N)(=O)=O.CC1=CC=CC=C1 IHRQVOBHLWHVSE-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000003672 ureas Chemical group 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 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
- D06P3/24—Polyamides; Polyurethanes
- D06P3/245—Polyamides; Polyurethanes using metallisable or mordant 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
- 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
-
- 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
-
- 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
- Y10S8/907—Nonionic emulsifiers for dyeing
-
- 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
Definitions
- Hydrophilic surface-active dye assistant consisting essentially of, per molecule, a hydrophobic organic radical and at least one polyglycol ether radical;
- This invention relates to the dyeing of synthetic polyamide fibers and textiles made up therefrom, in particular to the dyeing of textile fabrics and other articles manufactured from these fibers.
- the invention also concerns aqueous dyestuff preparations suitable for this dyeing process and, as industrial product, the materials dyed according to the process.
- levelling agents serve very well also for the dyeing of synthetic polyamide, particularly in an alkaline dye bath, provided dyeing is performed with uniform dyestuffs of high afiinity to the treated fiber, they are unsatisfactory when fashion shades are be dyed with mixtures of dyestuffs under the conditions described, because very light differences in the affinity of the individual dyestuffs to polyamide fibers and in the stability of the dyestuff- I CC polyglycol ether complex lead, particularly on polyamide fabrics to uneven, cloudy, streaky dyeings and, in the case of larger batches, to dyeings with end-to-cnd and side-to-center unlevelness.
- a hydrophilic non-ionogenic surface-active polyaminoether which contains a hydrophobic organic radical and at least one hydrophilic polyglycol ether radical, from 0 to not more than about 5 ethyleneoxy groups, of which are C-alkyl and/or C-phenyl substituted; preferred polyamino-ether being defined further below, espe cially condensation products of formaldehyde with ammonia or Mannich bases;
- the dyestuff preparation to be used according to the invention consists of a dye liquor having conventional contents of from about 0.1 to 6% by weight of commercial dyestutf and of 0.5 to 3% by weight of auxiliaries, calculated on the weight of the polyamide material to be dyed.
- Dyeing is performed at temperatures of about C. to about 130 C. at the boil or under static pressure, and preferably at temperatures of over C. in a closed, vessel.
- Dyestuff preparations to be used according to the invention contain, apart from dyestuff of the types described further below, a critical dye assistant combination consisting of:
- hydrophilic, surface-active compounds those which contain, as hydrophobic radical, hydrocarbon radicals such as alkyl or alkenyl radicals having at least 10 and preferably 12 to 18 carbon atoms, alkylaryl radicals the alkyl substituents of which contain at least 5 and preferably 6 to 12 carbon atoms, or alicyclic hydrocarbon radicals, and they contain at least one hydrophilic polyglycol ether group of the above-defined length.
- hydrocarbon radicals such as alkyl or alkenyl radicals having at least 10 and preferably 12 to 18 carbon atoms
- alkylaryl radicals the alkyl substituents of which contain at least 5 and preferably 6 to 12 carbon atoms
- alicyclic hydrocarbon radicals or alicyclic hydrocarbon radicals
- polyglycol ethers of higher acylaminoalkyl monoand polyamines have proved to be particularly valuable in the process according to the invention, particularly those of lauryl-, myristyl-, oleyl-, palmityl-, stearylaminoethylamine, -ethylenediamine, -diethylenetriamine, as well as of higher monoalkylor alkenylethylenediamine, -diethylenetri-amine, -triethylenetetramine having in all at least 15, preferably more than 25 to about 100 ethyleneoxy radicals, which can be arranged in one sole or in different chains, and their ethyleneoxy groups, some of which can also be alkyl-substituted, particularly methyl-substituted, or phenyl-substituted to strengthen the lipophilic character of this moiety.
- the hydrophilic character can be strengthened, if desired, optionally by esterification of aliphatic hydroxyl groups with polybasic inorganic or organic acids to form acid esters or soluble salts thereof.
- Good results are obtained with technical mixtures of homologous and analogous compounds and mixtures with the soluble salts of acid esters, eg of the sulfates, phosphates, maleates, etc. with unesterified compound.
- A represents an alkylene radical selected from the group consisting of CH CH and radicals,
- X represents a member selected from the group consisting of NH-- and -O-, and
- n one of the numbers to 2
- styrene oxide preferably first with 1 mol of styrene oxide, preferably at a temperature of about 100 to 200 C., and then reacting the resulting intermediate in any order desired with 50 to 150 mols, preferably 70 to 100 mols of ethylene oxide and 0 to 2 mols of another oxide selected from the group consisting of styrene oxide and propylene oxide, at a temperature of about 80 to 200 C.; or directly reacting the polyamine of the above general formula with the aforesaid amounts of ethylene oxide and the other oxide; and
- condensation products containing basic nitrogen those derived from lower aliphatic aldehydes and ammonia or from lower organic amines, especially lower alkyl amines.
- the preferred condensation product is hexamethylenetetramine.
- the mixture of the dye assistants consists of surfaceactive polyglycol ethers and basic nitrogen-containing aldehyde condensation product, in a weight ratio of about 4:1 to 1:4.
- Mixtures consisting of mono-stearyl diethylenetriamine polyglycol ethers having over 30 ethyleneoxy radicals and hexamethylenetetramine in a ratio of about 3:2 to 2:3 are particularly suitable.
- the inorganic and, preferably, organic acids usual in dyeing used as acids to adjust the pH of the aqueous dyestutf preparation to the critical range stated hereinbefore, are, for example, sulfuric acid, phosphoric acid or their acid salts such as sodium or potassium bisulfate, monoand di-sodium or ammonium phosphate, toluene sulfonic acid, tetraline sulfonic acid and, particularly, lower aliphatic carboxylic acids such as formic acid and, preferably, acetic acid.
- a particularly favorable result is obtained in the process according to the invention when the ratio of the preferred hexamethylenetetramine to an acid which forms a salt therewith, is about one mol of amine per equivalent of acid; acetic acid, formic acid and sulfuric acid are particularly useful as such acids.
- a preferred method of the invention is the dyeing, by the exhaustion process, of fabrics or articles made from synthetic fibers which are produced from addition polyamides. This is performed preferably at temperatures of at least 100 C., e.g. under static pressure is a closed vessel and, particularly, at temperatures of over 100 C. to C. Good dyeing yield of very level dyeings in any desired depth are obtained by this method in relatively very short dyeing times.
- Dyeing is advantageously performed in short dyebaths using a ratio of liquor to textile material of 10:1 to 2021, the liquor containing about 0.5 to 3% of auxiliaries calculated on the Weight of the goods being dyed and depending on the amount of dyestutf or the desired depth of shade.
- the polyamide dyeings attained according to the invention are distinguished by excellent levelness, very good exhaustion of the bath and the dyeings can be reproduced very easily. Also the polyamide part of blended fabrics consisting of synthetic polyamide and other non-polyamide textile fibers can be dyed by the process according to the invention.
- dyestuffs there are usable in the process according to the invention, practically all neutral to weakly acid drawing anionic wool dyestuffs of the various known classes of fast wool dyestuffs.
- Particularly suitable in the new dyeing process is the use of neutral to weakly acid drawing azo and azomethine dyestuffs containing heavy metal, whereby fast, level dyeings on fabrics and articles made of synthetic addition polyamide fibers produced from lactams of aliphatic aminocarboxylic acids such as
- Particularly suitable are the chromium and cobalt complexes of o,o'-dihydroxy -monoazo, -disazo or -azomethine dyestuffs, of o-hydroxyl-o'-carboxy monoor dis-azo dyestuffs, of o-hydroxy d-amino monoor also dis-azo dyestuffs which, per heavy metal atom, contain two identical or different dyestuffs bound in complex linkage.
- the dyestuff components of these heavy metal complexes also contain known substituents to promote water-solubility, for example, lower alkylsulfonyl groups such as methylsulfonyl, chloromethylsulfonyl, oxymethylenesulfonyl, ethylsulfonyl, isopropylsulfonyl, n-butylsulfonyl groups, sulfamyl groups such as sulfonic acid amide, sulfonic acid monoor dilower alkylamide, lower hydroxyalkylamide, sulfonic acid phenylamide groups, or acylamido groups such as alkylsulfamide or arylsulfamide groups, e.g.
- methylsulfamide chloromethylsulfamide, chloroethylsulfamide, toluene sulfamide, acetamide, chloroacetamide, propionylamide, fi-chloroor bromo-propionlyamide, lower alkoxycarbamide groups.
- these heavy metalcontaining dyestuffs can also contain a salt-forming group which dissociates acid such as the carboxyl, the disulfimide and, particularly, the sulfonic acid groups, but advantageously they only contain one of these groups alone in a so-called 2:1 complex consisting of a monosulfonated and an unsulfonated basic dyestuff bound in complex linkage to a chromimurn or cobalt atom.
- a sulfonic acid substituent in so-called mixed heavy metal complex dyestuffs is particularly indicated if one of the basic dyestuffs forming the complex is a disazo dyestuff or an azomethine dyestuff containing arylazo groups, or if the dyestuff component containing no sulfonic acid groups also has no substituents which promote water-solubility.
- Metallized monoand dis-azo dyestuffs forming tridentate and polydentate metal complexes are also suitable which, per heavy metal atom, contain only one sole colored complex former and, optionally, in addition a non-colored complex former.
- the copper complexes of metallizable disazo dyestuffs of the formazane series are also very suitable; low-sulfonated copper phthalocyanins having substituents promoting water-solubility of the type listed above can also be used.
- heavy metal-containing dyestuffs also those types are very suitable which contain, bound to a heavy metal atom, particularly chromium, an unsulfonated, tridentate complex-forming, metallizable azo dyestuff and a colorless complex former which can contain substituents promoting water-solubility;
- the usual colorless complex formers in these dyestuffs are salicylic acid and, particularly, the amides, alkylamides or phenylamides of sulfosalicylic and sulfocresotic acids.
- all these heavy metal-containing azo and azomethine dyestuffs can also contain other substituents usual in azo dyestuffs, for example, low alkyl and alkoxy groups, halogens such as fluorine, chlorine or bromine, nitro groups etc.
- Dyestuffs not containing heavy metal which can be used according to the invention are, among others, neutral to quickly drawing acid wool dyestuffs of the azo series, for example, disazo dyestuffs containing sulfonic acid groups with diphenylether, diphenylamine, phenylnaphthylamine or phenylsulfonyloxyaryl groupings, also neutral or quickly drawing acid wool dyestuffs of the triphenylmethane or diphenyl-indolylmethane series, of the pyrene series, e.g. rhodamines such as halogenated rhodamine dyestuffs, of the anthraquinone series, e.g.
- dyestuffs can also contain in their aromatic nuclei substituents conventional in dyestuffs listed above.
- Synthetic polyamide fibers which can be evenly dyed according to the invention are, for example, the materials known in the textile industry by the following names:
- Nylon 66 a textile fiber from hexamethylene-diamine and adipic acid produced by condensation
- Nylon 610 a textile fiber from the same diamine and sebacic acid, produced by condensation
- Nylon 66/ 6 a textile fiber from mixed polymers produced by condensation of hexamethylene-diamine and adipic acid and addition of e-caprolactam;
- Nylon 6 a textile fiber produced from addition polymers of e-CilPlOlfiCtflHl;
- Nylon 11 a textile fiber from w-aminododecanoic acid produced by condensation, as well as polyamide fibers of the same or similar structure most of which are commercially available.
- the preferred polyaminoethers mentioned and others used in the composite dye assistants according to the invention are obtained, for example, from diprimary or diprimary-secondary or diprirnary-tertiary alkylene polyamines and from diprimary or diprimary-secondary or diprimary-tertiary dior triethers by condensing in the heat with an at most equimolecular amount of alkyl, alkylbenzyl, cycloalkyl or alkylcycloalkyl chlorides or bromides or of alkali metal salts of acid sulfates of the corresponding hydroxyl compounds. After liberating the bases obtained with strong alkalis, any more easily volatile components still present are distilled off, advantageously in vacuo, and the mixture of bases which is not easily volatile is used direct for the condensation with styrene oxide.
- condensation products which contain at least 50 and advantageously more than 70 ethyleneoxy radicals and have a low content of propyleneoxy radicals are generally still sufficiently watersoluble for direct use for the purposes intended. It is often advantageous for an intended use of the condensation products according to the invention if they contain more than one phenylethyleneoxy radical. It is possible, without difficulty, at any stage, i.e. before, during or after the reaction with alkylene oxide, to add single equivalents of styrene oxide.
- the epoxides are added under the usual conditions. Whereas for the addition of styrene oxide in the first step it is generally sufficient to react the component by heating to about 100 C. to 200 C. depending on the composition, generally a basic catalyst such as sodium or potassium hydroxide, carbonate or alcoholate, is necessary for the addition of the alkylene oxides. Depending on their reactivity, the alkylene oxides can be incorporated in the solutions of the starting materials and catalysts in inert organic solvents, or in the melts of the starting materials, if necessary under pressure. In general, raised temperatures of, for example 80 C. up to about 200 C. are indicated.
- EXAMPLE 1 A high temperature beam dyeing machine consisting of a closed system fitted with a circulation pump for circulating the liquor both from inside to the outside and vice versa is used.
- 1 kg. of a polyglycol ether produced by reacting 90 mols of ethylene oxide with N-stearyl diethylenetriamine and 0.6 kg. of hexamethylenetetramine are dis solved in 1500 liters of water, and the pH of the solution is adjusted to about 4.5 by the gradual addition of about 1.5 kg. of 40%-acetic acid.
- 110 kg. of warp-knit tricot of nylon 6 wound round the perforated beam are introduced, the apparatus is closed and the circulation pump is set in action. After minutes, a mixture of 1.0 kg.
- chromium-containing dyestulf obtained from 2 mols of 1 phenyl 3 methyl-4-(2'-carboxy-5-methy1- sulfonylphenylazo) -5-pyrazolone per chromium gram atom bound in complex linkage
- 0.6 kg. of the chromiumcontaining dyestuff obtained from 2 mols of l-acetylamino 7 hydroxy 8 (2 hydroxy-5'-ethylsulfonylphenylazo) naphthalene per chromium gram atom, bound in complex linkage, and 0.25 kg.
- the excess pressure is removed and the dyed goods are rinsed with circulating warm and cold water. Goods very evenly dyed in a stone grey-olive shade are obtained. The dyeings are Wetand light-fast.
- Acid Blue 168 C.I. Acid Black 60; C.I. Acid Red 300; C.I. Acid Brown 252;
- the polyglycol ether used in Example 1 is produced as follows: a
- EXAMPLE 2 100 kg. of nylon 6 velour are dyed on the perforated beam of a high temperature beam dyeing machine described in Example 1 in a liquor containing 0.6 kg-ofthe polyglycol ether used in Example 1; 0. 6 kg. of hexamethylenetetramine and about 1 kg. of aqueous 40%- acetic acid in 1500 liters of water. The liquor is circulated in the closed machine for 10 minutes at room temperature and then the mixture of 3 kg.
- EXAMPLE 3 In the dyeing machine described in Example 1, 100 kg. of nylon 6 fabric are dyed on the perforated beam in 1500 liters of water containing 1 kg. of polyglycol ether from monostearyl diethylenetriamine, 2 mols of styrene oxide, 100 mols of ethylene oxide, 5 mols of propylene oxide, 0.5 kg. of hexamethylenetetramine and 1.0 kg; of 40%-acetic acid. The liquor is first circulated for 10 minutes at room temperature, 2 to 4 atmospheres excess pressure being applied by an additional pump. Then the mixture of 1.5 kg.
- the orange dyestuff chromium complex produced by adding 2-hydroxybenzene-1-carboxylic 'acid-5-sulfonic acid phenyla-mide to the monoazo dyestuif metallized in a ratio of 1 chromium atom per 1-(3'chlorophenyl)-3-methyl-4-(2-hydroxy-5-sulfamido-phenyl)- azo-S-pyrazolone, with 15 liters of hot Water is then drawn in. The liquor is first circulated for 10 minutes at room temperature and then, in a closed vessel,'it is heated up within 40 minutes to Dyeing is performed for 25 minutes at this temperature. After cooling, the dyeing is rinsed with warm and then cold water. A very level, lightand wet-fast orange dyeing is obtained.
- the polyglycol ether used in Example 3 is produced as follows: i
- EXAMPLE 4 In a high temperature beam dyeing machine, 100 kg. of nylon 6 tafieta are dyed on the beam with a solution of 1 kg. of polyglycol ether from oleylethylenediamine, 1 mol of styrene oxide and 50 ml. of ethylene oxide, 0.8 kg. of hexamethylenetetramine and 2 liters of 40% H 50 in 1500 liters of water.
- the liquor is circulated for minutes at room temperature, then the mixture of 2 kg of the chromium-containing monoazo dyestutf 1- (2' hydroxy 4 nitrophenylazo) 2 (2" carboxy- 4" sulfamidophenylamino) naphthalene containing 1 chromium atom and 1 mol of 8-hydroxyquinoline bound in complex linkage, with liters of hot water is added, the liquor is circulated first for 10 minutes at room temperature then, in a closed vessel, it is heated to 120 within 30 minutes and then kept at this temperature for minutes. It is then cooled, the goods are rinsed, after removal of the liquor, with warm and cold water.
- Dyeings having similar properties are obtained if in this example, the dyestuff disclosed is replaced by the similarly constructed commercial brand C.I. Acid Green 57.
- EXAMPLE 5 In a high temperature beam dyeing machine fitted with a circulation pump, 100 kg. of nylon 6 shirting are dyed under the conditions described in Example 1 on the perforated beam by the method described in the previous examples. A liquor consisting of 2 kg. of polyglycol ether from stearylamine, 1 mol of styrene oxide and 70 mols of ethylene oxide, 0.5 kg. of hexamethylenetetramine and 1 kg. of %-acetic acid in 1500 liters of water is used. The goods are dyed with 3 kg.
- the disazo dyestuff produced from diazotized 3-aminobenzene-l-sulfonic acid-4'- cresol ester sulfonic acid, coupling with the technical mixture of 1-amino-naphthalene-6- and -7- sulfonic acid, diazotizing the aminoazo dyestutf and again coupling with 1- (4 methylphenylamino) naphthalene 8 sulfonic acid, by first pre-treating the goods for 10 minutes in the liquor containing the auxiliaries, then adding the mixture of the dyestuif with 15 liters of hot water circulating the liquor in a closed apparatus while heating to 120 within 45 minutes and further treating for 30 minutes at this liquor temperature. The liquor is then cooled to under removed and the dyed goods are rinsed with warm and cold water. A very level navy blue dyeing is obtained.
- the polyglycolether used in combination with hexamethylenetetramine as the dye assistant in Example 5 is produced as follows:
- N-stearylamine 67.5 parts of N-stearylamine are melted by heating to 70. 30 parts of styrene oxide dissolved in toluene are added dropwise to the melt withinabout 10 minutes. The mixture is then slowly heated to At this temperature, heat is generated to about 150. On completion of the reaction, the temperature is kept at 140150 by warming for about 4 hours. A brown wax is formed which gradually solidifies in the cold.
- the resulting N-stearylamino-2-phenylethanol mass obtained as described above is dissolved in 50 parts of alcohol in which 1 part of sodium has been dissolved. After thoroughly mixing, the alcohol is distilled 01f, the mixture is heated to l30 and then ethylene oxide is introduced until the increase in weight of the reaction product is 775 parts. The reaction product obtained solidifies on cooling and then completely dissolves in water.
- EXAMPLE 6 100 kg. of nylon 6 fabric are dyed on the beam in a dyeing machine described in Example 1 by pro-treating the goods for 10 minutes at room temperature with the solution of 1 kg. of the known polyglycol ether obtained by condensing a technical mixture of cetyl and oleyl alcohol with ethylene oxide, which product possesses 50 ether groups, 0.8 kg. of hexamethylenetetramine and 0.8 kg. of 40%-acetic acid in 1700 liters of water. The pressure is then raised to 3 atmospheres excess pressure, and aqueous solution of 1.5 kg.
- the known polyglycol ether obtained by condensing a technical mixture of cetyl and oleyl alcohol with ethylene oxide, which product possesses 50 ether groups, 0.8 kg. of hexamethylenetetramine and 0.8 kg. of 40%-acetic acid in 1700 liters of water.
- the pressure is then raised to 3 atmospheres excess pressure, and aqueous solution of 1.5 kg.
- Dyeings having similar properties are obtained if, instead of the neutral to weakly acid drawing acid anthraquinone dyestuif described in the example, the similarly constructed commercial brands; C.I. Acid Blue 226; C.I. Acid Green 59; C.I. Acid Green 69.
- EXAMPLE 7 100 kg. of nylon 6 knitted articles (tricot) are dyed in a modern type winch. The ends of the goods are sewn together and drawn through the liquor over a round or oval winch continuously. The goods are treated at room temperature for 10 minutes in a solution of 0.6 kg. of polyglycol ether from o ctadecyldiethylenetriamine, 2 mols of styrene oxide and i100 mols of ethylene oxide and also 0.35 kg. of hexamethylenetetramine and 0.6 kg. of 40%- -acetic acid in 1300 liters of water.
- Similar level dyeings are obtained if, instead of the formazine dyestuff used above, similar copper-containing dyestuffs are used which, instead of a sulfonic acid group, contain sulfarnide groups as substituents promoting water-insolubility.
- similarly constructed commercial dyestuffs such as C.I. Acid Yellow 79 can be used.
- Example 7 The polyglycol ether used in Example 7 is produced as follows:
- a process for dyeing of synthetic polyamide fiber textile material, com-prising beam-dyeing, the said material at a temperature of 100 to 130 C. with an aqueous dyestuif preparation which contains:
- a non-ionogenic surfactant ether which is the condensation product obtained by reacting 1 mol of a polyamine of the general formula:
- L represents a lipophilic alkyl or alkenyl radical having 16-18 carbon atoms
- A represents an alkenylene radical selected from the group consisting of -CH CH and radicals
- X represents a member selected from the group consisting of NH- and -O, and
- n one of the numbers 0 to 2
- m represents one of the numbers 0 to 2
- said surfactant ether defined under (b) is the polyglycol ether obtained from monostearyl diethylenetriamine, 2 mols of styrene oxide, 100 mols of ethylene oxide and 5 mols of propylene oxide.
- said surfactant ether defined under (b) is the polyglycolether from oleylethylenediamine, 1 mol of styrene oxide and 50 mols of ethylene oxide.
- said surfactant ether defined under (b) is the polyglycol ether from stearylamine, 1 mol of styrene oxide and 70 mols of ethylene oxide.
- said surfactant ether defined under (b) is the polyglycol ether from octadecyldiethylenetriamine, 2 mols of styrene oxide and 100 mols of ethylene oxide.
- a process 'for the dyeing of synthetic polyamide fiber textile material comprising beam dyeing, the said material at a temperature of 100 to C. with an aqueous dyestuff preparation which contains:
- a dyestuff selected from the group consisting of copper complexes of metallizable disazo dyestuffs of the formazane series; unmetallized disazo dyestuffs containing sulfonic acid groups, and 4,4'-bis-(4- amino 3 sulfo anthraquinonyl 1 amino)- diphenylalkane dyestuffs:
- a non-ionogenic surfactant ether which is the condensation product obtained by reacting 1 mol of a polyamine of the general formula:
- L represents a lipophilic alkyl or alkenyl radical having 16-18 carbon atoms
- A represents an alkylene radical selected from the group consisting of --CH CH and radicals,
- X represents a member selected from the group consisting, of --NH and -O--, and
- n one of the numbers 0 to 2
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Description
United States Patent 3,401,004 PROCESS FOR THE DYEING 0F SYNTHETIC POLYAMIDE FIBERS Horst Krumme, Munster, Westphalia, and Hans-Helmut Schoor and Giinter Jakob, Grenzach, Germany, assignors to J. R. Geigy A.G., Basel, Switzerland No Drawing. Filed June 8, 1964, Ser. No. 373,536 Claims priority, applicatiogn1 6S/vzizerland, Mar. 26, 1964,
8 Claims. (Cl. 8-55) ABSTRACT OF THE DISCLOSURE Process for the dyeing of synthetic polyamide fiber textile material, comprising dyeing the said material with an aqueous dyestuff preparation which contains:
(a) Neutralto weakly acid-drawing anionic wool dyestuff as coloring agent,
(b) Hydrophilic surface-active dye assistant consisting essentially of, per molecule, a hydrophobic organic radical and at least one polyglycol ether radical;
(c) At least one water-soluble aldehyde condensation product containing basic nitrogen, and
(d) The pH of said preparation at the beginning of dyeing being less than 7.5 but not less than 3.
This invention relates to the dyeing of synthetic polyamide fibers and textiles made up therefrom, in particular to the dyeing of textile fabrics and other articles manufactured from these fibers. The invention also concerns aqueous dyestuff preparations suitable for this dyeing process and, as industrial product, the materials dyed according to the process.
It is known that synthetic polyamide fibers and textiles manufactured therefrom can be dyed with anionic acid wool dyestuffs in fast shades. The term synthetic polyamides as used in this specification and the appended claims means polyamides which are produced by polycondensation from polyfunctional organic amines and polycarboxylic acids, e.g. from hexamethylenediamine or decamethylenediamine and adipic acid or sebacic acid, or by addition polymerization from lactams of aliphatic aminocarboxylic acids, e.g. from e-aminocaprolactam. It is also known that these polyamide fibers and the fabrics produced therefrom dye very differently if, in these fibers, the degree of orientation of the polyamides is different. As the degree of orientation can be influenced by stretching the fibers, often very undesirable streakiness of the dyeings occurs due to uneven mechanical strain of the warp and weft of fabrics. There are also other causes of streakiness such as nonuniform heattreatment of the fibers or differences in the terminal groupings of the nylon molecules. It is difiicult toiniprove the streaky appearance of such dyeings, for it is well known that the usual levelling agents hitherto used in wool dyeing, e.g. polyglycol ethers of alkanols having 1020 carbon atoms, alkyl phenols, alkylamines and polyalkylene polyamines substituted by higher alkyl or acyl radicals and having at least ethyleneoxy groups in the polyglycol ether chain or chains, form addition complexes with anionic dyestuffs which have reduced drawing power onto polyamide fibers. Moreover, while these levelling agents serve very well also for the dyeing of synthetic polyamide, particularly in an alkaline dye bath, provided dyeing is performed with uniform dyestuffs of high afiinity to the treated fiber, they are unsatisfactory when fashion shades are be dyed with mixtures of dyestuffs under the conditions described, because very light differences in the affinity of the individual dyestuffs to polyamide fibers and in the stability of the dyestuff- I CC polyglycol ether complex lead, particularly on polyamide fabrics to uneven, cloudy, streaky dyeings and, in the case of larger batches, to dyeings with end-to-cnd and side-to-center unlevelness.
As a consequence of the above mentioned complex formation, dyeing yield is often unsatisfactory because, in certain circumstances, a considerable part of the dyestuff remains in the dyebath. Reproduction of dyeings in identical shades, which is important in industrial practice, suffers thereby, and an undesirable amount of waste is produced.
It has now been found that these disadvantages can be overcome and synthetic polyamide fibers, particularly also textile fabrics and other articles manufactured from these fibers, can be very evenly dyed in all conventionally desired depths with good exhaustion of the dyebaths by using as the latter, or in their preparation, aqueous dyestuff compositions which contain as substantial components:
(a) Neutral to weakly acid drawing anionic wool dyestuff as coloring agent;
(b) A hydrophilic non-ionogenic surface-active polyaminoether which contains a hydrophobic organic radical and at least one hydrophilic polyglycol ether radical, from 0 to not more than about 5 ethyleneoxy groups, of which are C-alkyl and/or C-phenyl substituted; preferred polyamino-ether being defined further below, espe cially condensation products of formaldehyde with ammonia or Mannich bases;
(c) A water-soluble aldehyde condensation product containing from 1 to 4 basic nitrogen atoms per molecule, preferably hexamethylene tetramine, and
(d) Sufficient acid to adjust the pH value of the dyebath at the beginning of the dyeing treatment to less than 7.5 but not less than 3.
In dyeing of the above-defined fiber materials by the exhaustion process, the dyestuff preparation to be used according to the invention consists of a dye liquor having conventional contents of from about 0.1 to 6% by weight of commercial dyestutf and of 0.5 to 3% by weight of auxiliaries, calculated on the weight of the polyamide material to be dyed. Dyeing is performed at temperatures of about C. to about 130 C. at the boil or under static pressure, and preferably at temperatures of over C. in a closed, vessel.
Dyestuff preparations to be used according to the invention contain, apart from dyestuff of the types described further below, a critical dye assistant combination consisting of:
(I) As hydrophilic, surface-active compounds, those which contain, as hydrophobic radical, hydrocarbon radicals such as alkyl or alkenyl radicals having at least 10 and preferably 12 to 18 carbon atoms, alkylaryl radicals the alkyl substituents of which contain at least 5 and preferably 6 to 12 carbon atoms, or alicyclic hydrocarbon radicals, and they contain at least one hydrophilic polyglycol ether group of the above-defined length. The two characteristic moieties of these compounds can be linked together by way of various bridging atoms or groups, for example:
(a) By means of oxygen such as in the polyglycol ethers of higher alkanols and alkenols as well as in higher phenols alkylated in the ring,
(b) By means of sulfur, e.g. in the polyglycol ethers of higher alkylmercaptans and alkenylmercaptans and in the thiophenols the ring of which is higher alkyl-substituted,
(c) By way of nitrogen, e.g. in the polyglycol ethers of higher alkylated or alkenylated primary or secondary aliphatic monoamines or polyamines, or
(d) By the carboxy group --COO--, e.g. in the polyglycol ethers of higher saturated or unsaturated fatty acids, alkoxy and alkylthio fatty acids having higher alkyl groups, by means of the carbamide group CO-N e.g. in the polyglycol ethers of the amides of carboxylic acids listed above with ammonia monoalkyl-, monohydroxyalkyland dihydroxyalkylamines, as well as with aliphatic or alicyclic polyamines, in which a long polyglycol ether chain or several shorter ones can be bound by way of nitrogen.
The polyglycol ethers of higher acylaminoalkyl monoand polyamines have proved to be particularly valuable in the process according to the invention, particularly those of lauryl-, myristyl-, oleyl-, palmityl-, stearylaminoethylamine, -ethylenediamine, -diethylenetriamine, as well as of higher monoalkylor alkenylethylenediamine, -diethylenetri-amine, -triethylenetetramine having in all at least 15, preferably more than 25 to about 100 ethyleneoxy radicals, which can be arranged in one sole or in different chains, and their ethyleneoxy groups, some of which can also be alkyl-substituted, particularly methyl-substituted, or phenyl-substituted to strengthen the lipophilic character of this moiety. In the surface active compounds usable according to the invention, the hydrophilic character can be strengthened, if desired, optionally by esterification of aliphatic hydroxyl groups with polybasic inorganic or organic acids to form acid esters or soluble salts thereof. Good results are obtained with technical mixtures of homologous and analogous compounds and mixtures with the soluble salts of acid esters, eg of the sulfates, phosphates, maleates, etc. with unesterified compound.
Especially satisfactory results of broad applicability to a great variety of dyestuffs are obtained with those dye assistants in which the component (b), supra, is a nonionogenic capillary active ether, which is obtained by reacting 1 mol of a polyamine of the general formula:
LNHA (X-A) NH wherein L represents a lipophilic alkyl or alkenyl radical having 16-18 carbon atoms,
A represents an alkylene radical selected from the group consisting of CH CH and radicals,
X represents a member selected from the group consisting of NH-- and -O-, and
m represents one of the numbers to 2,
preferably first with 1 mol of styrene oxide, preferably at a temperature of about 100 to 200 C., and then reacting the resulting intermediate in any order desired with 50 to 150 mols, preferably 70 to 100 mols of ethylene oxide and 0 to 2 mols of another oxide selected from the group consisting of styrene oxide and propylene oxide, at a temperature of about 80 to 200 C.; or directly reacting the polyamine of the above general formula with the aforesaid amounts of ethylene oxide and the other oxide; and
(II) As water-soluble aldehyde condensation products containing basic nitrogen those derived from lower aliphatic aldehydes and ammonia or from lower organic amines, especially lower alkyl amines. The preferred condensation product is hexamethylenetetramine.
The mixture of the dye assistants consists of surfaceactive polyglycol ethers and basic nitrogen-containing aldehyde condensation product, in a weight ratio of about 4:1 to 1:4.
Optimal dyeings on nylon textile materials, free from streakiness and in good yield are obtained when using in Octadecyl-NI-I,CH CH (NH-CH CH NH wherein m represents one of the numbers 0 to 2,
first with 1 to 2 mols of styrene oxide and then with to mols of ethylene oxide, under the conditions specified hereinbefore, and
(2) Hexamethylene tetramine, in a weight ratio of (1):(2) ranging from about 3:1 to 1:3.
Mixtures consisting of mono-stearyl diethylenetriamine polyglycol ethers having over 30 ethyleneoxy radicals and hexamethylenetetramine in a ratio of about 3:2 to 2:3 are particularly suitable.
The inorganic and, preferably, organic acids usual in dyeing used as acids to adjust the pH of the aqueous dyestutf preparation to the critical range stated hereinbefore, are, for example, sulfuric acid, phosphoric acid or their acid salts such as sodium or potassium bisulfate, monoand di-sodium or ammonium phosphate, toluene sulfonic acid, tetraline sulfonic acid and, particularly, lower aliphatic carboxylic acids such as formic acid and, preferably, acetic acid. A particularly favorable result is obtained in the process according to the invention when the ratio of the preferred hexamethylenetetramine to an acid which forms a salt therewith, is about one mol of amine per equivalent of acid; acetic acid, formic acid and sulfuric acid are particularly useful as such acids.
A preferred method of the invention is the dyeing, by the exhaustion process, of fabrics or articles made from synthetic fibers which are produced from addition polyamides. This is performed preferably at temperatures of at least 100 C., e.g. under static pressure is a closed vessel and, particularly, at temperatures of over 100 C. to C. Good dyeing yield of very level dyeings in any desired depth are obtained by this method in relatively very short dyeing times. Dyeing is advantageously performed in short dyebaths using a ratio of liquor to textile material of 10:1 to 2021, the liquor containing about 0.5 to 3% of auxiliaries calculated on the Weight of the goods being dyed and depending on the amount of dyestutf or the desired depth of shade.
Large batches of fast and evenly dyed fabrics and articles made from synthetic polyamide are attained by the process according to the invention. The polyamide dyeings attained according to the invention are distinguished by excellent levelness, very good exhaustion of the bath and the dyeings can be reproduced very easily. Also the polyamide part of blended fabrics consisting of synthetic polyamide and other non-polyamide textile fibers can be dyed by the process according to the invention.
It is noteworthy that neither the use of the dye assistants enumerated above under (I) alone, nor the use of hexamethylenetetramine or another compound falling under the definition of (II) given above, permits the production of dyeings on the aforesaid fibers free from streakiness, while, surprisingly, dyeing with the composite dye assistant consisting, according to the invention, of (I) and (II) especially in the above stated Weight ratios, leads unexpectedly to perfectly level dyeings, free from streakiness, when using dyestuffs of the classes defined below.
The physico-chemical mechanism of this phenomenon is at present unknown.
As dyestuffs, there are usable in the process according to the invention, practically all neutral to weakly acid drawing anionic wool dyestuffs of the various known classes of fast wool dyestuffs. Particularly suitable in the new dyeing process is the use of neutral to weakly acid drawing azo and azomethine dyestuffs containing heavy metal, whereby fast, level dyeings on fabrics and articles made of synthetic addition polyamide fibers produced from lactams of aliphatic aminocarboxylic acids such as Particularly suitable are the chromium and cobalt complexes of o,o'-dihydroxy -monoazo, -disazo or -azomethine dyestuffs, of o-hydroxyl-o'-carboxy monoor dis-azo dyestuffs, of o-hydroxy d-amino monoor also dis-azo dyestuffs which, per heavy metal atom, contain two identical or different dyestuffs bound in complex linkage. In addition to complex-forming substituents, the dyestuff components of these heavy metal complexes also contain known substituents to promote water-solubility, for example, lower alkylsulfonyl groups such as methylsulfonyl, chloromethylsulfonyl, oxymethylenesulfonyl, ethylsulfonyl, isopropylsulfonyl, n-butylsulfonyl groups, sulfamyl groups such as sulfonic acid amide, sulfonic acid monoor dilower alkylamide, lower hydroxyalkylamide, sulfonic acid phenylamide groups, or acylamido groups such as alkylsulfamide or arylsulfamide groups, e.g. methylsulfamide, chloromethylsulfamide, chloroethylsulfamide, toluene sulfamide, acetamide, chloroacetamide, propionylamide, fi-chloroor bromo-propionlyamide, lower alkoxycarbamide groups. Uunder certain conditions, these heavy metalcontaining dyestuffs can also contain a salt-forming group which dissociates acid such as the carboxyl, the disulfimide and, particularly, the sulfonic acid groups, but advantageously they only contain one of these groups alone in a so-called 2:1 complex consisting of a monosulfonated and an unsulfonated basic dyestuff bound in complex linkage to a chromimurn or cobalt atom. The presence of a sulfonic acid substituent in so-called mixed heavy metal complex dyestuffs is particularly indicated if one of the basic dyestuffs forming the complex is a disazo dyestuff or an azomethine dyestuff containing arylazo groups, or if the dyestuff component containing no sulfonic acid groups also has no substituents which promote water-solubility. Metallized monoand dis-azo dyestuffs forming tridentate and polydentate metal complexes are also suitable which, per heavy metal atom, contain only one sole colored complex former and, optionally, in addition a non-colored complex former. These are, for example, complex chromium compounds of o-hyclroxy-o-arninoazo dyestuffs of the benzeneazonaphthalene series having a secondary amino group forming the complex, the substituent of which also has complex-forming properties. The copper complexes of metallizable disazo dyestuffs of the formazane series are also very suitable; low-sulfonated copper phthalocyanins having substituents promoting water-solubility of the type listed above can also be used. Of the class of heavy metal-containing dyestuffs, also those types are very suitable which contain, bound to a heavy metal atom, particularly chromium, an unsulfonated, tridentate complex-forming, metallizable azo dyestuff and a colorless complex former which can contain substituents promoting water-solubility; the usual colorless complex formers in these dyestuffs are salicylic acid and, particularly, the amides, alkylamides or phenylamides of sulfosalicylic and sulfocresotic acids. In addition to the complex-forming and the water solubility-promoting substituents, all these heavy metal-containing azo and azomethine dyestuffs can also contain other substituents usual in azo dyestuffs, for example, low alkyl and alkoxy groups, halogens such as fluorine, chlorine or bromine, nitro groups etc. Dyestuffs not containing heavy metal which can be used according to the invention are, among others, neutral to quickly drawing acid wool dyestuffs of the azo series, for example, disazo dyestuffs containing sulfonic acid groups with diphenylether, diphenylamine, phenylnaphthylamine or phenylsulfonyloxyaryl groupings, also neutral or quickly drawing acid wool dyestuffs of the triphenylmethane or diphenyl-indolylmethane series, of the pyrene series, e.g. rhodamines such as halogenated rhodamine dyestuffs, of the anthraquinone series, e.g. the 4,4- bis (4 amino 3 sulfo anthraquinonyl 1 amino)- diphenylalkane dyestuffs. These dyestuffs can also contain in their aromatic nuclei substituents conventional in dyestuffs listed above.
Synthetic polyamide fibers which can be evenly dyed according to the invention are, for example, the materials known in the textile industry by the following names:
Nylon 66, a textile fiber from hexamethylene-diamine and adipic acid produced by condensation;
Nylon 610, a textile fiber from the same diamine and sebacic acid, produced by condensation;
Nylon 66/ 6, a textile fiber from mixed polymers produced by condensation of hexamethylene-diamine and adipic acid and addition of e-caprolactam;
Nylon 6, a textile fiber produced from addition polymers of e-CilPlOlfiCtflHl;
Nylon 11, a textile fiber from w-aminododecanoic acid produced by condensation, as well as polyamide fibers of the same or similar structure most of which are commercially available.
The preferred polyaminoethers mentioned and others used in the composite dye assistants according to the invention are obtained, for example, from diprimary or diprimary-secondary or diprirnary-tertiary alkylene polyamines and from diprimary or diprimary-secondary or diprimary-tertiary dior triethers by condensing in the heat with an at most equimolecular amount of alkyl, alkylbenzyl, cycloalkyl or alkylcycloalkyl chlorides or bromides or of alkali metal salts of acid sulfates of the corresponding hydroxyl compounds. After liberating the bases obtained with strong alkalis, any more easily volatile components still present are distilled off, advantageously in vacuo, and the mixture of bases which is not easily volatile is used direct for the condensation with styrene oxide.
These starting materials which advantageously contain one primary amino group and, in all, at least 2 but advantageously not more than 4 basic nitrogen atoms, are reacted, according to the invention, first with an equimolecular amount of styrene oxide. In this reaction an amino group, particularly easily a primary amino group, is substituted by the fl-hydroxyphenethyl radical, probably by the fl-hydroxy-fi-phenylethyl radical. The reaction product is then reacted with a low molecular alkylene oxide, in particular with ethylene oxide or propylene oxide or with mixtures of the two, in such amounts and under such conditions that at least 50, in particular in all 70 to alkyleneoxy radicals are introduced. Depending on the desired properties of the end products, it is often advantageous if certain proportions of ethylene oxide and propylene oxide are reacted simultaneously or one after the other with the styrene oxide-polyamine condensation products. The condensation products which contain at least 50 and advantageously more than 70 ethyleneoxy radicals and have a low content of propyleneoxy radicals are generally still sufficiently watersoluble for direct use for the purposes intended. It is often advantageous for an intended use of the condensation products according to the invention if they contain more than one phenylethyleneoxy radical. It is possible, without difficulty, at any stage, i.e. before, during or after the reaction with alkylene oxide, to add single equivalents of styrene oxide. However, in order to attain sufficient water-solubility, it is indicated to limit the number of phenylethyleneoxy groups incorporated. This number should not be greater than the number of hydrogen atoms bound direct to basic nitrogen atoms in the starting material. Advantageously, in all there should not be more than three such groups.
The epoxides are added under the usual conditions. Whereas for the addition of styrene oxide in the first step it is generally sufficient to react the component by heating to about 100 C. to 200 C. depending on the composition, generally a basic catalyst such as sodium or potassium hydroxide, carbonate or alcoholate, is necessary for the addition of the alkylene oxides. Depending on their reactivity, the alkylene oxides can be incorporated in the solutions of the starting materials and catalysts in inert organic solvents, or in the melts of the starting materials, if necessary under pressure. In general, raised temperatures of, for example 80 C. up to about 200 C. are indicated.
The following examples illustrate the invention. Temperatures are given therein in degrees centigrade. Parts and percentages are by weight unless expressly stated otherwise. C.I. means Colour Index, second edition, 1956, published by the Society of Dyers and Colourists, Bradford, England, and the American Association of Textile Chemists and Colorists, Lowell, Mass, USA.
EXAMPLE 1 A high temperature beam dyeing machine consisting of a closed system fitted with a circulation pump for circulating the liquor both from inside to the outside and vice versa is used. In the vat for the dye liquor in this machine, 1 kg. of a polyglycol ether produced by reacting 90 mols of ethylene oxide with N-stearyl diethylenetriamine and 0.6 kg. of hexamethylenetetramine are dis solved in 1500 liters of water, and the pH of the solution is adjusted to about 4.5 by the gradual addition of about 1.5 kg. of 40%-acetic acid. 110 kg. of warp-knit tricot of nylon 6 wound round the perforated beam are introduced, the apparatus is closed and the circulation pump is set in action. After minutes, a mixture of 1.0 kg. of the chromium-containing dyestulf obtained from 2 mols of 1 phenyl 3 methyl-4-(2'-carboxy-5-methy1- sulfonylphenylazo) -5-pyrazolone per chromium gram atom bound in complex linkage, 0.6 kg. of the chromiumcontaining dyestuff obtained from 2 mols of l-acetylamino 7 hydroxy 8 (2 hydroxy-5'-ethylsulfonylphenylazo) naphthalene per chromium gram atom, bound in complex linkage, and 0.25 kg. of the chromiumcontaining dyestuff obtained from 2 mols of l-phenyl- 3-rnethyl 4 (2 hydroxy-S'-ethylsulfonyl-phenylazo)- 5-pyrazolone per chromium gram atom, bound in complex linkage, and liters of hot water is drawn in through the pump system and the liquor is circulated from inside to outside during the Whole dyeing process, first for 10 minutes at room temperature then for minutes while gradually and evenly raising the temperature to 120 and then for 20 minutes at this temperature. The liquor is then allowed to cool to below 100, V
the excess pressure is removed and the dyed goods are rinsed with circulating warm and cold water. Goods very evenly dyed in a stone grey-olive shade are obtained. The dyeings are Wetand light-fast.
Very similar results are obtained by using, in this example, instead of the dyestuffs disclosed, commercial products of similar structure, e.g. C.I. Acid Yellow 129, C.I. Acid Black and C.I. Acid Orange 86.
When in this or one of the following examples, 0.1 to 6% calculated on the weight of the textile material to be dyed, of one or more of the commercial dyestuffs given below are used, depending on the desired shade, then similar level and wet-fast dyeings of a corresponding shade are obtained. The following dyestuffs are thus used:
(a) Unsulfonated 1:2 metal complexes of monoazo dyestuffs containing lower alkylsulfonyl groups as groups promoting water-solubility: C.I. Acid Red 259; C.I. Acid Violet 78; C.I. Acid Brown 227; C.I. Acid Red 258; C.I. Acid Black 64;
(b) Monoazo dyestuffs, free from sulfonic acid groups, but having sulfamyl or sulfa-myl groups substituted at the nitrogen atom by lower alkyl .as groups promoting water-solubility: C.I. Acid Red 219; C.I. Acid Blue 166; C.I. Acid Yellow 116; C.I. Acid Orange 88; C.I. Acid Red 211; C.I. Acid Violet C.I. Acid Blue 171; C.I.
Acid Blue 168; C.I. Acid Black 60; C.I. Acid Red 300; C.I. Acid Brown 252;
(c) Monoazo dyestuffs containing an o-areno-oxymethylene-sulfonyl group: C.I. Acid Violet 96; C.I. Acid Blue 200; C.I. Acid Blue 199.
The polyglycol ether used in Example 1 is produced as follows: a
92 parts of N-stearyldiethylenetriamine produced by known methods from sulfatized stea'ryl alcohol and diethylenetriamine, are melted by heating to70-80". A solution of 2.3 parts of sodium inlOO parts of alcohol is then added to the reaction mixture. After mixing well, the alcohol is distilled off and 990 parts of ethylene oxide is introduced into the melt at a temperature of -120. On cooling, the reaction mixture solidifies into an almost colorless mass. The product dissolves well in water and foams very little in aqueous solution.
EXAMPLE 2 100 kg. of nylon 6 velour are dyed on the perforated beam of a high temperature beam dyeing machine described in Example 1 in a liquor containing 0.6 kg-ofthe polyglycol ether used in Example 1; 0. 6 kg. of hexamethylenetetramine and about 1 kg. of aqueous 40%- acetic acid in 1500 liters of water. The liquor is circulated in the closed machine for 10 minutes at room temperature and then the mixture of 3 kg. of the brown, mixed, monosulfonated dyestutf chromium complex obtained from 1- phenyl 3 methyl 4 (2-hyrlroxy-5'-sulfophenylazo)- S-pyrazolone and 1-(2-hydroxy-5-phenylazophenyl-azo)- 2-hydroxynaphthalene with 15 liters of hot Water is pumped in. The liquor is circulated for 10 minutes at room temperature, the pressure is brought to 2 to 4 atmospheres excess pressure by a pressure pump, the temperature is gradually and evenly raised within 30 minutes to 100 and dyeing is performed for 40 minutes at this temperature. The liquor is then cooled, excess pressure is removed and the dyed goods are rinsed first warm and then cold. Deep brown, very evenly dyed, wet-fast and light-fast goods are obtained.
When, in this example, analogous, so-called mixed dyestulf-chromium complexes are used, the two co-ordinated azo dyestuffs of which contain open sole sul-fonic acid group, e.g. C.I. Acid Blue 184 and C.I. A'cid Black 132, lightand wet-fast, very evenly dyed polyamide articles are also obtained.
EXAMPLE 3 In the dyeing machine described in Example 1, 100 kg. of nylon 6 fabric are dyed on the perforated beam in 1500 liters of water containing 1 kg. of polyglycol ether from monostearyl diethylenetriamine, 2 mols of styrene oxide, 100 mols of ethylene oxide, 5 mols of propylene oxide, 0.5 kg. of hexamethylenetetramine and 1.0 kg; of 40%-acetic acid. The liquor is first circulated for 10 minutes at room temperature, 2 to 4 atmospheres excess pressure being applied by an additional pump. Then the mixture of 1.5 kg. of the orange dyestuff chromium complex, produced by adding 2-hydroxybenzene-1-carboxylic 'acid-5-sulfonic acid phenyla-mide to the monoazo dyestuif metallized in a ratio of 1 chromium atom per 1-(3'chlorophenyl)-3-methyl-4-(2-hydroxy-5-sulfamido-phenyl)- azo-S-pyrazolone, with 15 liters of hot Water is then drawn in. The liquor is first circulated for 10 minutes at room temperature and then, in a closed vessel,'it is heated up within 40 minutes to Dyeing is performed for 25 minutes at this temperature. After cooling, the dyeing is rinsed with warm and then cold water. A very level, lightand wet-fast orange dyeing is obtained.
The polyglycol ether used in Example 3 is produced as follows: i
92 parts of N-stearyldiethylenetriamine are melted by heating to 7080. 62 parts of styrene oxide are then added to the melt and the whole is heated while stirring at 120. Heat is then generated and the temperature of the reaction mixture rises to 186. After cooling to 140- 150 the mixture is stirred for about hours at this temperature. Analysis shows that the reaction product obtained is N -stearyl-N N -bis-(B-phenyl-hydroxyethyl)- diethylenetriamine. A solution of 2.3 parts of sodium in 100 parts of alcohol is then added to the reaction mixture. After mixing well, the alcohol is distilled off and first 60 parts of propylene oxide and then 1100 parts of ethylene oxide are introduced into the melt at a temperature of 110-120". On cooling, the reaction mixture solidifies into an almost colorless mass. The product dissolves well in Water and foams very little in aqueous solution.
EXAMPLE 4 In a high temperature beam dyeing machine, 100 kg. of nylon 6 tafieta are dyed on the beam with a solution of 1 kg. of polyglycol ether from oleylethylenediamine, 1 mol of styrene oxide and 50 ml. of ethylene oxide, 0.8 kg. of hexamethylenetetramine and 2 liters of 40% H 50 in 1500 liters of water. After bringing the pressure to 2 to 4 atmospheres excess pressure, the liquor is circulated for minutes at room temperature, then the mixture of 2 kg of the chromium-containing monoazo dyestutf 1- (2' hydroxy 4 nitrophenylazo) 2 (2" carboxy- 4" sulfamidophenylamino) naphthalene containing 1 chromium atom and 1 mol of 8-hydroxyquinoline bound in complex linkage, with liters of hot water is added, the liquor is circulated first for 10 minutes at room temperature then, in a closed vessel, it is heated to 120 within 30 minutes and then kept at this temperature for minutes. It is then cooled, the goods are rinsed, after removal of the liquor, with warm and cold water.
A very level, lightand wet-fast green dyeing is obtained.
Dyeings having similar properties are obtained if in this example, the dyestuff disclosed is replaced by the similarly constructed commercial brand C.I. Acid Green 57.
Light-fast, level, pure blue dyeings are obtained also if, with otherwise the same procedure, in the above example 0.5 to 2 kg., depending on the desired depth of shade of a formazane dyestulf containing copper in a ratio of 1:1, (2 hydroxy 5' sulfoethylanilide 4" sulfonic acid phenylazo) (2 carboxyphenylazo) phenyl methane, (2 hydroxy 5' m sulfamidophenylsulfonylphenylazo) (2 carboxynaphthyl (3) azo) phenylmethane or -(2' hydroxy 4 sulfamido phenylazo) (5 chloro-2-carboxyphenylazo)-phenylmethane is used instead of the dyestutf disclosed.
77.5 parts of N-oleylethylene diamine obtained by condensing oleyl sulfonate with ethylene diamine are reacted at 140-150 with parts of styrene oxide. The mixture is stirred for about 4 hours at this temperature, then 1 part of sodium ethylate is added and then 550 parts of ethylene oxide are added at l10-120. The reaction is complete after a short time and the product solidifies on cooling.
EXAMPLE 5 In a high temperature beam dyeing machine fitted with a circulation pump, 100 kg. of nylon 6 shirting are dyed under the conditions described in Example 1 on the perforated beam by the method described in the previous examples. A liquor consisting of 2 kg. of polyglycol ether from stearylamine, 1 mol of styrene oxide and 70 mols of ethylene oxide, 0.5 kg. of hexamethylenetetramine and 1 kg. of %-acetic acid in 1500 liters of water is used. The goods are dyed with 3 kg. the disazo dyestuff produced from diazotized 3-aminobenzene-l-sulfonic acid-4'- cresol ester sulfonic acid, coupling with the technical mixture of 1-amino-naphthalene-6- and -7- sulfonic acid, diazotizing the aminoazo dyestutf and again coupling with 1- (4 methylphenylamino) naphthalene 8 sulfonic acid, by first pre-treating the goods for 10 minutes in the liquor containing the auxiliaries, then adding the mixture of the dyestuif with 15 liters of hot water circulating the liquor in a closed apparatus while heating to 120 within 45 minutes and further treating for 30 minutes at this liquor temperature. The liquor is then cooled to under removed and the dyed goods are rinsed with warm and cold water. A very level navy blue dyeing is obtained.
Level dyeings having good wet-fastness properties are also obtained if, instead of the neutral to weakly acid drawing dyestuff mentioned above, commercial brands are used which also contain the phenylsulfonic acid phenol ester groups and/or bis-arylamine groups which increase the afiinity to wool, for example, on C.I. Acid Red 119, C.I. Acid Yellow 79, C.I. Acid Orange 94, C.I. Acid Red 168.
The polyglycolether used in combination with hexamethylenetetramine as the dye assistant in Example 5, is produced as follows:
67.5 parts of N-stearylamine are melted by heating to 70. 30 parts of styrene oxide dissolved in toluene are added dropwise to the melt withinabout 10 minutes. The mixture is then slowly heated to At this temperature, heat is generated to about 150. On completion of the reaction, the temperature is kept at 140150 by warming for about 4 hours. A brown wax is formed which gradually solidifies in the cold.
The resulting N-stearylamino-2-phenylethanol mass obtained as described above is dissolved in 50 parts of alcohol in which 1 part of sodium has been dissolved. After thoroughly mixing, the alcohol is distilled 01f, the mixture is heated to l30 and then ethylene oxide is introduced until the increase in weight of the reaction product is 775 parts. The reaction product obtained solidifies on cooling and then completely dissolves in water.
EXAMPLE 6 100 kg. of nylon 6 fabric are dyed on the beam in a dyeing machine described in Example 1 by pro-treating the goods for 10 minutes at room temperature with the solution of 1 kg. of the known polyglycol ether obtained by condensing a technical mixture of cetyl and oleyl alcohol with ethylene oxide, which product possesses 50 ether groups, 0.8 kg. of hexamethylenetetramine and 0.8 kg. of 40%-acetic acid in 1700 liters of water. The pressure is then raised to 3 atmospheres excess pressure, and aqueous solution of 1.5 kg. of sodium saltof 1,4-bis-(2,6- dim-ethyl 4 phenoxyphenylamino)-anthraquinone disulfonic acid is added and, while circulating the liquor well, the tempearture is raised to 120 within 45 minutes and kept at this temperature for 25 minutes. The temperature is then cooled to under 100, the liquor is removed and the dyed goods are rinsed with warm and cold water.
A very level, strongly colored, wet-fast blue dyeing is obtained.
Dyeings having similar properties are obtained if, instead of the neutral to weakly acid drawing acid anthraquinone dyestuif described in the example, the similarly constructed commercial brands; C.I. Acid Blue 226; C.I. Acid Green 59; C.I. Acid Green 69.
EXAMPLE 7 100 kg. of nylon 6 knitted articles (tricot) are dyed in a modern type winch. The ends of the goods are sewn together and drawn through the liquor over a round or oval winch continuously. The goods are treated at room temperature for 10 minutes in a solution of 0.6 kg. of polyglycol ether from o ctadecyldiethylenetriamine, 2 mols of styrene oxide and i100 mols of ethylene oxide and also 0.35 kg. of hexamethylenetetramine and 0.6 kg. of 40%- -acetic acid in 1300 liters of water. The mixture of 1%- copper-containing formazane dyestulf [S-suIpho-ethylanilide 4 sulfonic acid 2 hydroxyphenylazo] [2- carboxyphenylazo]-phenylmethane containing 1 dyestuff molecule to 1 copper atom and of 2% disazo dyestutf obtained from tetrazotized 1,1-bis-[4'-(2-amino-benzenesulfonyloxy)phenyl]-cyclohexane coupled with 2 equiva- 1 1 lents of 1-(2-chloro-5-sulfophenyl)-3-methyl-5-aminopyrazole, with litersof hot water is added. The liquor is brought to the boil within minutes while circulating the goods Well and then dyeing is continued for minutes at the boil. The goods are then rinsed warm and cold.
A very level, full, light-fast green dyeing is obtained.
Similar level dyeings are obtained if, instead of the formazine dyestuff used above, similar copper-containing dyestuffs are used which, instead of a sulfonic acid group, contain sulfarnide groups as substituents promoting water-insolubility. Instead of the disazo dyestuff used above, similarly constructed commercial dyestuffs such as C.I. Acid Yellow 79 can be used.
The polyglycol ether used in Example 7 is produced as follows:
92 parts of N-stearyldiethylenetriamine are melted by heating to 7080."62 parts of styrene oxide are then added to the melt and the whole is heated while stirring at 120", Heat is then generated and the temperature of the reaction mixture rises to 186. After cooling to 140- 150 the mixture is stirred for about 5 hours at this temperature. Analysis shows that the reaction product obtained is N -stearyl-N ,N -bis- (B-phenyl-hydroxyethyl diethylenetriamine, A solution of 2.3 parts of sodium in 100 parts of alcohol is then added to the reaction mixture. After mixing well, the alcohol is distilled olf and 1100 parts of ethylene oxide are introduced into the melt at a temperature of 110-120". On cooling, the reaction mixture solidifies into an almost colorless mass. The product dissolves well in water and foams very little in aqueous solution.
We claim:
1. A process for dyeing of synthetic polyamide fiber textile material, com-prising beam-dyeing, the said material at a temperature of 100 to 130 C. with an aqueous dyestuif preparation which contains:
(a) as coloring agent, a neutralto weakly acid-drawing anionic wool dyestuif selected from the chromium and cobalt complexes of o,o-dihydroxy -mono- *azo, -disazo and -azomethine dyestuffs, of o-hydroxy-o' carboxy monoand dis-azo dyestuffs, of o-hydroxy-o-amino monoand dis-azo dyestuffs which, per heavy metal atom, contain two identical or different dyestuffs bound in complex linkage, and contain a group promoting water-s0lubility which is selected from the group consisting of a lower alkylsulfonyl group, a sulfamyl group or an acylamido group, and is free from or contains, inthe case of said dyestufi being a 2:1 complex consisting of a monosulfonated and an unsulfonated basic dyestuif bound in complex linkage to a chromium or cobalt atom, a salt-forming group which dissociates acid;
(b) a non-ionogenic surfactant ether, which is the condensation product obtained by reacting 1 mol of a polyamine of the general formula:
L represents a lipophilic alkyl or alkenyl radical having 16-18 carbon atoms,
A represents an alkenylene radical selected from the group consisting of -CH CH and radicals,
X represents a member selected from the group consisting of NH- and -O, and
m represents one of the numbers 0 to 2,
first with 1 mol of styrene oxide at a temperature of about 100 to, 200 C., and then reacting the resulting intermediate in any order desired with 50 to 150 mols of ethylene oxide and *0 to 2 mols of styrene oxide of propylene oxide, at a temperature of about to 200 C.,
(c) hexamethylenetetramine,
(d) the pH of said preparation at the beginning of dyeing being less than 7.5 but not less than 3; the weight ratio of (b) to (c) being in the range of from about 4:1 to 1:4.
, 2. A process accordingto claim 1 wherein the pH value of the dyestuff preparation is adjusted to the aforesaid range by addition of a lower aliphatic carboxylic acid.
3. A process as described in claim 1, wherein said ether defined under (b) is a polyaminoether obtained by reacting 1 mol of the polyamine of the general formula:
wherein m represents one of the numbers 0 to 2,
first with 1 to 2 mols of styrene oxide and then with 70 to mols of ethylene oxide, and the weight ratio of (b):(c) ranges from about 3:1 to 1:3.
4. A process as described in claim 1, wherein said surfactant ether defined under (b) is the polyglycol ether obtained from monostearyl diethylenetriamine, 2 mols of styrene oxide, 100 mols of ethylene oxide and 5 mols of propylene oxide.
5. A process as described in claim 1, wherein said surfactant ether defined under (b) is the polyglycolether from oleylethylenediamine, 1 mol of styrene oxide and 50 mols of ethylene oxide.
6. A process as described in claim 1, wherein said surfactant ether defined under (b) is the polyglycol ether from stearylamine, 1 mol of styrene oxide and 70 mols of ethylene oxide.
7. A process as described in claim 1, wherein said surfactant ether defined under (b) is the polyglycol ether from octadecyldiethylenetriamine, 2 mols of styrene oxide and 100 mols of ethylene oxide.
8. A process 'for the dyeing of synthetic polyamide fiber textile material, comprising beam dyeing, the said material at a temperature of 100 to C. with an aqueous dyestuff preparation which contains:
(a) a dyestuff selected from the group consisting of copper complexes of metallizable disazo dyestuffs of the formazane series; unmetallized disazo dyestuffs containing sulfonic acid groups, and 4,4'-bis-(4- amino 3 sulfo anthraquinonyl 1 amino)- diphenylalkane dyestuffs:
(b) a non-ionogenic surfactant ether, which is the condensation product obtained by reacting 1 mol of a polyamine of the general formula:
L represents a lipophilic alkyl or alkenyl radical having 16-18 carbon atoms,
A represents an alkylene radical selected from the group consisting of --CH CH and radicals,
X represents a member selected from the group consisting, of --NH and -O--, and
m represents one of the numbers 0 to 2,
13 14 first with 1 mol of styrene oxide at a temperature of References Cited about 100 to 200 C., and then reacting the result- UNITED STATES PATENTS ing intermediate in any order desired with 50 to 150 mols of ethylene oxide and 0 to 2 mols of styrene 5 g :3 x 5 as y e r oxide of poropylene oxlde, at a temperature of about 3,307,901 3/1967 Bindler et a1. 8 54 80 to 200 (3., (c) hexamethylenetetramine, FOREIGN PATENTS (d) the pH of said preparation at the beginning of 824,459 12/1959 Great Britain dyeing being less than 7.5 but not less than about 0 3; the weight ratio of (b) to (c) being in the range NORMAN G. TORCHIN, Primary Examiner.
of from about 4:1 to T. J. HERBERT, Assistant Examiner.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH391664 | 1964-03-26 |
Publications (1)
Publication Number | Publication Date |
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US3401004A true US3401004A (en) | 1968-09-10 |
Family
ID=4266245
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US373536A Expired - Lifetime US3401004A (en) | 1964-03-26 | 1964-06-08 | Process for the dyeing of synthetic polyamide fibers |
Country Status (7)
Country | Link |
---|---|
US (1) | US3401004A (en) |
BE (1) | BE661639A (en) |
CH (1) | CH391664A4 (en) |
DE (1) | DE1469753A1 (en) |
ES (1) | ES311249A1 (en) |
GB (1) | GB1090619A (en) |
NL (1) | NL6503824A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3606988A (en) * | 1967-08-08 | 1971-09-21 | Bayer Ag | Process for dyeing nitrogen-containing fibre materials |
US4563192A (en) * | 1983-09-19 | 1986-01-07 | Ciba-Geigy Corporation | Process for dyeing fibre material made of synthetic polyamides with anionic dyes and an auxiliary mixture |
CN1034515C (en) * | 1992-01-27 | 1997-04-09 | 湖南省原子能农业应用研究所 | Radiation method for preservation activity and sterilization of food grade saccharidase preparation |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB824459A (en) * | 1956-08-29 | 1959-12-02 | Bayer Ag | Dyeing of nitrogen-containing fibres |
US3049392A (en) * | 1962-08-14 | Process for dyeing nitrogenous mate- | ||
US3104931A (en) * | 1958-03-11 | 1963-09-24 | Ciba Geigy Corp | Process for dyeing wool |
US3307901A (en) * | 1961-05-24 | 1967-03-07 | Geigy Ag J R | Process for dyeing polyamide textile materials and auxiliaries therefor |
-
1964
- 1964-03-26 CH CH391664D patent/CH391664A4/en unknown
- 1964-04-01 DE DE19641469753 patent/DE1469753A1/en active Pending
- 1964-06-08 US US373536A patent/US3401004A/en not_active Expired - Lifetime
-
1965
- 1965-03-25 BE BE661639D patent/BE661639A/xx unknown
- 1965-03-25 ES ES0311249A patent/ES311249A1/en not_active Expired
- 1965-03-25 NL NL6503824A patent/NL6503824A/xx unknown
- 1965-03-25 GB GB12655/65A patent/GB1090619A/en not_active Expired
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3049392A (en) * | 1962-08-14 | Process for dyeing nitrogenous mate- | ||
GB824459A (en) * | 1956-08-29 | 1959-12-02 | Bayer Ag | Dyeing of nitrogen-containing fibres |
US3104931A (en) * | 1958-03-11 | 1963-09-24 | Ciba Geigy Corp | Process for dyeing wool |
US3307901A (en) * | 1961-05-24 | 1967-03-07 | Geigy Ag J R | Process for dyeing polyamide textile materials and auxiliaries therefor |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3606988A (en) * | 1967-08-08 | 1971-09-21 | Bayer Ag | Process for dyeing nitrogen-containing fibre materials |
US4563192A (en) * | 1983-09-19 | 1986-01-07 | Ciba-Geigy Corporation | Process for dyeing fibre material made of synthetic polyamides with anionic dyes and an auxiliary mixture |
CN1034515C (en) * | 1992-01-27 | 1997-04-09 | 湖南省原子能农业应用研究所 | Radiation method for preservation activity and sterilization of food grade saccharidase preparation |
Also Published As
Publication number | Publication date |
---|---|
DE1469753A1 (en) | 1968-12-19 |
NL6503824A (en) | 1965-09-27 |
BE661639A (en) | 1965-09-27 |
ES311249A1 (en) | 1966-02-01 |
CH391664A4 (en) | 1966-02-28 |
GB1090619A (en) | 1967-11-08 |
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