US3049392A - Process for dyeing nitrogenous mate- - Google Patents
Process for dyeing nitrogenous mate- Download PDFInfo
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- US3049392A US3049392A US3049392DA US3049392A US 3049392 A US3049392 A US 3049392A US 3049392D A US3049392D A US 3049392DA US 3049392 A US3049392 A US 3049392A
- Authority
- US
- United States
- Prior art keywords
- dyeing
- acid
- dye
- ethylene oxide
- wool
- 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
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- 238000004043 dyeing Methods 0.000 title claims description 56
- 238000000034 method Methods 0.000 title claims description 40
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title description 16
- 239000002253 acid Substances 0.000 claims description 42
- 150000001875 compounds Chemical class 0.000 claims description 38
- 239000000463 material Substances 0.000 claims description 24
- RBTKNAXYKSUFRK-UHFFFAOYSA-N Heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 claims description 22
- 239000002657 fibrous material Substances 0.000 claims description 16
- LSNNMFCWUKXFEE-UHFFFAOYSA-L Sulphite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims 2
- 239000000975 dye Substances 0.000 description 66
- 229940117927 Ethylene Oxide Drugs 0.000 description 54
- IAYPIBMASNFSPL-UHFFFAOYSA-N oxane Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 54
- 210000002268 Wool Anatomy 0.000 description 44
- -1 for example silk Substances 0.000 description 44
- 239000000047 product Substances 0.000 description 32
- 125000004432 carbon atoms Chemical group C* 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 30
- 150000001412 amines Chemical class 0.000 description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 24
- 239000000835 fiber Substances 0.000 description 22
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (Z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000009835 boiling Methods 0.000 description 12
- 239000007795 chemical reaction product Substances 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 230000000875 corresponding Effects 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 239000004952 Polyamide Substances 0.000 description 8
- 125000002947 alkylene group Chemical group 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 150000004665 fatty acids Chemical class 0.000 description 8
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 229920002647 polyamide Polymers 0.000 description 8
- 239000011528 polyamide (building material) Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 6
- 229940093470 Ethylene Drugs 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 150000002829 nitrogen Chemical group 0.000 description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N Adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N Hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N Lauric acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 229960004011 Methenamine Drugs 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M NaHCO3 Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N Tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 4
- 229960001124 Trientine Drugs 0.000 description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N Triethylenetetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 4
- 230000001476 alcoholic Effects 0.000 description 4
- 150000001447 alkali salts Chemical class 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 150000001879 copper Chemical class 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- VPNOHCYAOXWMAR-UHFFFAOYSA-N docosan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCCCN VPNOHCYAOXWMAR-UHFFFAOYSA-N 0.000 description 4
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecan-1-amine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 4
- 125000001033 ether group Chemical group 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000004312 hexamethylene tetramine Substances 0.000 description 4
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 4
- BUHXFUSLEBPCEB-UHFFFAOYSA-N icosan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCN BUHXFUSLEBPCEB-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 235000011007 phosphoric acid Nutrition 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- REYJJPSVUYRZGE-UHFFFAOYSA-N stearylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 4
- 125000000542 sulfonic acid group Chemical group 0.000 description 4
- 239000003760 tallow Substances 0.000 description 4
- 125000001302 tertiary amino group Chemical group 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 229940100198 ALKYLATING AGENTS Drugs 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N Caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N Diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N Dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N Hexamethylenediamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N Hexylamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N N-Butylamine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N Octadecanoic acid Natural products CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N Phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 241000083869 Polyommatus dorylas Species 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- 101710030983 RNF138 Proteins 0.000 description 2
- 229910006069 SO3H Inorganic materials 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N Sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 2
- 101710029702 TICAM1 Proteins 0.000 description 2
- 101710021425 TRIM69 Proteins 0.000 description 2
- 102100003447 TRIM69 Human genes 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Tris Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- YXZRCLVVNRLPTP-UHFFFAOYSA-J Turquoise Blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Cu+2].NC1=NC(Cl)=NC(NC=2C=C(NS(=O)(=O)C3=CC=4C(=C5NC=4NC=4[N-]C(=C6C=CC(=CC6=4)S([O-])(=O)=O)NC=4NC(=C6C=C(C=CC6=4)S([O-])(=O)=O)NC=4[N-]C(=C6C=CC(=CC6=4)S([O-])(=O)=O)N5)C=C3)C(=CC=2)S([O-])(=O)=O)=N1 YXZRCLVVNRLPTP-UHFFFAOYSA-J 0.000 description 2
- WREBNDYJJMUWAO-LWYYNNOASA-N [(1R,4aR,4bR,10aR)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthren-1-yl]methanamine Chemical compound NC[C@]1(C)CCC[C@]2(C)[C@@H](CCC(C(C)C)=C3)C3=CC[C@H]21 WREBNDYJJMUWAO-LWYYNNOASA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 239000002168 alkylating agent Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001409 amidines Chemical class 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000000987 azo dye Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 150000004700 cobalt complex Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 150000002169 ethanolamines Chemical class 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- CTKINSOISVBQLD-UHFFFAOYSA-N glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 2
- FJLUATLTXUNBOT-UHFFFAOYSA-N hexadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 150000002790 naphthalenes Chemical class 0.000 description 2
- 230000001264 neutralization Effects 0.000 description 2
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 229920000151 polyglycol Polymers 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N sulfonic acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 239000000979 synthetic dye Substances 0.000 description 2
- 239000003784 tall oil Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
- C09B47/24—Obtaining compounds having —COOH or —SO3H radicals, or derivatives thereof, directly bound to the phthalocyanine radical
- C09B47/26—Amide radicals
-
- 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
- Y10S8/916—Natural fiber dyeing
- Y10S8/917—Wool or silk
Definitions
- the process may be applied to any nitrogen-containing fibrous material, for example silk, polyamide fibers consisting of e-caprolactam or polyamide fibers consisting of condensates of adipic acid and hexamethylene diamine.
- any nitrogen-containing fibrous material for example silk, polyamide fibers consisting of e-caprolactam or polyamide fibers consisting of condensates of adipic acid and hexamethylene diamine.
- any nitrogen-containing fibrous material for example silk, polyamide fibers consisting of e-caprolactam or polyamide fibers consisting of condensates of adipic acid and hexamethylene diamine.
- the sulfonated copper phthalocyanines employed may contain, for example, two, three or four sulfonic acid groups and, if desired, also further substituents such as halogen atoms, more especially chlorine, or sulfonic acid amide groups.
- Dye mixtures may also be employed, for example sulfonation mixtures whose components diifer in the number of sulfonic acid groups, or mixtures of sulfonated copper phthalocyanines with other dyes suitable for dyeing nitrogenous fibers from an acid bath. These latter may be, for example, dyes which contain a mobile halogen atom, i.e.
- one reactable with the fiber material preferably a chlorine atom, or dyes consisting substantially of 1:2-chromium or cobalt complex compounds of azo dyes (preferably monoazo dyes) which contain at least two acid water-solubilizing groups in the molecule of the metal complex.
- azo dyes preferably monoazo dyes
- the dyeing is eifected in the presence of auxiliary compounds which contain at least one basic nitrogen atom, to which there is attached at least one radical containing a glycol ether chain.
- This chain contains at least two groupings of the structure I set forth above and may be attached to the nitrogen atom either directly or through a bridge member, for example an alkylene radical, such as an npropylene radical.
- the molecule of the auxiliary compound should contain in total, at least three groups of structure I, preferably groups of the structure:
- the auxiliary compound must contain at least four carbon atoms not belonging to a group of structure 1.
- it may advantageously contain at least one aliphatic or alicyclic radical comprising at least eight, or preferably twelve, interlinked carbon atoms, or
- a,fi-alkylene oxides such as ethylene oxide, propylene oxide or glycidol. Particularly valuable products are obtained using ethylene oxide.
- organic compounds containing at least one primary or secondary amino group, or containing a basic tertiary amino group and in addition an alcoholic hydroxyl group there may be used amines of the aliphatic and of the aromatic and alicyclic series.
- Suitable aliphatic amines are monoarnines for example diethylamine, butylamine, hexylamine, dodecylamine, cetylamine, oleylamine, octadecylamine, arachidylamine, behenylamine, or mixtures of any of these monoamines.
- Suitable polyamines are triethylene tetramine and the corresponding N-alkylpolyamines comprising alkyl radicals of higher molecular weight and containing from 8 to 22 carbon atoms.
- Basic derivatives of such amines may also be employed, such as esters of hydroxyamines with higher fatty acids, for example triethanolamine cocinic acid esters, or partial amides of polyamines with fatty acids, for example triethylene tetramine monoacylated with cocinic acid.
- Particularly suitable aromatic amines are amines of the benzene and naphthalene series with alkyl side chains containing, for example, from 8 to 18 carbon atoms.
- resin amines such as abietylamine, abietyl methylamine, the amine mixture corresponding to tall oil (which contains resin amines in addition to higher alkylamines), or hydrogenated abietylamines.
- amidines such as lauric acid or stearic acid amidine, may be employed as starting material.
- Products suitable for the purpose of the present-invem tion are those obtainable by reaction of 1 mol of an amine as aforesaid with at least 3 mols, for example 3 to 20 mols, of an alkylene oxide, for example:
- alkyl radical corresponds to the radicals of tallow fatty acids, with 8 mols of ethylene oxide
- R represents an aliphatic hydrocarbon radical preferably unbranched and containing at least 12 and preferably 16 to 22 carbon atoms
- rm and 11 represent integers of a value of at most 2
- p, q and r represent integers, the sum p+q+(m1)(r1) amounting to at least 3 and at most and at least one of the values p, q and r-l being greater than 1.
- R represents an aliphatic hydrocarbon radical, preferably unbranched and containing at least 12 and preferably from 16 to 20 carbon atoms
- p and q are integers, and the sum p+q amounts to at least 3 and preferably to 8 to 16, are preferred Compounds for use in the present invention.
- the foregoing compounds contain free hydroxy-alkyl groups and there may be used, instead of the free hydroxyl-alkyl compounds, the corresponding esters thereof, e.g. those formed from polybasic acids, for example phosphoric acid or sulfuric acid, or the water-soluble salts of these esters, for example alkali or ammonium or amine salts thereof.
- the corresponding esters thereof e.g. those formed from polybasic acids, for example phosphoric acid or sulfuric acid, or the water-soluble salts of these esters, for example alkali or ammonium or amine salts thereof.
- auxiliary compounds referred to above and employed in the present invention may be produced by methods usual to the production of ethylene oxide addition products, for example by the reaction of the alkylene oxide with the amine at elevated temperature.
- the alkylene oxide is added to the amine only gradually, for example by adding it in gaseous or liquid form to the amine, or introducing it into the latter at a temperature at which the alkylene oxide reacts, for example at 50-200 C.
- the operation may be carried out in a closed vessel and under pressure, advantageously at a pressure of from 2 to 10 atmospheres gauge.
- catalysts may be added to the reaction mixture.
- Such catalysts may with advantage be substances having an alkaline reaction, such as metallic sodium, alkali metal hydroxides, alkali metal carbonates or alkali metal salts of carboxylic acids of low molecular weight.
- the products of condensation employed in accordance with the invention are soluble in water or can be readily dispersed therein.
- the water solubility may if desired be increased by introducing groups which favor water solubility.
- the auxiliary compounds may be formed as quaternary ammonium salts produced by treat ment with alkylating agents.
- the re action product of oleylamine with 6 to 10 mole of eth ylene oxide may be quaternized by treatment with dimethyl sulfate.
- the auxiliary compounds used in the present invention may be obtained by the introduction of polyglycol ether chains with a corresponding number of ether groups into the amines.
- the quantities of substances which must be added to the dye baths may vary within relatively wide limits.
- the quantity of dye naturally depends upon the desired color strength. It is desirable to adapt the quantity of the auxiliary compounds to that of the dye in such manner that the proportion by weight is about 1:8 to 1:2.
- the quantity of auxiliary compound should be at least (calculated on the weight of fiber) even in the case of light dyeing for which less than 1% of dyealso calculated on the fiber weight-is used.
- they may be previously made up as a stable preparation in suitable proportion and this preparation then added.
- the dyeing is advantageously carried out in an acetic acid medium, that is to say, in such manner than the dye bath exhibits an acetic acid reaction at least at the beginning of the dyeing. Therefore, there is preferably added to the dye bath at the beginning of the dyeing at least so much acetic acid that the desired pH value is obtained, account having to be taken of the fact that some acid is lost by reaction both with the nitrogenous fibrous material and by the dyes which are generally present in the form of alkali salts.
- the dyeing operation is preferably carried out at elevated temperature, and most suitably by commencing the actual dyeing process at about 50 to 70 C., heating to boiling temperature and continuing and completing the process at this temperature. After heating to about C., the dye bath may be maintained at this temperature for some time and brought to boiling temperature only when the dye has been substantially completely absorbed by the fiber. In suitable apparatus dyeing may if desired be carried out at temperatures above C., e.g. at about 107 C.
- the pH value of the bath is raised to a value above 6.
- Any water-soluble compound having an alkaline reaction is suitable for increasing the pH value, but in order to avoid damage to the fiber, especially in the dyeing of wool, it is desirable to add substances having an alkaline reaction, which raise the pH to a value not exceeding 9.
- the pH value is with advantage raised to 6.5 to 9.
- Nitrogenous bases may advantageously be employed for raising the pH value, for example amines such as ethanolamines. In some cases ammonia yields good results and hexarnethylene tetramine has proved particularly suitable.
- Alkali salts of phosphoric acids, more especially dialkali or trialkali orthophosphates or polyphosphates, are also useful for this purpose.
- a mixture of two or more substances having an alkaline reaction for example ammonia and hexamethylene tetramine, may be employed.
- the after-treatment at the raised pH value need take only a relatively short time, for example about 10 to 30 minutes. It preferably takes place at about the same temperature as that at which the dyeing was effected.
- the dye bath may be maintained at boiling temperature throughout the after-treatment, or the temperature may be allowed to fall slightly during this aftertreatment, for example by supplying no further heat after the increase of the pH value.
- the dyed fibrous material may be rinsed and dried as usual with warm and/or cold water.
- Example 1 A dye bath is formed consisting of 3,000 parts of water, 1 part of copper phthalocyanine trisulfonic acid, 5 parts of 40% acetic acid and 0.5 part of the hereinafter described addition product of oleylamine and ethylene oxide. 100 parts of wool yarn are introduced into the bath at 40 the temperature is raised to 90 during 20 minutes and dyeing is effected at this temperature for about 30 minutes until the dye bath is substantially exhausted.
- Example 4 The procedure of the preceding examples is followed,
- Wool yarn is dyed in accordance with the procedure but there is added to the y bath, to increase i116 P of Example 1, using copper phthalocyanine-3,3,3,3- value, instead of ammonia and hexamethylene tet-ramine, tetrasulfonic acid or copper phthalocyanine-3,4',4,4'"- ammonia alone, sodium bicarbonate, sodium triphosphate tetrasulfonic acid instead of copper phthalocyanine trif triethanolarnine.
- the dyeings thus after-treated are sulfonic acid, and the pH value is also increased by the also distinguished by good W t faStIleSS P p addition of ammonia at the end of the dyeing operation. Blue dyeings are obtained with good wet fastnesses.
- Green dyeings are obtained when a mixture of copper A mixed fabric or blended yarn consisting of wool and phthalocyanine trior tetrasulfonic acid and the dye of polyamide fibers in equal proportions, is dyed in accordthe formula ance with the procedure of one of Examples 1 to 3, the
- a process for dyeing nitrogenous fibrous material which comprises subjecting said material to treatment in an acid bath containing a sulfonated copper phthalocyanine in the presence of an auxiliary compound of the (a) N-alkyl-propylenedlamine, of which the alkyl radical f m la corresponds to the radicals of tallow fatty acids, 8
- Wool yarn is dyed in the manner indicated in Example 1. Instead of the product of reaction of oleylamine and ethylene oxide, however, one of the following products is employed:
- the reaction temperature is initially 140 to 1 150 and can gradually be lowered to to There are added to 30.75 parts X mol) of the re- 75 in which R represents an aliphatic hydrocarbon radical containing at least 12 carbon atoms, in each of the group ings --CHXCHX-O at least one of the two Xs represent a hydrogen atom and any X not representing hydrogen stands for a methyl group, m and n are integers of at the most 2, and p, q and r are integers, the sum p+q+(m--1)(r1) amounting to at least 3 and to at most 20, and, after the material has absorbed the required amount of dye, increasing the pH value of the dyebath to above 6.
- a process for dyeing wool which comprises subjecting the wool to treatment in an acid bath containing a sulfo nated copper phthalocyanine in the presence of an aux RLN 7...
- R represents an aliphatic hydrocarbon radical containing at least 12 and at the most 22 carbon atoms
- In and n are integers of at most 2
- p, q and r are integers, the sum p+q+(m-l) (r1) amounting to at least 3 and to at most 20, and, after the material has absorbed the required amount of dye, increasing the pH value of the dyebath to above 6.
- a process for dyeing wool which comprises subjecting the wool to treatment in an acid bath containing a sulfonated copper phthalocyanine in the presence of an auxiliary compound of the formula in which R represents an aliphatic hydrocarbon radical containing 12 to 20 carbon atoms, and p and q are integers, the sum p-l-q amounting to at least 3 and to at the most 22, and, after the material has absorbed the required amount of dye, increasing the pH value of the dyebath to above 6.
- a process for dyeing wool which comprises subjecting the wool to treatment in an acid bath containin a copper phthalocyanine trisulfonic acid in the presence of an auxiliary compound of the formula in which R represents an aliphatic hydrocarbon radical containing at least 12 carbon atoms, in each of the groupings CHXCHXO-- at least one of the two Xs represents a hydrogen atom and any X not representing hydrogen stands for a methyl group, in and n are integers of at the most 2, and p, q and r are integers, the sum p+q+(m-1)(r--1) amounting to at least 3 and to at most 20, and, after the material has absorbed the required in which R represents an aliphatic hydrocarbon radical containing at least 12 carbon atoms, in each of the groupings CHX-CHX-O at least one of the two Xs represents a hydrogen atom and any X not representing hydrogen stands for a methyl group, m and n are integers of at the most 2, and,
- a process for dyeing wool which comprises subjecting the wool to treatment in an acid bath containing a sulfonated copper phthalocyanine in the presence of an ethylene oxide addition product obtained from one molecular proportion of oleylamine and about 7 molecular proportions of ethylene oxide, and, after the material has absorbed the required amount of dye, increasing the pH value of the dyebath to above 6.
- a process for dyeing wool which comprises subjecting the wool to treatment in an acid bath containing a copper phthalocyanine trisulfonic acid in the presence of an ethylene oxide addition product obtained from one molecular proportion of oleylamine and about 7 molecular proportions of ethylene oxide, and, after the material has absorbed the required amount of dye, increasing the pH value of the dyebath to above 6.
- a process for dyeing wool which comprises subjecting the wool to treatment in an acid bath containing a copper phthalocyanine tetrasulfonic acid in the presence of an ethylene oxide addition product obtained from one molecular proportion of oleylamine and about 7 molecular proportions of ethylene oxide, and, after the material has absorbed the required amount of dye, increasing the pH value of the dyebath to above 6.
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Description
United States Patent Ofiiice 3,049,392 Patented Aug. 14, 1962 3,049,392 I PROCESS FOR DYEING NITROGENOUS MATE RIAL WITH SULFONATED COEPER PHTHALO- CYANINES Richard Casty, Kaiseraugst, and Heinz Abel, Reinach,
Switzerland, assignors to Ciba Limited, Basel, Switzerland No Drawing. Filed July 29, 1959, Ser. No. 830,189 Claims priority, application Switzerland Aug. 6, 1958 l Claims. (Cl. 8-1) wherein the molecule contains at least three groups of the structure (preferably --CH CH -Ogroups) and at least 4 carbon atoms not belonging to such a group, and, after the material has absorbed the required amount of dye, increasing the pH value of the dye bath to above 6.
The process may be applied to any nitrogen-containing fibrous material, for example silk, polyamide fibers consisting of e-caprolactam or polyamide fibers consisting of condensates of adipic acid and hexamethylene diamine. However, particular advantages are afiorded by the process in the dyeing of wool and of fibrous material containing both fibers of wool and of polyamide.
The sulfonated copper phthalocyanines employed may contain, for example, two, three or four sulfonic acid groups and, if desired, also further substituents such as halogen atoms, more especially chlorine, or sulfonic acid amide groups. Dye mixtures may also be employed, for example sulfonation mixtures whose components diifer in the number of sulfonic acid groups, or mixtures of sulfonated copper phthalocyanines with other dyes suitable for dyeing nitrogenous fibers from an acid bath. These latter may be, for example, dyes which contain a mobile halogen atom, i.e. one reactable with the fiber material, preferably a chlorine atom, or dyes consisting substantially of 1:2-chromium or cobalt complex compounds of azo dyes (preferably monoazo dyes) which contain at least two acid water-solubilizing groups in the molecule of the metal complex.
It is characteristic of the present invention that the dyeing is eifected in the presence of auxiliary compounds which contain at least one basic nitrogen atom, to which there is attached at least one radical containing a glycol ether chain. This chain contains at least two groupings of the structure I set forth above and may be attached to the nitrogen atom either directly or through a bridge member, for example an alkylene radical, such as an npropylene radical. The molecule of the auxiliary compound should contain in total, at least three groups of structure I, preferably groups of the structure:
In addition, the auxiliary compound must contain at least four carbon atoms not belonging to a group of structure 1. Thus, it may advantageously contain at least one aliphatic or alicyclic radical comprising at least eight, or preferably twelve, interlinked carbon atoms, or
an aromatic radical with an aliphatic side chain, attached to the basic nitrogen atom by an aryl carbon atom.
There are advantageously employed in the present process as nitrogen-containing components of the aforesaid type products of reaction of at least three mols of an a,(3-alkylene oxide with 1 mol of an organic compound which contains at least one basic primary or secondary amino group or one basic tertiary amino group and in addition an alcoholic hydroxyl group.
As starting materials for the preparation of such products of reaction there may be employed a,fi-alkylene oxides such as ethylene oxide, propylene oxide or glycidol. Particularly valuable products are obtained using ethylene oxide.
As organic compounds containing at least one primary or secondary amino group, or containing a basic tertiary amino group and in addition an alcoholic hydroxyl group, there may be used amines of the aliphatic and of the aromatic and alicyclic series. Suitable aliphatic amines are monoarnines for example diethylamine, butylamine, hexylamine, dodecylamine, cetylamine, oleylamine, octadecylamine, arachidylamine, behenylamine, or mixtures of any of these monoamines. Suitable polyamines are triethylene tetramine and the corresponding N-alkylpolyamines comprising alkyl radicals of higher molecular weight and containing from 8 to 22 carbon atoms. Basic derivatives of such amines may also be employed, such as esters of hydroxyamines with higher fatty acids, for example triethanolamine cocinic acid esters, or partial amides of polyamines with fatty acids, for example triethylene tetramine monoacylated with cocinic acid. Particularly suitable aromatic amines are amines of the benzene and naphthalene series with alkyl side chains containing, for example, from 8 to 18 carbon atoms.
' Among alicyclic amines there are preferably employed resin amines such as abietylamine, abietyl methylamine, the amine mixture corresponding to tall oil (which contains resin amines in addition to higher alkylamines), or hydrogenated abietylamines. In addition, amidines, such as lauric acid or stearic acid amidine, may be employed as starting material.
Products suitable for the purpose of the present-invem tion are those obtainable by reaction of 1 mol of an amine as aforesaid with at least 3 mols, for example 3 to 20 mols, of an alkylene oxide, for example:
The reaction product of 1 mol of dodecylamine With about 6 mols of ethylene oxide,
The reaction product of 1 mol of oleylamine, with 6, 8 or 16 mols of ethylene oxide,
The reaction product of 1 mol of stearylamine with 4, '8
or 16 mols of ethylene oxide,
The reaction product of monoalkylpropylene diamine, of
which the alkyl radical corresponds to the radicals of tallow fatty acids, with 8 mols of ethylene oxide,
The reaction product of monoalkylpropylene diamine, of which the alkyl radical is unbranched and contains from 16 to 18 carbon atoms, and 6 mols of ethylene oxide.
The two last mentioned compounds correspond, for example, to the formula:
in which R represents an aliphatic hydrocarbon radical preferably unbranched and containing at least 12 and preferably 16 to 22 carbon atoms, rm and 11 represent integers of a value of at most 2, and p, q and r represent integers, the sum p+q+(m1)(r1) amounting to at least 3 and at most and at least one of the values p, q and r-l being greater than 1.
Compounds of the formula:
wherein R represents an aliphatic hydrocarbon radical, preferably unbranched and containing at least 12 and preferably from 16 to 20 carbon atoms, p and q are integers, and the sum p+q amounts to at least 3 and preferably to 8 to 16, are preferred Compounds for use in the present invention.
The foregoing compounds contain free hydroxy-alkyl groups and there may be used, instead of the free hydroxyl-alkyl compounds, the corresponding esters thereof, e.g. those formed from polybasic acids, for example phosphoric acid or sulfuric acid, or the water-soluble salts of these esters, for example alkali or ammonium or amine salts thereof.
The auxiliary compounds referred to above and employed in the present invention may be produced by methods usual to the production of ethylene oxide addition products, for example by the reaction of the alkylene oxide with the amine at elevated temperature. Preferably, the alkylene oxide is added to the amine only gradually, for example by adding it in gaseous or liquid form to the amine, or introducing it into the latter at a temperature at which the alkylene oxide reacts, for example at 50-200 C. If desired, the operation may be carried out in a closed vessel and under pressure, advantageously at a pressure of from 2 to 10 atmospheres gauge. If desired, catalysts may be added to the reaction mixture. Such catalysts may with advantage be substances having an alkaline reaction, such as metallic sodium, alkali metal hydroxides, alkali metal carbonates or alkali metal salts of carboxylic acids of low molecular weight.
The products of condensation employed in accordance with the invention are soluble in water or can be readily dispersed therein. The water solubility may if desired be increased by introducing groups which favor water solubility. Thus, the auxiliary compounds may be formed as quaternary ammonium salts produced by treat ment with alkylating agents. Thus, for example the re action product of oleylamine with 6 to 10 mole of eth ylene oxide may be quaternized by treatment with dimethyl sulfate.
In an alternative method of preparation the auxiliary compounds used in the present invention may be obtained by the introduction of polyglycol ether chains with a corresponding number of ether groups into the amines.
The quantities of substances which must be added to the dye baths may vary within relatively wide limits. The quantity of dye naturally depends upon the desired color strength. It is desirable to adapt the quantity of the auxiliary compounds to that of the dye in such manner that the proportion by weight is about 1:8 to 1:2. The quantity of auxiliary compound, however, should be at least (calculated on the weight of fiber) even in the case of light dyeing for which less than 1% of dyealso calculated on the fiber weight-is used. Instead of adding the auxiliary compounds and the dyes separately to the dye bath, they may be previously made up as a stable preparation in suitable proportion and this preparation then added.
The dyeing is advantageously carried out in an acetic acid medium, that is to say, in such manner than the dye bath exhibits an acetic acid reaction at least at the beginning of the dyeing. Therefore, there is preferably added to the dye bath at the beginning of the dyeing at least so much acetic acid that the desired pH value is obtained, account having to be taken of the fact that some acid is lost by reaction both with the nitrogenous fibrous material and by the dyes which are generally present in the form of alkali salts.
As is generally usual in the dyeing of nitrogenous fibrous material, more especially wool, the dyeing operation is preferably carried out at elevated temperature, and most suitably by commencing the actual dyeing process at about 50 to 70 C., heating to boiling temperature and continuing and completing the process at this temperature. After heating to about C., the dye bath may be maintained at this temperature for some time and brought to boiling temperature only when the dye has been substantially completely absorbed by the fiber. In suitable apparatus dyeing may if desired be carried out at temperatures above C., e.g. at about 107 C.
On completion of the actual dyeing operation, the pH value of the bath is raised to a value above 6. Any water-soluble compound having an alkaline reaction is suitable for increasing the pH value, but in order to avoid damage to the fiber, especially in the dyeing of wool, it is desirable to add substances having an alkaline reaction, which raise the pH to a value not exceeding 9. The pH value is with advantage raised to 6.5 to 9. Nitrogenous bases may advantageously be employed for raising the pH value, for example amines such as ethanolamines. In some cases ammonia yields good results and hexarnethylene tetramine has proved particularly suitable. Alkali salts of phosphoric acids, more especially dialkali or trialkali orthophosphates or polyphosphates, are also useful for this purpose. A mixture of two or more substances having an alkaline reaction, for example ammonia and hexamethylene tetramine, may be employed.
The after-treatment at the raised pH value need take only a relatively short time, for example about 10 to 30 minutes. It preferably takes place at about the same temperature as that at which the dyeing was effected. For example, the dye bath may be maintained at boiling temperature throughout the after-treatment, or the temperature may be allowed to fall slightly during this aftertreatment, for example by supplying no further heat after the increase of the pH value. Finally, the dyed fibrous material may be rinsed and dried as usual with warm and/or cold water.
As a result of the after-treatment at elevated pH value, a part of the dye situated on the fiber returns into the dye bath, but this is dye which is not fixed, or is not properly fixed to the fiber, so that the dyeings obtained by the process of the present invention have better wet fastness properties than the corresponding dyeings produced without subsequent increase of the pH value.
The following examples, in which the parts are by weight, the percentages by weight, and the temperatures, as in the foregoing description, are in degrees centigrade, unless otherwise stated, will serve to illustrate this invention:
Example 1 A dye bath is formed consisting of 3,000 parts of water, 1 part of copper phthalocyanine trisulfonic acid, 5 parts of 40% acetic acid and 0.5 part of the hereinafter described addition product of oleylamine and ethylene oxide. 100 parts of wool yarn are introduced into the bath at 40 the temperature is raised to 90 during 20 minutes and dyeing is effected at this temperature for about 30 minutes until the dye bath is substantially exhausted. The
bath is then brought to boiling temperature and the dyeweaker, very skittery and therefore substantially unusable sulting ethylene'oxide addition product in a stirrer-type dyeing is obtained. By the addition of the substances of vessel at 60 during 15 minutes 5.4 parts of urea, and alkaline reaction towards the end of the dyeing operathen during 30 minutes 5.4 parts of sulfamic acid 5 tion, the wet fastnesses (fastness to washing, milling, water mol and 10%), and the mixture is maintained on a and perspiration) are considerably increased. boiling water bath for 5 to 6 hours in a current of The ethylene oxide addition product referred to above nitrogen. The product obtained (41 parts) is readily is prepared as follows: water-soluble and has a neutral reaction.
1 part of finely divided sodium is added to 100 parts of commercial oleylamine and the mixture is heated to 140. As soon as the ethylene oxide is being rapidly absorbed, the reaction temperature is lowered to 120 to 125 and the introduction of ethylene oxide is continued As indicated in Example 1, the pH value of the dye bath is increased by the addition of ammonia and hexarnethylene tetramine, the treatment is continued for minutes in the boiling bath and cold rinsing is then efuntil 11 parts of ethylene oxide have been absorbed fected. Level, turquoise-blue dyeings of pure color shade The reaction product thus obtainable is substantially and having good Wet fasmess Propertles are obtained clearly soluble in water. 15 Example 4 Example 2 The procedure of the preceding examples is followed,
Wool yarn is dyed in accordance with the procedure but there is added to the y bath, to increase i116 P of Example 1, using copper phthalocyanine-3,3,3,3- value, instead of ammonia and hexamethylene tet-ramine, tetrasulfonic acid or copper phthalocyanine-3,4',4,4'"- ammonia alone, sodium bicarbonate, sodium triphosphate tetrasulfonic acid instead of copper phthalocyanine trif triethanolarnine. The dyeings thus after-treated are sulfonic acid, and the pH value is also increased by the also distinguished by good W t faStIleSS P p addition of ammonia at the end of the dyeing operation. Blue dyeings are obtained with good wet fastnesses.
Green dyeings are obtained when a mixture of copper A mixed fabric or blended yarn consisting of wool and phthalocyanine trior tetrasulfonic acid and the dye of polyamide fibers in equal proportions, is dyed in accordthe formula ance with the procedure of one of Examples 1 to 3, the
Example 5 HO3S NHC /N on HN-OSOaH G-N SO3H a Q N=NO\ OH 0 1 a HaC (V) is employed. pH value also being increased in the manner indicated.
Example 3 Level dyeings are obtained.
What is claimed is: 1. A process for dyeing nitrogenous fibrous material, which comprises subjecting said material to treatment in an acid bath containing a sulfonated copper phthalocyanine in the presence of an auxiliary compound of the (a) N-alkyl-propylenedlamine, of which the alkyl radical f m la corresponds to the radicals of tallow fatty acids, 8
Wool yarn is dyed in the manner indicated in Example 1. Instead of the product of reaction of oleylamine and ethylene oxide, however, one of the following products is employed:
mols of ethylene oxide, (b) N-alkyl-propylene diamine, of which the alkyl radi- 7 cals are unbranched and saturated and contain from 2)n+l -N 16 to 18 carbon atoms, 6 mols of ethylene oxide, (c) Mixture of behenylamine and arachidylamine 8 (CHXGHXO7H 7 or 12 mols of ethylene oxide, 111-1 (d) Mixture of theamines obtainable by reduction of in which R represents an aliphatic hydrocarbon radical thdtanow fatty acld amldes to 8 mols of ethylene containing at least 12 carbon atoms, in each of the group- OXI ings -CHXCHXO- at least one of the two XS N-dodecyl'propylenedlamme 6 mols of ethylene represents a hydrogen atom and any X not representing (ffxlisigecylamine 3 mols of ethylene oxide hgdrogin stands 2for admethyl grgup, m and n are firtegers oattemost,an an rareintee,teurn (g) Dodecylarnine 3 mols of propylene oxide parts afnognting to at leasf g 2 at of commerclal dodecylamlne are w i to f the most 20, and, after the material has absorbed the required g liizgfzf l fig3;:nP 211312 123;ogg iii ofig gafigri agioun of dye, increasing the pH value of the dyebath to a CV: after introduced until 19.5 parts thereof have been ab- 2 A process for dyeing wool which comprises Subject, Sorbed), ing the wool to treatment in an acid bath containing a (h) The Sulfuric and ester obtalied the following sulfonated copper phthalocyanine in the presence of an procedure: 79 parts of a fatty amine mixture (W mol), auxiliary compound of the formula consisting of 30% of hexadecylarnme, 25% of octadecyl- 7 amine and 45% of octadecenylamine are reacted with ethylene oxide in the presence of 08 part of sodium I 7: until 106 parts mol) of ethylene oxide have been R OH2N absorbed. The reaction temperature is initially 140 to 1 150 and can gradually be lowered to to There are added to 30.75 parts X mol) of the re- 75 in which R represents an aliphatic hydrocarbon radical containing at least 12 carbon atoms, in each of the group ings --CHXCHX-O at least one of the two Xs represent a hydrogen atom and any X not representing hydrogen stands for a methyl group, m and n are integers of at the most 2, and p, q and r are integers, the sum p+q+(m--1)(r1) amounting to at least 3 and to at most 20, and, after the material has absorbed the required amount of dye, increasing the pH value of the dyebath to above 6.
3. A process for dyeing wool which comprises subjecting the wool to treatment in an acid bath containing a sulfo nated copper phthalocyanine in the presence of an aux RLN 7...
/I-1 in which R represents an aliphatic hydrocarbon radical containing at least 12 and at the most 22 carbon atoms, In and n are integers of at most 2, and p, q and r are are integers, the sum p+q+(m-l) (r1) amounting to at least 3 and to at most 20, and, after the material has absorbed the required amount of dye, increasing the pH value of the dyebath to above 6.
4. A process for dyeing wool which comprises subjecting the wool to treatment in an acid bath containing a sulfonated copper phthalocyanine in the presence of an auxiliary compound of the formula in which R represents an aliphatic hydrocarbon radical containing 12 to 20 carbon atoms, and p and q are integers, the sum p-l-q amounting to at least 3 and to at the most 22, and, after the material has absorbed the required amount of dye, increasing the pH value of the dyebath to above 6.
5. A process for dyeing wool which comprises subjecting the wool to treatment in an acid bath containin a copper phthalocyanine trisulfonic acid in the presence of an auxiliary compound of the formula in which R represents an aliphatic hydrocarbon radical containing at least 12 carbon atoms, in each of the groupings CHXCHXO-- at least one of the two Xs represents a hydrogen atom and any X not representing hydrogen stands for a methyl group, in and n are integers of at the most 2, and p, q and r are integers, the sum p+q+(m-1)(r--1) amounting to at least 3 and to at most 20, and, after the material has absorbed the required in which R represents an aliphatic hydrocarbon radical containing at least 12 carbon atoms, in each of the groupings CHX-CHX-O at least one of the two Xs represents a hydrogen atom and any X not representing hydrogen stands for a methyl group, m and n are integers of at the most 2, and p, q and r are integers, the sum p+q+(m1)(r1) amounting to at least 3 and to at most 20, and, after the material has absorbed the required amount of dye, increasing the pH value of the dyebath to above 6.
7. A process for dyeing wool which comprises subjecting the wool to treatment in an acid bath containing a sulfonated copper phthalocyanine in the presence of an ethylene oxide addition product obtained from one molecular proportion of oleylamine and about 7 molecular proportions of ethylene oxide, and, after the material has absorbed the required amount of dye, increasing the pH value of the dyebath to above 6.
8. A process for dyeing wool which comprises subjecting the wool to treatment in an acid bath containing a copper phthalocyanine trisulfonic acid in the presence of an ethylene oxide addition product obtained from one molecular proportion of oleylamine and about 7 molecular proportions of ethylene oxide, and, after the material has absorbed the required amount of dye, increasing the pH value of the dyebath to above 6.
9. A process for dyeing wool which comprises subjecting the wool to treatment in an acid bath containing a copper phthalocyanine tetrasulfonic acid in the presence of an ethylene oxide addition product obtained from one molecular proportion of oleylamine and about 7 molecular proportions of ethylene oxide, and, after the material has absorbed the required amount of dye, increasing the pH value of the dyebath to above 6.
References Cited in the file of this patent UNITED STATES PATENTS 1,970,578 Schoeller Aug. 21, 1934 2,484,300 Mayhew Oct. 11, 1949 2,681,845 Luttringhaus June 22, 1954 2,761,868 Lacey Sept. 4, 1956 2,914,538 Randall Nov. 24, 1959 2,967,755 Keller Jan. 10, 1961 OTHER REFERENCES Vankataraman: Synthetic Dyes, vol. II, pub. 1952 by Academic Press Inc., N.Y.C., pages 1128-1135.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,049,392 August 14, 1962 Richard Casty et a1.
It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.
Column 5, lines 28 to 38, for that portion of the formula reading C-N- --N- -C read -C 0:1? :N
H C H C column 6, line 20, for "of" read or Signed and sealed this 3rd day of September 1963.
(SEAL) Attest:
ERNEST W. SWIDER DAVID L. LADD Attesting Officer Commissioner of Patents
Claims (1)
1. A PROCESS FOR DYEING NITROGENOUS FIBROUS MATERIAL, WHICH COMPRISES SUBJECTING SAID MATERIAL TO TREATEMENT IN AN ACID BATH CONTAINING A SULFONATE COPPER PHTHALOCYANINE IN THE PRESENCE OF AN AUXILIARY COMPOUND OF THE FORMULA
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Cited By (5)
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US3129052A (en) * | 1964-04-14 | New dyeing process | ||
US3211512A (en) * | 1961-05-25 | 1965-10-12 | Ciba Ltd | Paraffin oil dye assistant and wool dyeing therewith |
US3307901A (en) * | 1961-05-24 | 1967-03-07 | Geigy Ag J R | Process for dyeing polyamide textile materials and auxiliaries therefor |
US3401004A (en) * | 1964-03-26 | 1968-09-10 | Geigy Ag J R | Process for the dyeing of synthetic polyamide fibers |
US4101690A (en) * | 1973-11-26 | 1978-07-18 | Fuji Photo Film Co., Ltd. | Desensitizing composition |
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US2681845A (en) * | 1951-01-15 | 1954-06-22 | Gen Dyestuff Corp | Acid vat dyeing of animal fibers |
US2761868A (en) * | 1953-05-13 | 1956-09-04 | American Cyanamid Co | Sulfonated and unsulfonated imidomethyl, carboxyamidomethyl and aminomethyl phthalocyanines |
US2914538A (en) * | 1957-01-25 | 1959-11-24 | Gen Aniline & Film Corp | Solvent soluble phthalocyanine dyes |
US2967755A (en) * | 1957-02-05 | 1961-01-10 | Sandoz Ltd | Leveling and stripping agents |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3129052A (en) * | 1964-04-14 | New dyeing process | ||
US3307901A (en) * | 1961-05-24 | 1967-03-07 | Geigy Ag J R | Process for dyeing polyamide textile materials and auxiliaries therefor |
US3211512A (en) * | 1961-05-25 | 1965-10-12 | Ciba Ltd | Paraffin oil dye assistant and wool dyeing therewith |
US3401004A (en) * | 1964-03-26 | 1968-09-10 | Geigy Ag J R | Process for the dyeing of synthetic polyamide fibers |
US4101690A (en) * | 1973-11-26 | 1978-07-18 | Fuji Photo Film Co., Ltd. | Desensitizing composition |
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