US1918938A - Azo-dyestuffs containing chromium and process of making same - Google Patents
Azo-dyestuffs containing chromium and process of making same Download PDFInfo
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- US1918938A US1918938A US573300A US57330031A US1918938A US 1918938 A US1918938 A US 1918938A US 573300 A US573300 A US 573300A US 57330031 A US57330031 A US 57330031A US 1918938 A US1918938 A US 1918938A
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- chromium
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- azo
- acid
- diazo
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- 239000011651 chromium Substances 0.000 title description 17
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title description 16
- 229910052804 chromium Inorganic materials 0.000 title description 14
- 238000000034 method Methods 0.000 title description 4
- 150000001845 chromium compounds Chemical class 0.000 description 20
- 239000000975 dye Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 18
- 239000002253 acid Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 229940107218 chromium Drugs 0.000 description 13
- 238000004043 dyeing Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 235000012721 chromium Nutrition 0.000 description 12
- 238000001704 evaporation Methods 0.000 description 11
- 210000002268 wool Anatomy 0.000 description 10
- 235000002639 sodium chloride Nutrition 0.000 description 8
- 229910001413 alkali metal ion Inorganic materials 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229950011260 betanaphthol Drugs 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- 239000004280 Sodium formate Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- UBFMILMLANTYEU-UHFFFAOYSA-H chromium(3+);oxalate Chemical compound [Cr+3].[Cr+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UBFMILMLANTYEU-UHFFFAOYSA-H 0.000 description 3
- 230000003292 diminished effect Effects 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 229940013688 formic acid Drugs 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 3
- 235000019254 sodium formate Nutrition 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N beta-hydroxynaphthyl Natural products C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- VBVRWWZABFQIAA-UHFFFAOYSA-H chromium(3+);trisulfite Chemical compound [Cr+3].[Cr+3].[O-]S([O-])=O.[O-]S([O-])=O.[O-]S([O-])=O VBVRWWZABFQIAA-UHFFFAOYSA-H 0.000 description 2
- 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 2
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- NHLAPJMCARJFOG-UHFFFAOYSA-N 3-methyl-1,4-dihydropyrazol-5-one Chemical compound CC1=NNC(=O)C1 NHLAPJMCARJFOG-UHFFFAOYSA-N 0.000 description 1
- 241001233887 Ania Species 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- DTNDYLDEDKJVQY-UHFFFAOYSA-K S([O-])(O)=O.[Cr+3].S([O-])(O)=O.S([O-])(O)=O Chemical compound S([O-])(O)=O.[Cr+3].S([O-])(O)=O.S([O-])(O)=O DTNDYLDEDKJVQY-UHFFFAOYSA-K 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 229910021563 chromium fluoride Inorganic materials 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- QOWZHEWZFLTYQP-UHFFFAOYSA-K chromium(3+);triformate Chemical compound [Cr+3].[O-]C=O.[O-]C=O.[O-]C=O QOWZHEWZFLTYQP-UHFFFAOYSA-K 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- -1 diazo 2hydroxynaphthalene Chemical compound 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- QELUYTUMUWHWMC-UHFFFAOYSA-N edaravone Chemical compound O=C1CC(C)=NN1C1=CC=CC=C1 QELUYTUMUWHWMC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009963 fulling Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 description 1
- 239000002966 varnish 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
- C09B45/01—Complex metal compounds of azo dyes characterised by the method of metallisation
Definitions
- the present invention relates to the manufacture of new azo-dyestuffs containing chromium. It comprises the process of making these dyestuffs as well as the new dyestuffs themselves.
- valuable new dyestuffs containing chromium are obtained by heating in an aqueous solution a mixture of a chromium compound with at least one o-hydroxy-azo-dyestuff, which chromium compound is capable-of forming complex chro mium compounds, and which mixture contains at least two o-hydroxy-azo-dyestuffs, of which at least one is an azo-dyestuff from a l-dia-zo-2-hydroxynaphthalene 4-sulfonic acid and a naphthol, in presence of a proportion of alkali metal ions which neither have a salting out action on the dyestuff, nor unfavorably influence the tinctorial properties of the product, and then evaporating the reaction solution.
- the new dyestuffs containing chromium may be regarded as intermediate products of the hitherto known chromium compounds. They are sensitive towards dilute mineral acids in that they partly precipitate forinstance in a dye-bath containing the usual quantities of sulfuric acid, and do not, therefore, yield fast dyeings from such abath. They are further characterized by such an easy solubility in water that they are incapable of being precipitated from the'reaction solution by means of a saturated solution of common salt; They must therefore, if necessary after filtration, be obtained by evaporation of the reaction solution, preferably in a vacuum.
- the present chroming process is carried out in such a manner that the mixture of the chromium compound with the o-hydroxyazo-dyestuifs is heated in an aqueous medium.
- chromium compounds which are capable of forming complex chromium coinpounds the usual agents yielding-chromium may be used, such as chromium chloride, chromium fluoride, chromium sulfate, chromium sulfite, chromium acetate, chromium formate, chromium hydroxide, a chromium salt of an aromatic sulfonic acid, or the like, or a mixture of any of these chroming agents.
- chromium oxalate alone or mixed with another chroming agent (for instance a mixture of chromium sulfate or chromium sulfite and chromium oxalate) is used.
- another chroming agent for instance a mixture of chromium sulfate or chromium sulfite and chromium oxalate
- an azodyestuii' containing chromium made in the usual manner or as described in British Patent No. 364,147 may also be used asa chromof alkali metal ions by means of which the best effect is obtained, must be determined in each case by experiment.
- the proportions in which the d used are to be mixed mayvary within wide limits.
- the new chromium compounds can be used for dyeing animal fibers in the manner simieach case the most lar to that described in the copending specifi- 5: 3
- Thenew dyestuffs are useful not only for dyeing animal fibers, but also for printing, for dyeing leather, and for coloring varnishes.
- Example 2 Into'SOOO parts of Water are introduced 308 parts of the azo-dyestufi from nitrated 1- diazo-Q-hydroxynaphthal.ene-4sulfonic acid and B-naphthol, 98.5 parts of the azo-dyestufli tr 0 n1 1-diazo-2-hydroxynaphtha1ene-4-sultonic acid and a-naphthol and 25.2 parts of the azo-dyestufl from 4-nitro-2-diazo-1-phen0l-6-sulfonic and 1-phenyl-3-methyl-5-pyrazolone.
- the dyestufi' dyes wool pure black tints'of very good fastness In an acid bath the dyestufi' dyes wool pure black tints'of very good fastness.
- the sulfuric acidus'ed for dissolving the chromium hydroxide may be exchanged for the equivalent quantity of hydrochloric acid with a like result.
- Example 4 I 86 parts of the complex chromiumrcompound obtained as described in Example 1 of British Patent No. 364,147, are dissolved in 900 parts of water, 12.5 parts of the azo-' dyestuff from nitrated 1-diazo-2-h'ydroxy naphthalene 4-sulfonic acid and ,Bmaphthol are added and the whole is boiled for 4 hours in a reflux apparatus.
- the chrome complex" dyestutl is isolated byevaporating the soludi 'einqca tion undendiminished pressurei' It is'a bla ck powder. very-easily.soluble in water toi a; vio- :QE
- a bath is prepared with 2000 parts of water at a temperature of 85-90 C. and 1 part of formic acid; 100 parts of wool are entered and the liquor is circulated for a short time in a dyeing apparatus; there are then added a further quantity of 12 parts of formic acid and 78 parts of the chromium compounddescribed in Example 1. Dyeing is continued at the same temperature for about 10 minutes and then the bath is raised to the boil and boiled for minutes. There are then added two parts of concentrated sulfuric acid diluted with water in the course of 10 minutes, and after a further 20 minutes 6 parts of concentrated sulfuric acid diluted with water are added. The dyeing is developed by boiling for 1 hour. The wool is dyed black tints of very good properties of fastness.
- a manufacture of chromiferous dyestuffs wherein a mixture of a chromium com pound with orthohydroxyazodyestuifs, which chromium compound is capable of forming complex chromium compounds, and which mixture contains at least two ortho-hydroxyazodyestuffs, of which at least one is an azodyestuff from a 1-diazo-Q-hydroxynaphthalenet-sulfonic acid.
- chromiferous dyestuffs wherein a mixture of a chromium compound with orthohydroxyazodyestufi's, which chromium compound is capable of forming complex chromium compounds, and which ustufifs, whereina mixture of mixture contains an azo' d yestuff I from the ni- -trated 1 diazosQ hydroxyrraphthalene-t sulfoni'cacid and a naphtholand an azo-dyestuff from i the 1 diazo 2hydroxynaphthalene lsulfronic acid andia" naphthol, isheat'ed in an zzaqueousflsoliutiongi and in presence of sucha proportion of all ral-i metal ions as will neither serve to salt out'thedyestuff; nor exert an: un- -fav'orableinfinence on the tii'rctorial: properties of the product, and then evaporating
- a manufacture of a chromiferous dyestufl' wherein a mixture of the dyestuff containing chromium from the nitrated l-diazo- Q-hydroxynaphthalene--sulfonic acid and ,B-haphthol, with the dyestuff from the nitrated 1-diazo-2-hydroxynaphthaleneA-sulfonic acid and ,B-naphthol, is heated in an aqueous solution, and in presence of such proportion of alkali metal ions as will neither serve to salt out! the dyestufi', nor exert an unfavorable influence on the tinctorial properties of the product, and then evaporating the reaction solutionto dryness.
- the new chromium compounds which are obtained by heating a mixture of a chromium compound with ortho-hydroxyaz'odyestuffs, which chromium compound is capable offorming complex chromium compoundsf and which mixture contains at least two orthohydroxyazodyestufl's, of which at least one is .an azo-dyestuff from a 1-diazo-2-hydroxynaphthalene--siilfonic acid and a naphthol, in an aqueous solution, and in the presence of such a proportion of aklali metal ions as will neither serve to salt out the dyestufl, nor exert an unfavorable influence on the tinctorial properties of the product, and then evaporating the reaction solution to dryness, which products are dark to black powders which are very easily soluble in water, and dye wool grey to black shades of very good fastness.
- The'newchromium compound which is obtained by heating a mixture of the dyestufi containing chromium from the nitrated l-diazo- 2 -hydroxynaphthalene -sulfonic acid and ,B-naphthol with the dyestufffrom the nitrated 1-diazo-2-hydroxynaphthalene- -s'ulfonic acidand fl-naphthol, in an aqueous .solution, and in the presence of such a proportion of alkali metal ions as will neither serve to salt out the dyestufl', 'nor exert an unfavorable influence on the tinctorial properties'of the product, and then evaporating the reaction. solution to dryness, which product isa black powder which is very easily soluble in Water, and dyes wool grey to. black shades of very good fastness.
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Description
Patented July 18, 1933 UNITED --STATES PATENT QFFICE FRITZ STRAUB, OF BASEL, AND HERMANN SCHNEIDER, OF .RIEI-IEN, NEAR BASEL,
SWITZERLAND, ASSIGNORS 'lO .EIRM: SOCIETY OF BASEL, SWITZERLAND OF CHEMICAL INDUSTRY IN BASLE,
AZO-DYES'IUFFS CONTAINING CHROMIULM AND PROCESS OF MAKING SAME No Drawing. Application filed The present invention relates to the manufacture of new azo-dyestuffs containing chromium. It comprises the process of making these dyestuffs as well as the new dyestuffs themselves.
By this invention valuable new dyestuffs containing chromium are obtained by heating in an aqueous solution a mixture of a chromium compound with at least one o-hydroxy-azo-dyestuff, which chromium compound is capable-of forming complex chro mium compounds, and which mixture contains at least two o-hydroxy-azo-dyestuffs, of which at least one is an azo-dyestuff from a l-dia-zo-2-hydroxynaphthalene 4-sulfonic acid and a naphthol, in presence of a proportion of alkali metal ions which neither have a salting out action on the dyestuff, nor unfavorably influence the tinctorial properties of the product, and then evaporating the reaction solution.
The new dyestuffs containing chromium may be regarded as intermediate products of the hitherto known chromium compounds. They are sensitive towards dilute mineral acids in that they partly precipitate forinstance in a dye-bath containing the usual quantities of sulfuric acid, and do not, therefore, yield fast dyeings from such abath. They are further characterized by such an easy solubility in water that they are incapable of being precipitated from the'reaction solution by means of a saturated solution of common salt; They must therefore, if necessary after filtration, be obtained by evaporation of the reaction solution, preferably in a vacuum.
The present chroming process is carried out in such a manner that the mixture of the chromium compound with the o-hydroxyazo-dyestuifs is heated in an aqueous medium. As chromium compounds which are capable of forming complex chromium coinpounds the usual agents yielding-chromium may be used, such as chromium chloride, chromium fluoride, chromium sulfate, chromium sulfite, chromium acetate, chromium formate, chromium hydroxide, a chromium salt of an aromatic sulfonic acid, or the like, or a mixture of any of these chroming agents.
Eoveniber 5,1931, Serial No. 573,300, and in Switzerland November 14, 1930-.
Particularly good results are obtained when chromium oxalate alone or mixed with another chroming agent (for instance a mixture of chromium sulfate or chromium sulfite and chromium oxalate) is used.
Besides these chroming agents, an azodyestuii' containing chromium, made in the usual manner or as described in British Patent No. 364,147 may also be used asa chromof alkali metal ions by means of which the best effect is obtained, must be determined in each case by experiment.
The proportions in which the d used are to be mixed mayvary within wide limits.
The good result of the chroming is, however, dependent not only on the chroming (Bil agent or the proportion of alkali metal ions,
but also on other conditions, temperature, diluent and hydrogen ion concentration, under which the chroming ocsuch as time,
curs; these conditions can be varied in many ways and it is a matter of manlpulative working to determine in favorable conditions.
The new chromium compounds can be used for dyeing animal fibers in the manner simieach case the most lar to that described in the copending specifi- 5: 3
cation Serial No. 482,155, filed September 15, 1930, i. e. conducting the dyeing operation first in weak acid baths, and then developing the dyeings by treatment in dye-baths of strongeracidity. The grey or black dyeings thus produced are fast, particularly to fulling and potting. 'In the second stage, i. e. the development of the dyeings, a new complex is formed on the fiber.
Thenew dyestuffs are useful not only for dyeing animal fibers, but also for printing, for dyeing leather, and for coloring varnishes.
The following examples illustrate the in vention, the parts being by weight Emample 1 303 parts of the azo-dyestufi from nitrated 1-diazo-2-hydroxynaphthalene-4-s u l f o n i c acid and B-naphthol of the formula 98.5 parts of dyestufi from l-diazo-2- hydroxynaphthalene l sulfonic acid and rx-lllPl'lllhOl of the formula are together Suspended in 8000 parts of water. There are added22 parts of caustic soda solution of 30 per cent. strength and 3epart-s of sodium formate followed by a solution of chromium-bisulfite of 4.4 per cent. strength,
corresponding with 76 parts of Cr O and a chromium oxalate solution containing '7 .6 parts of Cr o The whole is now heated and boiled for 28 hours while stirring, whereupon the chromium compound of the three dyestuffs is isolatated by evaporation to dryness under diminished pressure. The product is a dark powder and dyes wool in an acid bath pure black tints of remarkable fastness. Grey tints areobtained if the dyeing is performed in dye-baths of weaker dyestufi concentration.
Example 2 Into'SOOO parts of Water are introduced 308 parts of the azo-dyestufi from nitrated 1- diazo-Q-hydroxynaphthal.ene-4sulfonic acid and B-naphthol, 98.5 parts of the azo-dyestufli tr 0 n1 1-diazo-2-hydroxynaphtha1ene-4-sultonic acid and a-naphthol and 25.2 parts of the azo-dyestufl from 4-nitro-2-diazo-1-phen0l-6-sulfonic and 1-phenyl-3-methyl-5-pyrazolone. After thorough intermixture,there are further added 80 parts of sodium formate, parts of calcined sodium sulfite, followed by a chrome solution corresponding with 83.6 parts of Cr O made by means of 95 parts of crystallized oxalic acid and 63 parts of hy drofiuoric acid of '50 per cent. strength. Nhile stirring well, the whole is brought to the boil and maintained boiling for 2-3 hours. The black violet solution of the chromium complex is then evaporated to dryness on the water-bath under diminished pressure. It dyes wool in an acid bath pure black tints of good'fastness.
If in this example there are used insteadof he 303 parts of the azo-dyestufl from thenitrated 1-diazo-2-hydroxynaphthalene-t-sultonic acid and ,B-naphthol 352.3 parts ofthis dyestuif, and instead of the 98.5 parts of the azo-dyestufi' from l-diazo-Q-hydroxynaphthalenebsulfonic acid and a-naphthol there are used 49.3 parts of this dyestufi, the com plex produced dyes wool black tints which are somewhat more reddish.
Example 3 parts of the azo-dyestufi from 4-nitro-2- diazo-l-phenol-6-sulfonic acid and 1-phenyl= 3-methyl-5-pyrazolone are introduced into 8000 parts of water and there are added 68 parts of crystallized sodium formate, parts of calcined sodium sulfite and then a chrome solution corresponding with 83.6 parts of C130 and made by dissolving'chromium hydroxide paste with aid of 63 parts of crystallized oxalic acid and 115 parts ofsulfuric acid of '93 per cent. strength. After heatine' the solution to boiling, it is maintained in thiscondition for 1 to 2 hours and then the chromium compound is isolated by evaporation ,todryness under diminished pressure. In an acid bath the dyestufi' dyes wool pure black tints'of very good fastness. In this example, the sulfuric acidus'ed for dissolving the chromium hydroxide may be exchanged for the equivalent quantity of hydrochloric acid with a like result.-
- Example 4 I 86 parts of the complex chromiumrcompound obtained as described in Example 1 of British Patent No. 364,147, are dissolved in 900 parts of water, 12.5 parts of the azo-' dyestuff from nitrated 1-diazo-2-h'ydroxy naphthalene 4-sulfonic acid and ,Bmaphthol are added and the whole is boiled for 4 hours in a reflux apparatus. The chrome complex" dyestutlis isolated byevaporating the soludi 'einqca tion undendiminished pressurei' It is'a bla ck powder. very-easily.soluble in water toi a; vio- :QE
- WirOi' black tints of good ftISt-DESSk blaclrisol-ution-s f In ania'cid ibat'h i t dyes I Ewa zii ple 5 A dye bath is prepared with 2000ipartsof (LS parts of formic-acid, which in the Ii hedis'tribu'te'd 'as'desire'd parts of the ch'romimn compound-niade as described in Example 1 of Bri'tislr'Patent NOI36P;147 and part of the dyestufifxfromnitrated 1- diazo2=livdroxvnaphthalene-s esu-lfonic; acid tered at, (3;, dyeing is continuedfor- /ghour andi'n the course ofhalfian h'ourthe hath is tained for'soine' time until the dyestu'ifis exof-concentratedsulfuric acid are added and boiling i'sjcontinued until the color tint is:fullfy.develbped which happens" in about 1 hour. The Word dyed deepblacktints ofqverygoodfastness.
' Ewampljegd- 5 A bath is prepared with 2000 parts of water at a temperature of 85-90 C. and 1 part of formic acid; 100 parts of wool are entered and the liquor is circulated for a short time in a dyeing apparatus; there are then added a further quantity of 12 parts of formic acid and 78 parts of the chromium compounddescribed in Example 1. Dyeing is continued at the same temperature for about 10 minutes and then the bath is raised to the boil and boiled for minutes. There are then added two parts of concentrated sulfuric acid diluted with water in the course of 10 minutes, and after a further 20 minutes 6 parts of concentrated sulfuric acid diluted with water are added. The dyeing is developed by boiling for 1 hour. The wool is dyed black tints of very good properties of fastness.
hat we claim is 1. A manufacture of chromiferous dyestuffs. wherein a mixture of a chromium com pound with orthohydroxyazodyestuifs, which chromium compound is capable of forming complex chromium compounds, and which mixture contains at least two ortho-hydroxyazodyestuffs, of which at least one is an azodyestuff from a 1-diazo-Q-hydroxynaphthalenet-sulfonic acid. and a naphthol, is heated in an aqueous solution and in presence of such a proportion of alkali metal ions as will neither serve to salt out the dyestufi', nor exert an unfavorable influence on the tinctorial properties of the product, and then evaporating the reaction solution to dryness.
2. A manufacture of chromiferous dyestuffs. wherein a mixture of a chromium compound with orthohydroxyazodyestufi's, which chromium compound is capable of forming complex chromium compounds, and which ustufifs, whereina mixture of mixture contains an azo' d yestuff I from the ni- -trated 1 diazosQ hydroxyrraphthalene-t sulfoni'cacid and a naphtholand an azo-dyestuff from i the 1 diazo 2hydroxynaphthalene lsulfronic acid andia" naphthol, isheat'ed in an zzaqueousflsoliutiongi and in presence of sucha proportion of all ral-i metal ions as will neither serve to salt out'thedyestuff; nor exert an: un- -fav'orableinfinence on the tii'rctorial: properties of the product, and then evaporating the 'reaction solution to dryness. 1
w 3.,A manufacture of chromiferous *d'yea chromium compound with orthohydroxyazodyestuffs,which =Jchromi=umcompound is capable of forming complex chromium .rcompoundd and wh ch mixture contains the az'o -dyestufi' from theznitrated *1 -diaz'o'#2 hydroxynaphthaleneA suled-in an aqueous solution, and iir-pres-encebf such a' proportion of-a l lra'li me'tal'ions as will neither serve to salt-out the dyestufi', nor exert i an unfavorable influence on the I tinctorial properties-of the-product; andthenevaporating the reaction solution to dryness.
4. A manufacture of a chromiferous dyestufl', wherein a mixture of the dyestuff containing chromium from the nitrated l-diazo- Q-hydroxynaphthalene--sulfonic acid and ,B-haphthol, with the dyestuff from the nitrated 1-diazo-2-hydroxynaphthaleneA-sulfonic acid and ,B-naphthol, is heated in an aqueous solution, and in presence of such proportion of alkali metal ions as will neither serve to salt out! the dyestufi', nor exert an unfavorable influence on the tinctorial properties of the product, and then evaporating the reaction solutionto dryness.
5. The new chromium compounds which are obtained by heating a mixture of a chromium compound with ortho-hydroxyaz'odyestuffs, which chromium compound is capable offorming complex chromium compoundsf and which mixture contains at least two orthohydroxyazodyestufl's, of which at least one is .an azo-dyestuff from a 1-diazo-2-hydroxynaphthalene--siilfonic acid and a naphthol, in an aqueous solution, and in the presence of such a proportion of aklali metal ions as will neither serve to salt out the dyestufl, nor exert an unfavorable influence on the tinctorial properties of the product, and then evaporating the reaction solution to dryness, which products are dark to black powders which are very easily soluble in water, and dye wool grey to black shades of very good fastness.
and which Inixturecontains an azo-dyestulf till) 6. The new chromium compounds which from the nitrated 1-diazo-2 hydroxynaphthalene-l-sulfonio acid and'anaphthol and an azo-dyestuff from the -1-diazo2-hydrox'ynaphthalene-L-sulfonic acid and a naphthol, in an aqueous solution, and in the presence of such a proportion of alkali metal ions as will neither serve to salt out the dye'stufi, nor exert an unfavorable influence on thetinctorial properties of the product, and then evaporating the reaction solution to dryness, which products are dark to black powders which are very easily soluble in water, and
dye wool grey to black shadesof very good i will neither serve to salt out the dyestufi, nor
exert, an unfavorable influence on the tinctorial properties of the product, and then evaporating the reaction solution to dryness, which products are dark to black powders which are very easily soluble in water, and dye wool grey to black shades of very good fastness; 4
8. The'newchromium compound which is obtained by heating a mixture of the dyestufi containing chromium from the nitrated l-diazo- 2 -hydroxynaphthalene -sulfonic acid and ,B-naphthol with the dyestufffrom the nitrated 1-diazo-2-hydroxynaphthalene- -s'ulfonic acidand fl-naphthol, in an aqueous .solution, and in the presence of such a proportion of alkali metal ions as will neither serve to salt out the dyestufl', 'nor exert an unfavorable influence on the tinctorial properties'of the product, and then evaporating the reaction. solution to dryness, which product isa black powder which is very easily soluble in Water, and dyes wool grey to. black shades of very good fastness.
' HERMANN SCHNEIDER.
FRITZ STRAUB.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1918938X | 1930-11-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US1918938A true US1918938A (en) | 1933-07-18 |
Family
ID=4566784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US573300A Expired - Lifetime US1918938A (en) | 1930-11-14 | 1931-11-05 | Azo-dyestuffs containing chromium and process of making same |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US1918938A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2727031A (en) * | 1951-08-07 | 1955-12-13 | Ciba Ltd | Metalliferous pyrazolone azodyestuffs |
| US2784179A (en) * | 1952-07-14 | 1957-03-05 | Ciba Ltd | Metalliferous azo-dyestuffs |
| US3941765A (en) * | 1973-01-18 | 1976-03-02 | Ciba-Geigy Ag | Process for the manufacture of symmetric 1:2 chromium complexes of azo dyes |
| EP0085232A3 (en) * | 1982-01-25 | 1983-08-17 | Imperial Chemical Industries Plc | Metal complex dyestuffs |
| US4563412A (en) * | 1983-12-21 | 1986-01-07 | Polaroid Corporation | Black image dye-providing materials and photographic products and processes utilizing same |
-
1931
- 1931-11-05 US US573300A patent/US1918938A/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2727031A (en) * | 1951-08-07 | 1955-12-13 | Ciba Ltd | Metalliferous pyrazolone azodyestuffs |
| US2784179A (en) * | 1952-07-14 | 1957-03-05 | Ciba Ltd | Metalliferous azo-dyestuffs |
| US3941765A (en) * | 1973-01-18 | 1976-03-02 | Ciba-Geigy Ag | Process for the manufacture of symmetric 1:2 chromium complexes of azo dyes |
| EP0085232A3 (en) * | 1982-01-25 | 1983-08-17 | Imperial Chemical Industries Plc | Metal complex dyestuffs |
| US4563412A (en) * | 1983-12-21 | 1986-01-07 | Polaroid Corporation | Black image dye-providing materials and photographic products and processes utilizing same |
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