US2417735A - Method of chroming dyestuffs with ortho hydroxy carboxylic acid chromium complexes - Google Patents

Method of chroming dyestuffs with ortho hydroxy carboxylic acid chromium complexes Download PDF

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US2417735A
US2417735A US453132A US45313242A US2417735A US 2417735 A US2417735 A US 2417735A US 453132 A US453132 A US 453132A US 45313242 A US45313242 A US 45313242A US 2417735 A US2417735 A US 2417735A
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chromium
chroming
dyestuffs
dyestufi
complex
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US453132A
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Conzetti Achille
Schmid Otto
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JR Geigy AG
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JR Geigy AG
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B45/00Complex metal compounds of azo dyes
    • C09B45/01Complex metal compounds of azo dyes characterised by the method of metallisation

Description

Patented Mar. 18, 1947 METHOD OF CHROMING DYESTUFFS WITH ORTHO HYDROXY CARBOXYLIC ACID CHROMIUM COMPLEXES Achille Conzetti, Basel,
and Otto Schmid,
Muttenz, near Basel, Switzerland, assignorsto J. R. Geigy A. G., Basel, Switzerland, a Swiss No Drawing. Application July 31, 1942, Serial No. 453,132. In Switzerland October 15, 1941 In technical literature many processes for chroming mordant dyestuffs containing sulfonic acid groups have been published, which all consist in the use either of trivalent chromium salts or of chromium hydroxide or chromites.
According to all these known processes o-hydroxycarboxy dyestuffs, free from sulfonic acid groups, of the type of Eriochromazurol B (Schultz-Lehmann, Dyestuff tables, 7th edition, No. 838) or of Eriochromfiavin A (loc. cit. No. 258) become completely insoluble compounds.
It is further known that :o '-dihydroxy azo dyestuffs, free from sulfonic acid groups, can be converted into alcohol-soluble chromium compounds, which however are not water-soluble, by treatment with trivalent chromium salts in an aqueous alcoholic solution or by the action of chromium-yielding agents in alkaline medium in the presence of salts of aliphatic o-hydroxycarboxylic acids.
There has now been made the surprising discovery that mordant dyestuffs, free from sulfonic acid groups, of the above types can be converted into water-soluble chromium compounds by treating the same in an aqueous solution or suspension at a raised temperature, preferably at boiling temperature, open or under pressure, with complex chromium compounds of aromatic ohydroxycarboxylic acids of the benzene and naphthalene series and in doing so using at least one atom of chromium for each mordant group of the dyestuff capable of being chromed.
Complex chromium compounds of aromatic o-hydroxycarboxylic acids are obtained in the known manner by treating their alkali salt solutions with trivalent chromium salts. Suitable aromatic o-hydroxycarboxylic acids are for example salicylic acid, its homologues and substitution products, such as sulfosalicylic acid, sulfocresotinic acids, further o-hydroxynaphthoic acids and their substitution products, such as sulfo-B-hydroxynaphthoic acid and so on. Even diamine compounds of complex chromium compounds of aromatic o-hydroxycarboxylic acids, such as diamine chromium salicylic. acid or its alkali salts, which are obtained in form of redviolet crystallised compounds, for example from chromium salicylate alkali salts when standing with excess amines, such as ammonia, alkyl amines, ethylene diamine or pyridine, are suitable for use according to the present invention.
The formation of water-soluble chromium compounds of mordant dyestuffs, free from sulfonic acid groups, could not be foreseen and the very smooth course of the chroming is surprising,
10 Claims. (.Cl. 260145) particularly as complex chromium compounds of aliphatic o-hydroxycarb-oxylic acids, as shown by experiments, are not very suitable as chromiumyielding agents for chroming mordant dyestuffs.
The new water-soluble chromium compounds of o-hydroxycarboxy dyestuiis, free from sulfonic acid groups, extend the field of application of many dyestuffs known for a long time. They may be used for example for dyeing cellulose, such as cotton or paper, for dyeing silk from a weak acid bath or leather. In comparison with the analogous, completely water-insoluble chromium compounds, obtainable by known chroming processes, the new water-soluble chromium compounds constitute a substantial enrichment of technology.
ihe new water-soluble chromium compounds of o:o'-dil1ydroxy azo' dyestufis, free from sulfonic acid groups, draw uniformly, from a weak acid bath, on animal fibres and partially also on cotton. They are also suitable for dyeing leather.
The present invention is illustrated, but not limited, by the following examples. Their parts are by weight unless otherwise indicated.
EXAMPLE 1 9.6 parts of Eriochromazurol B (sodium salt) (Schultz, Dyestuii tables, 7th edition, No. 838) are dissolved in 190 parts of water and stirred for about 20 minutes at -100 C. with parts of a solution of ammonium chromium salicylate, containing 1 gram atom of chromium in 2500 g. of solution. The yellow-red solution changes within 5 minutes, with a temporary violet color-- ing, into a pure blue. By salting out the cooled solution, the new chromium compound can be isolated as a violet-blue powder. It is easily soluble in water with a pure blue coloration. From the organic acid bath it dyes animal and vegetable fibres with pure blue shades. Very pure.
3 EXAMPLE 2 9.7 parts of the dyestuff Eriochromefiavin A (Schultz No. 258) are dissolved in 100 parts of water and boiled: by reflux with a solution of so- 4 um sulfosalicylate is obtained from ammonium chromium sulfosalicylate as peach-bloom red little crystals by allowing the solution, saturated with NH3, to stand. Analogous compounds are obtained with amines such as ethylene diamine,
dium chromium salicylate, corresponding to 4.5 5 parts of chromium oxide. In a short time the alkyl ammes, pyl'ldme and plpendme and the brown-olive solution of the water-soluble chromium compound of the dye tufl is formed The By treating the above mentioned dyestufi with 7 new chromium-containing dyestufi can be obsodium chromium salicylate a water-soluble c r0- tained as an olive-yellow powder by saltin out. l0 mium compound i Obtained which is y Suit- It produces, from a weak acid bath, on animal able for dyeing leather.
Table l l vl l wi D i f l 33 Color ofthe ye ng woo licylate (W) Silk (S) Dyestufi Few/fits. chrommmmm leather (L) mium sulfo compound cellulose (C) salicylate (b) 1. Eriochrome-azurol B a S, L, 0: blue. 2. Eriochrome-azurol G a S, L, C: blue. 3. Napbthochrome-grecn G (Schultz No. 851)... a S, L, 0: green. 4. 2- (4'-diethylamino-2-oxy)-bcnzoyl benzoic acid condensed with B-reso a S, L, 0: red.
and oxidised. 5. Methylenedi-o-crcsotic acid hydrol condensed with l-phenyl-3-methyl-5-pyrazoa S, L,G: brown. lone and oxidised. 6. 4-dimethylamino-2-chlorobenzaldehyde condensed with o-cresotic acid and a S, L, O: v1olet.
oxidised. 7; Eriochromeflavin A (Schultz No. 258) Z gz pfifigfi 8. Anthranilic acid 1-phenyl-3-methyl-5-pyrazolone I) W, L: yellow. 9. Anthranilic acid 2:4-dihydroxyquinoline b Yellow-orange" W, L: orange. 10. 4-nitro-2-amino-phenol l-phenyl-3-methyl-5-pyrazolone (1 Orange W, L: orange. 11. 6-111ethyl-4-nitro-2-amino-pheno1 l-phenyl-S-rnethyl-apyrazolonc b d W, L: orange. 12. 4-nitro-2-amino-phenol 2:4-dihydroxy quinohne I) W, L: red. 13. Anthranilic acid p-cresol 0 W, L: Bordeaux. 14. i-chloro2-ainino-phenol 2:4-dihydroxy on D W, L: Bordeaux. 15. 4-nitr0-2-amino-phcnol p-cresol .4 o W, L:red-brown.
complex chromium solutions from homologous salicylic acids, salicylic acid monoor di-sulfonic acid, sulfo cresotinic acids, o-hydroxy-naphthoic acids and their sulfonic acids.
EXAMPLE 3 19.6 parts of the dyestuif, free from sulfonic acid groups, obtained from diazotised 4-nitro-2- amino-phenol and l-phenyl-3-methyl-5-pyrazolone are dissolved in 800 parts of hot water with 190 parts of 34% soda lye and boiled by reflux with 130 parts of a solution of sodium chromium suli'osalicylate (corresponding to 5 parts of chromium oxide). The orange colored solution thereby separates about 5 parts of brown little crystals of a Water-insoluble, but alcohol-soluble chromium complex compound, which are filtered off hot after 2 hours. The new water-soluble chromium compound is recovered from the filtrate by salting out. It produces, from the Weak acid bath, good light-fast, uniform yellow-orange dyeings on animal fibres.
Similar products are obtained with ammonium chromium sulfosalicylate andv ammonium diamine chromium sulfosalicylate.
The said chroming agents are obtained by dissolving 1 gram atom of chromium hydroxide in a solution of 2 gram atoms of sulfosalicylic acid in 1 litre of water and neutralisation with sodium carbonateor ammonia until the reaction remains neutral to litmus. Ammonium diamine chromi- What we claimis:
1. Process for chroming dyestuffs capable of being chromed and free from sulfonic acid groups consisting in chroming such a dyestufi in an aqueous medium at a raised temperature with a complex chromium compound of a member selected from the group consisting of the aromatic o-hydroxycarbcxylic acids of the benzene and naphthalene series, using at least one atom of chromium for each mordant group of the dyestufi capable of being chromed.
2. Process for chroming dyestufis capable of being chromed and free from sulfonic acid groups consisting in chroming such a dyestuff in an aqueous medium at boiling temperature with a complex chromium compound of an o-hydroxybenzoic acid, using at least one atom of chromium for each mordant group of the dyestufi capable of being chromed.
3; Process for chroming Eriochromazurol B, consisting in chroming this dyestufi in an aqueous medium at 90-100 C. with ammonium chromium salicylate, using at least one atom of chromium for each o-hydroxy-carboxy group of the temperature with sodium chromium sulfosalicylate using at least one atom of chromium for each mordant group-of the dyestufi.
6. A dyestufi which is free from sulfonic acid groups and which contains, in complex union, trivalent' chromium and anaromatic o-hydroxycarboxylic acid, said dyestufi being obtained by chroming a chromable dyestufi which is free from sulfonic acid groups with a complex chromium compound of a member selected from the group consisting of the aromatic o-hydroxycarboxylic acids of the benzene and naphthalene series, at least one atom of chromium being present for each mordant group of the chromable dyestufi.
7. A dyestufi which is free from sulfonic acid groups and which contains, in complex union, trivalent chromium and an o-hydroxybenzoic acid, said dyestuff being obtained by chroming a chromable dyestufi which is free from sulfonic acid groups with a complex chromium compound of the o-hydroxybenzoic acid, at least one atom of chromium being present for each mordant group of the chromable dyestuff.
8. A dyestufi which is free from sulfonic acid groups and which contains, in complex union, trivalent chromium and ammonium salicylate, said dyestufi being obtained by chroming Eriochromazurol B with a complex chromium compound of ammonium salicylate, at least one atom of chromium being present for each o-hydroxycarboxy group of the chromable dyestufi.
9. A dyestuff which is free from sulfonic acid groups and which contains, in complex union, trivalent chromium and sodium salicylate, said dyestuff being obtained by chroming Eriochromfiavin A with a complex chromium compound of sodium salicylate, at least one atom of chromium being present for each o-hydroxycarboxy group of the chromable dyestuff.
10. A dyestufi which is free from sulfonic acid groups and which contains, in complex union, trivalent chromium and sodium sulfosalicylate, said dyestuff being obtained by chroming the azo dyestufi from diazotized -nitro-Z-aminophenol and 1-phenyl-3-methy15-pyrazolone with a complex chromium compound of sodium sulfosalicylate, at least one atom of chromium being present for each mordant group of the chromable dyestuff. ACHILLE CONZETTI. OTTO SCHMID,
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2565898A (en) * 1946-09-30 1951-08-28 Ciba Ltd Process for the manufacture of metalliferous azo dyestuffs
US2708193A (en) * 1950-06-29 1955-05-10 Basf Ag Water-soluble chromium-containing azo dyestuffs
US3185676A (en) * 1960-08-12 1965-05-25 Gen Aniline & Film Corp Method of azo dye chromation

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1081166B (en) * 1954-02-23 1960-05-05 Sandoz Ag Process for the production of azo dyes of the pyrazolone series and their chromium complex compounds
US6615026B1 (en) 1999-02-01 2003-09-02 A. W. Technologies, Llc Portable telephone with directional transmission antenna

Citations (12)

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FR758264A (en) * 1932-07-22 1934-01-13 Ste Ind Chim Bale Production of unsulfonated metalliferous dyestuffs
GB418622A (en) * 1933-01-25 1934-10-29 Chem Ind Basel Manufacture of chromiferous dyestuffs
US1989569A (en) * 1933-04-04 1935-01-29 Soc Of Chemical Ind Chromiferous dyestuff and process of making same
FR782389A (en) * 1933-12-23 1935-06-04 Ig Farbenindustrie Ag Process for preparing complex metal compounds of dyes
US2054489A (en) * 1932-02-02 1936-09-15 Gen Aniline Works Inc Azodyestuffs containing chromium
US2090432A (en) * 1935-01-24 1937-08-17 Chem Ind Basel Azo dyestuffs containing metal in complex union
US2180776A (en) * 1936-06-17 1939-11-21 Soc Of Chemical Ind Process for the manufacture of complex metal compounds of polyazo dyestuffs
US2193228A (en) * 1936-10-30 1940-03-12 Gen Aniline & Film Corp Copper containing azo dyestuffs
US2230686A (en) * 1938-08-19 1941-02-04 Gen Aniline & Film Corp Method of preparing azo dyestuffs containing metal
US2243020A (en) * 1938-07-25 1941-05-20 Soc Of Chemical Ind Process for producing fast tints on cellulose fibers
US2305747A (en) * 1939-06-06 1942-12-22 Chem Ind Basel Complex chromium compounds of ortho-hydroxyazo dyestuffs and process of making same
US2317671A (en) * 1941-06-06 1943-04-27 Albert L Reed Chemical compound

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2054489A (en) * 1932-02-02 1936-09-15 Gen Aniline Works Inc Azodyestuffs containing chromium
FR758264A (en) * 1932-07-22 1934-01-13 Ste Ind Chim Bale Production of unsulfonated metalliferous dyestuffs
GB418622A (en) * 1933-01-25 1934-10-29 Chem Ind Basel Manufacture of chromiferous dyestuffs
US1989569A (en) * 1933-04-04 1935-01-29 Soc Of Chemical Ind Chromiferous dyestuff and process of making same
FR782389A (en) * 1933-12-23 1935-06-04 Ig Farbenindustrie Ag Process for preparing complex metal compounds of dyes
US2090432A (en) * 1935-01-24 1937-08-17 Chem Ind Basel Azo dyestuffs containing metal in complex union
US2180776A (en) * 1936-06-17 1939-11-21 Soc Of Chemical Ind Process for the manufacture of complex metal compounds of polyazo dyestuffs
US2193228A (en) * 1936-10-30 1940-03-12 Gen Aniline & Film Corp Copper containing azo dyestuffs
US2243020A (en) * 1938-07-25 1941-05-20 Soc Of Chemical Ind Process for producing fast tints on cellulose fibers
US2230686A (en) * 1938-08-19 1941-02-04 Gen Aniline & Film Corp Method of preparing azo dyestuffs containing metal
US2305747A (en) * 1939-06-06 1942-12-22 Chem Ind Basel Complex chromium compounds of ortho-hydroxyazo dyestuffs and process of making same
US2317671A (en) * 1941-06-06 1943-04-27 Albert L Reed Chemical compound

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2565898A (en) * 1946-09-30 1951-08-28 Ciba Ltd Process for the manufacture of metalliferous azo dyestuffs
US2708193A (en) * 1950-06-29 1955-05-10 Basf Ag Water-soluble chromium-containing azo dyestuffs
US3185676A (en) * 1960-08-12 1965-05-25 Gen Aniline & Film Corp Method of azo dye chromation

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