US2674515A - Process of dyeing nitrogenous mate - Google Patents
Process of dyeing nitrogenous mate Download PDFInfo
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- US2674515A US2674515A US2674515DA US2674515A US 2674515 A US2674515 A US 2674515A US 2674515D A US2674515D A US 2674515DA US 2674515 A US2674515 A US 2674515A
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- ortho
- dyeing
- dyestuffs
- acid
- monoazo
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- 238000004043 dyeing Methods 0.000 title claims description 50
- 238000000034 method Methods 0.000 title claims description 35
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title description 2
- 239000002253 acid Substances 0.000 claims description 26
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 20
- 229910052804 chromium Inorganic materials 0.000 claims description 20
- 239000011651 chromium Substances 0.000 claims description 19
- 239000000975 dye Substances 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 150000001869 cobalt compounds Chemical class 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 2
- 229940107218 chromium Drugs 0.000 description 18
- 235000012721 chromium Nutrition 0.000 description 18
- 125000004429 atom Chemical group 0.000 description 15
- 210000002268 wool Anatomy 0.000 description 12
- 150000001845 chromium compounds Chemical class 0.000 description 11
- 229910017052 cobalt Inorganic materials 0.000 description 10
- 239000010941 cobalt Substances 0.000 description 10
- 150000002736 metal compounds Chemical class 0.000 description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000010985 leather Substances 0.000 description 4
- -1 silk Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 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
- 238000000354 decomposition reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- DOPJTDJKZNWLRB-UHFFFAOYSA-N 2-Amino-5-nitrophenol Chemical compound NC1=CC=C([N+]([O-])=O)C=C1O DOPJTDJKZNWLRB-UHFFFAOYSA-N 0.000 description 1
- POWXVFIRWRUILN-UHFFFAOYSA-N 2-[4-(bromomethyl)phenyl]benzamide Chemical compound NC(=O)C1=CC=CC=C1C1=CC=C(CBr)C=C1 POWXVFIRWRUILN-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical group O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- DYRDKSSFIWVSNM-UHFFFAOYSA-N acetoacetanilide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1 DYRDKSSFIWVSNM-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229940055042 chromic sulfate Drugs 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- 229910000356 chromium(III) sulfate Inorganic materials 0.000 description 1
- 239000011696 chromium(III) sulphate Substances 0.000 description 1
- 235000015217 chromium(III) sulphate Nutrition 0.000 description 1
- GSOLWAFGMNOBSY-UHFFFAOYSA-N cobalt Chemical compound [Co][Co][Co][Co][Co][Co][Co][Co] GSOLWAFGMNOBSY-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 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
- 238000010992 reflux Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000004552 water soluble powder Substances 0.000 description 1
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
- C09B45/00—Complex metal compounds of azo dyes
- C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
- C09B45/14—Monoazo compounds
- C09B45/16—Monoazo compounds containing chromium
-
- 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
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
- C09B62/503—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
- C09B62/507—Azo dyes
- C09B62/513—Disazo or polyazo 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
- D06P1/36—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 mordant dyes ; using metallisable 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
- D06P1/38—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 reactive 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
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/14—Wool
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- 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
-
- 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
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
- D06P3/66—Natural or regenerated cellulose using reactive dyes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/916—Natural fiber dyeing
- Y10S8/917—Wool or silk
-
- 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
- Patented Apr. 6, 1954 PROCESS OF DYEING NITROGENOUS MATE- RIALS WITH METALLIZED AZO DYES Willy Widmer, Bottmin endraht, Binningen, Ciba Limited, Basel,
- the present invention is based on the observation that materials, which, owing to their nitrogen content are capable of being dyed with acid dyestuffs, ar advantageously dyed with a cobalt or chromium compound in which each atom of cobalt or chromium is bound in complex union to one molecule of each of two different ortho ortho'- dihydroxy-monoazo-dyestuffs or to one molecule of an ortho:ortho'-dihydroXy-monoazo-dyestulf and one molecule of an ortho-hydroxy-ortho'- aminoazo-dyestufi, one of which dyestuffs is free from groups imparting solubility and the other of which contains as the sole group imparting solubility a sulfonic acid amide group, and by using an acid dyebath having a pH value which is at least sufficiently high to ensure that no 'demetallization occurs at the dye temperature used.
- the dyestuffs used in the present process are complex metal compounds which contain one atom of cobalt or chromium bound in complex union to one molecule of each of two difierent ortho:ortho--dihydroxy-monoazo-dyestuffs or to one molecule of an crtho:ortho'-dihydroxy-monoazo-dyestufi and one molecule of an ortho-hydroxy-ortho-aminoazo-dyestufi.
- the metal forming the complex chromium is preferred.
- the metalliferous dyestuffs used in the present invention therefore correspond to the composition in which Me represents cobalt or chromium, F1 represents an ortho:ortho'-dihydroXy-monoazo dyestufi and F2 represents an ortho:ortho'-dihydroxy-monoazo-dyestulf difierent from F1 or an ortho-hydroxy-ortho-aminoazo-dyestuff, and in which the dotted lines represent complex bonds.
- One of the two monoazo-dyestuiis F1 and F2 bound together in complex union by the same cobalt or chromium atom contains no groups imparting solubility and the other contains as the sole group imparting solubility a sulfonic acid amide group, which may contain substituents at the nitrogen atom, for example, a lower alkyl radical such as methyl, ethyl or hydroxyethyl. Hydroxyl groups are not to be considered as groups imparting solubility.
- the dyestufi can be made by methods in themselves known by coupling an orthohydroxy-diazo-compound, advantageously one of the benzene series, with a compound capable of coupling in a position vicinal to an aromatically bound hydroxyl group or enolizable or enolized keto group.
- the complex metal compounds in the present process can be prepared, for example, by reacting in approximately the molecular ratio 1:1:1 an agent yielding cobalt or chromium with two orthotortho dihydroxy monoazo dyestuffs, of which one contains no groups imparting solubility and the other of which contains as the sole group imparting solubility a sulfonic acid amide group.
- the treatment with the agent yielding metal is advantageously conducted in a weakly acid to alkaline medium. Accordingly, there come into consideration as agents yielding metal more especially those metal compounds which are stable in alkaline media, for example, metal, and especially chromium, compounds of aliphatic hydroxycarboxylic acids or advantageously aromatic ortho-hydroxy-carboxylic acids, which contain the metal in complex union.
- aliphatic hydroxycarboxylic acids there may be mentioned among others, lactic acid, glycollic acid, citric acid and especially tartaric acid, and as aromatic ortho-hydroxycarboxylic acids there may be mentioned, for example, those of the benzene series such as 4-, 5- or G-methyl-l-hydroxybenzene-2-carboxylic acid and above all l-hydroxybenzene-2-carboxylic acid, which is free from further substituents.
- the complex metal compounds used in the present process can also be prepared by reacting a metal compound, especially a chromium compound, of an ortho:ortho-dihydroxymonoazodyestuff containing one atom of metal compound in complex union per molecule of dyestuff (1:1- complex) with a metal-free ortho:orthodihydroxymonoazo-dyestuff, and so choosing the starting materials that one of them is free from groups imparting solubility and th other contains as the sole group imparting solubility a sulfonic acid amide group. In general it is of advantage to have the sulfonic acid amide group present in the metalliferous dyestuff.
- the 1:1- complex which is used as starting material, can itself be prepared by methods in themselves known, for example, by reacting the metal-free monoazo-dyestuff advantageously in an acid medium with an excess of an agent yielding metal at the boiling temperature or if desired at a temperature exceeding 100 C.
- the reaction of the lzl-metal complex with the metal-free dyestuff is advantageously conducted in an aqueous neutral to alkaline medium at ordinary or a raised temperature.
- orthozortho-dihydroxy-monoazo-dyestuffs and their metal complexes apply also to ortho-hydr0xy-ortho'- amino-monoazo-dyestufis and complex metal compounds which contain one atom of cobalt or chromium bound to one molecule of an orthozortho-dihydroxy-monoazo-dyestuif and one molecule of an ortho-hydroxy-ortho'-aminoazo-dyestuff.
- the dyeing process of this invention is conducted in a weakly acid dyebath (pl-I value not higher than 6.5), but the pH value must be at least sufiiciently high to ensure that no decomposition of the complex occurs at the dyeing temperature, that is to say, at a raised temperature which is generally the boiling temperature of the dyebath or is only slightly lower than the boiling temperature. Such decomposition can generally be avoided when the pH value of the dyebath is higher than 3.0. It is of advantage to conduct the dyeing in an acetic acid bath.
- the complex metal compounds used in the present invention exhibit a very good absorptive capacity with respect to the above-mentioned nitrogenous materials. Furthermore, they are surprisingly soluble in these baths or are taken up therein in an extremely finely divided form.
- the dyeings obtained by the present process especially dyeings on wool, are distinguished by their uniformity, good properties of wet fastness and very good fastness to light.
- Example 1 3 parts of the chromium compound which conand I O 2NO bound to one atomic proportion of chromium, are dissolved in 4000 parts of water, 10 parts of crystalline sodium sulfate are added, and parts of well wetted wool are entered at 4050 C. into the resulting dyebath. 2 parts of acetic acid of 40 per cent strength are then added, the bath is raised to the boil in the course of 30 minutes and dyeing is carried on for 45 minutes at the boil. Finally the wool is rinsed with cold water and dried. There is obtained blackish navy blue dyeing of good fastness to washing and light.
- the complex chromium compound used in this example may be prepared as follows:
- the whole After the addition of 6 parts of sulfonated castor oil the whole is heated to the boil and maintained at that temperature under reflux for 3 hours. At the end of this period the whole is allowed to cool, and the dyestuff is precipitated by the addition of sodium chloride. After being filtered off and dried, the dyestuif is a black watersoluble powder.
- the dark green solution of sodium-potassium chromosalicylate is obtained by boiling 362 parts of an aqueous chromic sulfate solution having a chromium content of 7.2 per cent. with 138 parts of salicylic acid, dissolving the resulting chromosalicylic acid by the addition of 166 parts of sodium hydroxide solution of 30 per cent. strength and a sufiicient quantity of potassium hydroxide solution of 37 per cent. strength to render the medium alkaline to phenolphthalein, and making up the mixture to 1000 parts with water.
- a process for dyeing materials which owing to their nitrogen content are capable of being Diazotizcd 2-amino-1- hydroxybenzene-b sulfonic acid amide 1-phenyl-3- meith yl-5-pyrazolone.
- Example 3 dyebath containing a amounting to three leather, and there is containing 0.5 part of stufi No. 6 of the tab Water.
- g materials which owing to their nitrogen content are capable of being dyed with acid dyestufis, w dyeing with a member s consisting of chromium a which each atom of said plex union to one molec stuffs one of which is an.
- monoazo-dyestufi and the other of lected from the group consisting of o dihydroxy-monoazo-dyestufis droXy-ortho-amino-monoazo-dyestufis hich process comprises elected from the group nd cobalt compounds in metals is bound in comule of two diiierent dyeortho :ortho -dihydroxywhich is se rtho ortho and ortho-hyone of In groups imparting which contains as the bility a sulfonic acid comprises furtherth of which the pH h to ensure that no dyed with acid dyestuifs, which process comprises dyeing with a cobalt compound in which each atom of cobalt is bound in complex union to one molecule of two different ortho:ortho'-dihydroxymonoazo-dyestuiis, one of which is free from groups imparting solubility and the other of which contains as the sole group imparting solubility a sulfonic acid
- a process for dyeing materials which owing to their nitrogen content are capable of being dyed with acid dyestuiTs, which process comprises dyeing with a chromium compound in which each atom of chromium is bound in complex union to one molecule of two diflerent ortho:ortho-dihydroxy-monoazo-dyestuffs, one of which is free from groups imparting solubility and the other of which contains as the sole group imparting solubility a sulfonic acid amide group, which process comprises furthermore dyeing in an acid dyebath of which the pH value is at least high enough to ensure that no demetallization occurs at the dyeing temperature.
- a process for dyeing materials which owing to their nitrogen content are capable of being dyed with acid dyestuffs which process comprises dyeing with a chromium compound in which each atom of chromium is bound in complex union to one molecule of an ortho:ortho-dihydroxymonoazo-dyestuif which contains as the sole 5 group imparting solubility a sulfonic acid amide group, and to one molecule of an ortho-hydroxyortho'-amino-monoazo-dyestuif which is free from groups imparting solubility, which process comprises furthermore dyeing in an acid dyebath of which the pH value is at least high enough to ensure that no demetallization occurs at the dyeing temperature.
- a process for dyeing wool which comprises dyeing with a cobalt compound in which each dyeing temperature, atom of cobalt is bound in complex union to one molecule of two different orthozortho'-dihy droxy-monoazo-dyestuffs, one of which is free from groups imparting solubility and the other of which contains as the sole group imparting solubility a sulfonic acid amide group, which process comprises furthermore dyein in an acid dyebath of which the pI-I value is at least high enough to ensure that no demetallization occurs at the dyeing temperature.
- a process for dyeing wool which comprises dyeing with a chromium compound in which each atom of chromium is bound in complex union to one molecule of two different ortho:ortho'-dihydroxy-monoazo-dyestuffs, one of which is free from groups imparting solubility and the other of which contains as the sole group imparting solubility a sulfonic acid amide group, which process comprises furthermore dyeing in an acid dyebath of which the pH value is at least high enough to ensure that no demetallization occurs at the dyeing temperature.
- a process for dyeing wool which comprises dyeing with a chromium compound in which each atom of chromium is bound in complex union to one molecule of an ortho:ortho'-dihydroxymonoazo-dyestuff which contains as the sole group imparting solubility a sulfonic acid amide group, and to one molecule of an ortho-hydroxyortho-amino-monoazo-dyestuff which is free from groups impartin solubility, which process comprises furthermore dyeing in an acid dyebath of which the pH value is at least high enough to ensure that no demetallization occurs at the dyeing temperature.
- a process which comprises dyeing wool in an acid dyebath of which the pH value is at least high enough to ensure that no demetallization occurs at the dyeing temperature with a chromium compound in which each atom of chromium is bound in complex union to one molecule of the dyestuff corresponding to the formula O zNHn and to one molecule of the dyestufi corresponding to the formula and to one molecule of the dyestuff corresponding to the formula 10.
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Description
Patented Apr. 6, 1954 PROCESS OF DYEING NITROGENOUS MATE- RIALS WITH METALLIZED AZO DYES Willy Widmer, Bottmin endraht, Binningen, Ciba Limited, Basel,
gen, and Christian Zick- Switzerland, assignors to Switzerland, a Swiss firm N Drawing. Application February 6, 1951, Serial No. 209,706
Claims priority, application Switzerland February 28, 1950 12 Claims. 1
The present invention is based on the observation that materials, which, owing to their nitrogen content are capable of being dyed with acid dyestuffs, ar advantageously dyed with a cobalt or chromium compound in which each atom of cobalt or chromium is bound in complex union to one molecule of each of two different ortho ortho'- dihydroxy-monoazo-dyestuffs or to one molecule of an ortho:ortho'-dihydroXy-monoazo-dyestulf and one molecule of an ortho-hydroxy-ortho'- aminoazo-dyestufi, one of which dyestuffs is free from groups imparting solubility and the other of which contains as the sole group imparting solubility a sulfonic acid amide group, and by using an acid dyebath having a pH value which is at least sufficiently high to ensure that no 'demetallization occurs at the dye temperature used.
As examples of materials which owing to their nitrogen content are capable of being dyed with acid dyesufis and are therefore suitable for being dyed by the present process, there may be mentioned leather, silk, synthetic fibers of superpolyamides (nylon) or superpolyurethanes, and above all wool.
The dyestuffs used in the present process are complex metal compounds which contain one atom of cobalt or chromium bound in complex union to one molecule of each of two difierent ortho:ortho--dihydroxy-monoazo-dyestuffs or to one molecule of an crtho:ortho'-dihydroxy-monoazo-dyestufi and one molecule of an ortho-hydroxy-ortho-aminoazo-dyestufi. As the metal forming the complex chromium is preferred.
The metalliferous dyestuffs used in the present invention therefore correspond to the composition in which Me represents cobalt or chromium, F1 represents an ortho:ortho'-dihydroXy-monoazo dyestufi and F2 represents an ortho:ortho'-dihydroxy-monoazo-dyestulf difierent from F1 or an ortho-hydroxy-ortho-aminoazo-dyestuff, and in which the dotted lines represent complex bonds. One of the two monoazo-dyestuiis F1 and F2 bound together in complex union by the same cobalt or chromium atom contains no groups imparting solubility and the other contains as the sole group imparting solubility a sulfonic acid amide group, which may contain substituents at the nitrogen atom, for example, a lower alkyl radical such as methyl, ethyl or hydroxyethyl. Hydroxyl groups are not to be considered as groups imparting solubility.
A large number of ortho:orth0'-dihydroxymonoazo-dyestuffs of the foregoing constitution are known. The dyestufi can be made by methods in themselves known by coupling an orthohydroxy-diazo-compound, advantageously one of the benzene series, with a compound capable of coupling in a position vicinal to an aromatically bound hydroxyl group or enolizable or enolized keto group.
The complex metal compounds in the present process can be prepared, for example, by reacting in approximately the molecular ratio 1:1:1 an agent yielding cobalt or chromium with two orthotortho dihydroxy monoazo dyestuffs, of which one contains no groups imparting solubility and the other of which contains as the sole group imparting solubility a sulfonic acid amide group. The treatment with the agent yielding metal is advantageously conducted in a weakly acid to alkaline medium. Accordingly, there come into consideration as agents yielding metal more especially those metal compounds which are stable in alkaline media, for example, metal, and especially chromium, compounds of aliphatic hydroxycarboxylic acids or advantageously aromatic ortho-hydroxy-carboxylic acids, which contain the metal in complex union. As examples of aliphatic hydroxycarboxylic acids there may be mentioned among others, lactic acid, glycollic acid, citric acid and especially tartaric acid, and as aromatic ortho-hydroxycarboxylic acids there may be mentioned, for example, those of the benzene series such as 4-, 5- or G-methyl-l-hydroxybenzene-2-carboxylic acid and above all l-hydroxybenzene-2-carboxylic acid, which is free from further substituents.
The complex metal compounds used in the present process can also be prepared by reacting a metal compound, especially a chromium compound, of an ortho:ortho-dihydroxymonoazodyestuff containing one atom of metal compound in complex union per molecule of dyestuff (1:1- complex) with a metal-free ortho:orthodihydroxymonoazo-dyestuff, and so choosing the starting materials that one of them is free from groups imparting solubility and th other contains as the sole group imparting solubility a sulfonic acid amide group. In general it is of advantage to have the sulfonic acid amide group present in the metalliferous dyestuff. The 1:1- complex, which is used as starting material, can itself be prepared by methods in themselves known, for example, by reacting the metal-free monoazo-dyestuff advantageously in an acid medium with an excess of an agent yielding metal at the boiling temperature or if desired at a temperature exceeding 100 C. The reaction of the lzl-metal complex with the metal-free dyestuff is advantageously conducted in an aqueous neutral to alkaline medium at ordinary or a raised temperature.
The above statements with regard to orthozortho-dihydroxy-monoazo-dyestuffs and their metal complexes apply also to ortho-hydr0xy-ortho'- amino-monoazo-dyestufis and complex metal compounds which contain one atom of cobalt or chromium bound to one molecule of an orthozortho-dihydroxy-monoazo-dyestuif and one molecule of an ortho-hydroxy-ortho'-aminoazo-dyestuff.
The dyeing process of this invention is conducted in a weakly acid dyebath (pl-I value not higher than 6.5), but the pH value must be at least sufiiciently high to ensure that no decomposition of the complex occurs at the dyeing temperature, that is to say, at a raised temperature which is generally the boiling temperature of the dyebath or is only slightly lower than the boiling temperature. Such decomposition can generally be avoided when the pH value of the dyebath is higher than 3.0. It is of advantage to conduct the dyeing in an acetic acid bath.
In dyebaths which fulfill the above conditions the complex metal compounds used in the present invention exhibit a very good absorptive capacity with respect to the above-mentioned nitrogenous materials. Furthermore, they are surprisingly soluble in these baths or are taken up therein in an extremely finely divided form. The dyeings obtained by the present process, especially dyeings on wool, are distinguished by their uniformity, good properties of wet fastness and very good fastness to light.
The following examples illustrate the invention, the parts and percentages being by weight.
Example 1 3 parts of the chromium compound which conand I O 2NO bound to one atomic proportion of chromium, are dissolved in 4000 parts of water, 10 parts of crystalline sodium sulfate are added, and parts of well wetted wool are entered at 4050 C. into the resulting dyebath. 2 parts of acetic acid of 40 per cent strength are then added, the bath is raised to the boil in the course of 30 minutes and dyeing is carried on for 45 minutes at the boil. Finally the wool is rinsed with cold water and dried. There is obtained blackish navy blue dyeing of good fastness to washing and light.
The complex chromium compound used in this example may be prepared as follows:
3.65 parts of the sodium salt of the dyestufi from diazotized 2-amino-l-hydroxybenzene-esulfonic acid amide and 2-hydroxynaphthalene and 3.31 parts of the sodium salt of the dyestuff from diazotized 5-nitro-2-amino-1-hydroxybenzene and Z-hydroxynaphthalene, both dyestuffs being in the form of a moist paste (filter cake), are stirred in 300 parts of water and mixed with 25 parts of a solution of sodium-potassium chromosalicylate having a chromium content of 2.6 per cent.
After the addition of 6 parts of sulfonated castor oil the whole is heated to the boil and maintained at that temperature under reflux for 3 hours. At the end of this period the whole is allowed to cool, and the dyestuff is precipitated by the addition of sodium chloride. After being filtered off and dried, the dyestuif is a black watersoluble powder.
The dark green solution of sodium-potassium chromosalicylate is obtained by boiling 362 parts of an aqueous chromic sulfate solution having a chromium content of 7.2 per cent. with 138 parts of salicylic acid, dissolving the resulting chromosalicylic acid by the addition of 166 parts of sodium hydroxide solution of 30 per cent. strength and a sufiicient quantity of potassium hydroxide solution of 37 per cent. strength to render the medium alkaline to phenolphthalein, and making up the mixture to 1000 parts with water.
In the following table are given a few further complex metal compounds with which valuable dyeings on wool fast to washing and light can also be obtained in the manner described above. In column I is given the complex-forming metal, in columns II and III the two ortho:ortho-dihydroxy-monoazo-dyestufis or the ortho:ortho-dihydroxy-monoazo-dyestufi and the ortho-hydroxy-ortho-aminoazo-dyestufi bound to the metal, and in column IV the tints obtainable on wool with the various complex metal compounds:
III
2. A process for dyeing materials, which owing to their nitrogen content are capable of being Diazotizcd 2-amino-1- hydroxybenzene-b sulfonic acid amide 1-phenyl-3- meith yl-5-pyrazolone.
diazotized 2-amino-1- hydroxybenzene-isulfonic acid amide 2-hydroxynaphthalene. diazotized 4-nitro-2- amino-l-hydroxybenzene Z-hydroxynaphthalene-G- sulfonic acid amide. diazotized 2-amino-1- hydroxybenzene-4- sulfonic acid amide l-phenyl-3- methyl-5-pyrazolene. diazotized 2-amino-1- hydroxybenzeneisulfonic acid amide 2-hydroxynaphthalene.
diazotized 2-amino-1- hydroxybenzene-4- sulfom'c acid amide 1-phenyl-3- methyl-S-pyrazolone.
Diazotized E-nitro-Z- amino-l-hydroxybenzene 2-hydroxynaphthalene.
diazotized 4-nitro-2- amino-l-hydroxybenzone Z-hydroxynaphthalene.
diazotized 4-nitro-2- amino-l-hydroxybenzone acetoacetic acid anilide.
diazotized 4-nitro-2- amino-l-hydroxybenz e n e E 2 -h ydroxynaphthalene.
diazotized 4-nitro-6- acetylammo z-aminol-hydroxybenzene 2:6-dihydroxynaphthalene. diazotized 4-chloro-2- amino-Lhydroxybenzene 5:8-dichloro-l-hydroxynaphthalene. diazotized 4-chloro-2- amino-l-hydroxyben- (ziene Eh h l2'hyoxynap t aene. diazotized 4-chloro-5- nitro-2-amino-1-hydroxybenzene 2-aminonaphthalene.
brown.
violet-brown.
reddish grey.
yellow-brown.
bluish bordeaux.
bordeaux.
brown.
100 parts of nylon dyebath at 50 of water 2 parts tained as describ ample 1, 40 parts 0.5 part of aceti The temperatur Emmple 2 hour at that temperature.
deep navy blue dyeing of v Washing and rubbing.
Example 3 dyebath containing a amounting to three leather, and there is containing 0.5 part of stufi No. 6 of the tab Water.
then fat-liquored in th The leather is dyed a bl What is claimed is:
1. A process for dyein which dyestuffs is free fro solubility and the other of sole grou imparting solu amide group,
e is raised to 95 of minutes and dyeing is car which process more dyeing in an acid dyeba value is at least high enoug demetallization occurs at the yarn are introduced into a 0., which contains in 4000 parts of the chromiferous dyestuif obed in the first paragraph of Exof crystalline sodium sulfate and 0 acid of 40 per cent. strength. C. in the course ried on for one There is obtained a cry good fastness to The leather is dyed for 45 minutes, and e same or a fresh bath. uish bordeaux tint.
g materials, which owing to their nitrogen content are capable of being dyed with acid dyestufis, w dyeing with a member s consisting of chromium a which each atom of said plex union to one molec stuffs one of which is an. monoazo-dyestufi and the other of lected from the group consisting of o dihydroxy-monoazo-dyestufis droXy-ortho-amino-monoazo-dyestufis hich process comprises elected from the group nd cobalt compounds in metals is bound in comule of two diiierent dyeortho :ortho -dihydroxywhich is se rtho ortho and ortho-hyone of In groups imparting which contains as the bility a sulfonic acid comprises furtherth of which the pH h to ensure that no dyed with acid dyestuifs, which process comprises dyeing with a cobalt compound in which each atom of cobalt is bound in complex union to one molecule of two different ortho:ortho'-dihydroxymonoazo-dyestuiis, one of which is free from groups imparting solubility and the other of which contains as the sole group imparting solubility a sulfonic acid amide group, which process 40 comprises furthermore dyeing in an acid dyebath of which the pH value is at least high enough to ensure that no demetallization occurs at the dyeing temperature.
3. A process for dyeing materials, which owing to their nitrogen content are capable of being dyed with acid dyestuiTs, which process comprises dyeing with a chromium compound in which each atom of chromium is bound in complex union to one molecule of two diflerent ortho:ortho-dihydroxy-monoazo-dyestuffs, one of which is free from groups imparting solubility and the other of which contains as the sole group imparting solubility a sulfonic acid amide group, which process comprises furthermore dyeing in an acid dyebath of which the pH value is at least high enough to ensure that no demetallization occurs at the dyeing temperature.
4. A process for dyeing materials which owing to their nitrogen content are capable of being dyed with acid dyestuffs, which process comprises dyeing with a chromium compound in which each atom of chromium is bound in complex union to one molecule of an ortho:ortho-dihydroxymonoazo-dyestuif which contains as the sole 5 group imparting solubility a sulfonic acid amide group, and to one molecule of an ortho-hydroxyortho'-amino-monoazo-dyestuif which is free from groups imparting solubility, which process comprises furthermore dyeing in an acid dyebath of which the pH value is at least high enough to ensure that no demetallization occurs at the dyeing temperature.
5. A process for dyeing wool which comprises dyeing with a cobalt compound in which each dyeing temperature, atom of cobalt is bound in complex union to one molecule of two different orthozortho'-dihy droxy-monoazo-dyestuffs, one of which is free from groups imparting solubility and the other of which contains as the sole group imparting solubility a sulfonic acid amide group, which process comprises furthermore dyein in an acid dyebath of which the pI-I value is at least high enough to ensure that no demetallization occurs at the dyeing temperature.
6. A process for dyeing wool which comprises dyeing with a chromium compound in which each atom of chromium is bound in complex union to one molecule of two different ortho:ortho'-dihydroxy-monoazo-dyestuffs, one of which is free from groups imparting solubility and the other of which contains as the sole group imparting solubility a sulfonic acid amide group, which process comprises furthermore dyeing in an acid dyebath of which the pH value is at least high enough to ensure that no demetallization occurs at the dyeing temperature.
'7. A process for dyeing wool which comprises dyeing with a chromium compound in which each atom of chromium is bound in complex union to one molecule of an ortho:ortho'-dihydroxymonoazo-dyestuff which contains as the sole group imparting solubility a sulfonic acid amide group, and to one molecule of an ortho-hydroxyortho-amino-monoazo-dyestuff which is free from groups impartin solubility, which process comprises furthermore dyeing in an acid dyebath of which the pH value is at least high enough to ensure that no demetallization occurs at the dyeing temperature.
8. A process which comprises dyeing wool in an acid dyebath of which the pH value is at least high enough to ensure that no demetallization occurs at the dyeing temperature with a chromium compound in which each atom of chromium is bound in complex union to one molecule of the dyestuff corresponding to the formula O zNHn and to one molecule of the dyestufi corresponding to the formula and to one molecule of the dyestuff corresponding to the formula 10. A process which comprises dyeing wool in an acid dyebath of which the pH value is at least high enough to ensure that no demetallization occurs at the dyeing temperature with a chromium compound in which each atom of chromium is bound-in complex union to one molecule ofthe dyestuff corresponding to the formula HO OH I and to one molecule of the dyestufi corresponding to the formula 11. A process which comprises dyeing woo1 in an acid dyebath of which the pH value is at least high enough to ensure that no demetallization occurs at the dyeing temperature with a chro mium compound in which each atom of chromium is bound in complex union to one molecule of the dyestuff corresponding to the formula and to one molecule of the dyestufi corresponding to the formula 12. A process which comprises dyeing wool in an acid dyebath of which the pH value is at least high enough to ensure that no demetallization occurs at the dyeing temperature with a cobalt compound in which each atom of cobalt is bound in complex union to one molecule of the dyestuff corresponding to the formula 0 H H O O zNHz and to one molecule of the dyestuff corresponding to the formula References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 1,623,005 Gubler Mar. 29, 1927 1,887,602 Straub Nov. 15, 1932 1,887,603 Straub Nov. 15, 1932
Claims (1)
1. A PROCESS FOR DYEING MATERIALS, WHICH OWING TO THEIR NITROGEN CONTENT ARE CAPABLE OF BEING DYED WITH ACID DYESTUFFS, WHICH PROCESS COMPRISES DYEING WITH A MEMBER SELECTED FROM THE GROUP CONSISTING OF CHROMIUM AND COBALT COMPOUNDS IN WHICH EACH ATOM OF SAID METALS IS BOUND IN COMPLEX UNION TO ONE MOLECULE OF TWO DIFFERENT DYESTUFFS ONE OF WHICH IS AN ORTHO:ORTHO''-DIHYDROXYMONOAZO-DYESTUFF AND THE OTHER OF WHICH IS SELECTED FROM THE GROUP CONSISTING OF ORTHO:ORTHO''DIHYDROXY-MONOAZO-DYESTUFFS AND ORTHO-HYDROXY-ORTHO''-AMINO-MONOAZO-DYESTUFFS, ONE OF WHICH DYESTUFFS IS FREE FROM GROUPS IMPARTING SOLUBILITY AND THE OTHER OF WHICH CONTAINS AS THE SOLE GROUP IMPARTING SOLUBILITY A SULFONIC ACID AMIDE GROUP, WHICH PROCESS COMPRISES FURTHERMORE DYEING IN AN ACID DYEBATH OF WHICH THE PH VALUE IS AT LEAST HIGH ENOUGH TO ENSURE THAT NO DEMETALLIZATION OCCURS AT THE DYEING TEMPERATURE.
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| Publication Number | Publication Date |
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| US2674515A true US2674515A (en) | 1954-04-06 |
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| Application Number | Title | Priority Date | Filing Date |
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| US2674515D Expired - Lifetime US2674515A (en) | Process of dyeing nitrogenous mate |
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Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2776956A (en) * | 1957-01-08 | Soinhi | ||
| US2778816A (en) * | 1951-08-17 | 1957-01-22 | Ciba Ltd | Cobaltiferous and chromiferous azo-dyestuffs |
| US2784179A (en) * | 1952-07-14 | 1957-03-05 | Ciba Ltd | Metalliferous azo-dyestuffs |
| US2806760A (en) * | 1953-06-10 | 1957-09-17 | Ciba Ltd | Process for dyeing nitrogenous fibers with metalliferous monoazo dyestuffs |
| US2819259A (en) * | 1953-02-27 | 1958-01-07 | Ciba Ltd | New metalliferous azo-dyestuffs |
| US2820784A (en) * | 1958-01-21 | Soichi | ||
| US2824864A (en) * | 1953-02-11 | 1958-02-25 | Ciba Ltd | Complex cobalt compounds |
| US2829139A (en) * | 1953-10-30 | 1958-04-01 | Gen Aniline & Film Corp | Metalliferous azo dyestuff |
| US2835550A (en) * | 1954-08-24 | 1958-05-20 | Du Pont | Process of dyeing wool |
| US2841576A (en) * | 1955-04-21 | 1958-07-01 | Ciba Ltd | Complex metal compounds of azo-dyestuffs |
| US2852502A (en) * | 1956-09-11 | 1958-09-16 | American Cyanamid Co | Half metal complexes of acylacetonitrile azo dyes containing the sulfonamide group |
| US2855392A (en) * | 1958-10-07 | Oxnxi | ||
| US2856397A (en) * | 1952-10-09 | 1958-10-14 | Basf Ag | Production of metal-containing azo dyestuffs |
| US2885392A (en) * | 1956-11-21 | 1959-05-05 | Du Pont | Process of producing high-purity, half-chromed azo dyes |
| US2906746A (en) * | 1959-09-29 | Metalliferous azo dyestuffs | ||
| US3005813A (en) * | 1953-05-22 | 1961-10-24 | Ciba Ltd | Metalliferous azo-dyestuffs |
| US3097039A (en) * | 1963-07-09 | Hoas oh | ||
| US3163634A (en) * | 1959-11-19 | 1964-12-29 | Allied Chem | Dyestuffs containing metal in complex combination |
| US3189594A (en) * | 1965-06-15 | Oh xsojxnhx chjxo chjxohx chi chi | ||
| US3252963A (en) * | 1959-06-12 | 1966-05-24 | Ici Ltd | Cobalt- and chromium-complex azo dyestuffs free from sulfonic and carboxylic acid groups, and carrying an acryloylamino radical |
| USB190679I5 (en) * | 1968-05-14 | 1975-01-28 |
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| US1623005A (en) * | 1925-07-03 | 1927-03-29 | Soc Of Chemical Ind | Azo dyestuffs containing chromium and process of making same |
| US1887602A (en) * | 1927-09-17 | 1932-11-15 | Chem Ind Basel | Metal compound of azo-dyestuffs and process of making same |
| US1887603A (en) * | 1928-09-10 | 1932-11-15 | Soc Of Chemical Ind | Process for the production of metal compounds of azo-dyestuffs on animal fibers |
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|---|---|---|---|---|
| US1623005A (en) * | 1925-07-03 | 1927-03-29 | Soc Of Chemical Ind | Azo dyestuffs containing chromium and process of making same |
| US1887602A (en) * | 1927-09-17 | 1932-11-15 | Chem Ind Basel | Metal compound of azo-dyestuffs and process of making same |
| US1887603A (en) * | 1928-09-10 | 1932-11-15 | Soc Of Chemical Ind | Process for the production of metal compounds of azo-dyestuffs on animal fibers |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2855392A (en) * | 1958-10-07 | Oxnxi | ||
| US3189594A (en) * | 1965-06-15 | Oh xsojxnhx chjxo chjxohx chi chi | ||
| US2820784A (en) * | 1958-01-21 | Soichi | ||
| US3097039A (en) * | 1963-07-09 | Hoas oh | ||
| US2776956A (en) * | 1957-01-08 | Soinhi | ||
| US2906746A (en) * | 1959-09-29 | Metalliferous azo dyestuffs | ||
| US2778816A (en) * | 1951-08-17 | 1957-01-22 | Ciba Ltd | Cobaltiferous and chromiferous azo-dyestuffs |
| US2784179A (en) * | 1952-07-14 | 1957-03-05 | Ciba Ltd | Metalliferous azo-dyestuffs |
| US2856397A (en) * | 1952-10-09 | 1958-10-14 | Basf Ag | Production of metal-containing azo dyestuffs |
| US2824864A (en) * | 1953-02-11 | 1958-02-25 | Ciba Ltd | Complex cobalt compounds |
| US2819259A (en) * | 1953-02-27 | 1958-01-07 | Ciba Ltd | New metalliferous azo-dyestuffs |
| US3005813A (en) * | 1953-05-22 | 1961-10-24 | Ciba Ltd | Metalliferous azo-dyestuffs |
| US2806760A (en) * | 1953-06-10 | 1957-09-17 | Ciba Ltd | Process for dyeing nitrogenous fibers with metalliferous monoazo dyestuffs |
| US2829139A (en) * | 1953-10-30 | 1958-04-01 | Gen Aniline & Film Corp | Metalliferous azo dyestuff |
| US2835550A (en) * | 1954-08-24 | 1958-05-20 | Du Pont | Process of dyeing wool |
| US2841576A (en) * | 1955-04-21 | 1958-07-01 | Ciba Ltd | Complex metal compounds of azo-dyestuffs |
| US2852502A (en) * | 1956-09-11 | 1958-09-16 | American Cyanamid Co | Half metal complexes of acylacetonitrile azo dyes containing the sulfonamide group |
| US2885392A (en) * | 1956-11-21 | 1959-05-05 | Du Pont | Process of producing high-purity, half-chromed azo dyes |
| US3252963A (en) * | 1959-06-12 | 1966-05-24 | Ici Ltd | Cobalt- and chromium-complex azo dyestuffs free from sulfonic and carboxylic acid groups, and carrying an acryloylamino radical |
| US3163634A (en) * | 1959-11-19 | 1964-12-29 | Allied Chem | Dyestuffs containing metal in complex combination |
| USB190679I5 (en) * | 1968-05-14 | 1975-01-28 | ||
| US3925346A (en) * | 1968-05-14 | 1975-12-09 | Ciba Geigy Ag | Mixed chromium-containing azo dyestuffs containing, per atom of chromium, one molecule of an o,o'-dihydroxy-sulphophenylene-azo-naphthalene and one molecule of an -o-hydroxyphenylene-azo-acetoacetamide |
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