CH639116A5 - METHOD FOR PRODUCING 1: 2 CR COMPLEXES OF DYES, SULFOGROUP-FREE. - Google Patents
METHOD FOR PRODUCING 1: 2 CR COMPLEXES OF DYES, SULFOGROUP-FREE. Download PDFInfo
- Publication number
- CH639116A5 CH639116A5 CH26579A CH26579A CH639116A5 CH 639116 A5 CH639116 A5 CH 639116A5 CH 26579 A CH26579 A CH 26579A CH 26579 A CH26579 A CH 26579A CH 639116 A5 CH639116 A5 CH 639116A5
- Authority
- CH
- Switzerland
- Prior art keywords
- alkyl
- free
- dyes
- dye
- complexes
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title claims 2
- 239000000975 dye Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000011651 chromium Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000008878 coupling Effects 0.000 claims description 5
- 238000010168 coupling process Methods 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 239000012736 aqueous medium Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 2
- GCPWJFKTWGFEHH-UHFFFAOYSA-N acetoacetamide Chemical compound CC(=O)CC(N)=O GCPWJFKTWGFEHH-UHFFFAOYSA-N 0.000 claims description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 2
- 125000005521 carbonamide group Chemical class 0.000 claims description 2
- 229960003742 phenol Drugs 0.000 claims description 2
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 3
- 125000003118 aryl group Chemical group 0.000 claims 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 2
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 1
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000203 mixture Substances 0.000 description 6
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000004043 dyeing Methods 0.000 description 4
- -1 Q-C5-alkyl sulfone Chemical class 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 3
- 238000004532 chromating Methods 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- KIEOKOFEPABQKJ-UHFFFAOYSA-N sodium dichromate Chemical compound [Na+].[Na+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KIEOKOFEPABQKJ-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000005362 aryl sulfone group Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000008121 dextrose Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 210000002268 wool Anatomy 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyamides (AREA)
Description
Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung von sulfogruppenfreien 1:2-Cr-Komplexen von Farbstoffen auf Basis mindestens eines Farbstoffs der all-35 gemeinen Formel I The present invention relates to a process for the preparation of sulfo-free 1: 2-Cr complexes of dyes based on at least one dye of the general formula I
COOH COOH
40 40
(I) (I)
45 45
worin wherein
K = Rest einer in o-Stellung zur Azogruppe kuppelnden phenolischen oder enolischen Kupplungskomponente der Hydroxybenzol-, Hydroxynaphthalin-, Acetessigsäureamid-oder Pyrazolonreihe bedeutet und 50 K = the remainder of a phenolic or enolic coupling component of the hydroxybenzene, hydroxynaphthalene, acetoacetic acid amide or pyrazolone series coupling in the o-position to the azo group and 50
A gegebenenfalls durch nichtionogene Substituenten weitersubstituiert sein kann, das dadurch gekennzeichnet ist, dass man den metallfreien Farbstoff (I) in Form der freien Säure in wässrigem Medium in Gegenwart von 1-6 Mol eines Trialka-nolamins, insbesondere Triäthanolamin, insbesondere min- 55 destens 1,5 Mol, bevorzugt 2-3 Mol, mit der stöchiometrischen Menge einer Verbindung des 6-wertigen Chroms in Gegenwart von Reduktionsmitteln bei ca. 80-105 °C chromiert. Geeignetes Reduktionsmittel ist insbesondere Traubenzucker. 60 A can optionally be further substituted by nonionic substituents, which is characterized in that the metal-free dye (I) in the form of the free acid in an aqueous medium in the presence of 1-6 mol of a trialkanolamine, in particular triethanolamine, in particular at least 55 1.5 moles, preferably 2-3 moles, with the stoichiometric amount of a compound of hexavalent chromium in the presence of reducing agents at about 80-105 ° C. A particularly suitable reducing agent is glucose. 60
Geeignete Verbindugen mit 6-wertigem Chrom sind beispielsweise Alkali- oder Ammoniumbichromate, insbesondere Natriumbichromat. Suitable compounds with hexavalent chromium are, for example, alkali or ammonium bichromates, in particular sodium bichromate.
Geeignete nichtionogene Substituenten sind beispielsweise C1-C5-Alkyl, C1-C5-Alkoxy, Halogen wie F, Cl, Br; es NOj, gegebenenfalls Q-Q-alkylsubstituiertes Sulfonamid, gegebenenfalls C rC5-alkylsubstituiertes Carbonamid, Q-C5-Alkylsulfon, Arylsulfon. Suitable nonionic substituents are, for example, C1-C5-alkyl, C1-C5-alkoxy, halogen such as F, Cl, Br; es NOj, optionally Q-Q-alkyl-substituted sulfonamide, optionally C rC5-alkyl-substituted carbonamide, Q-C5-alkyl sulfone, aryl sulfone.
worin wherein
R2 = C[-C5-Alkyl, Phenyl und worin die Reste C und B nichtionogen substituiert sein können, beispielsweise durch Halogen wie F, Cl, Br, durch Q-Q-Alkyl oder N02, wobei die Alkylreste nicht weitersubstituiert sind. R2 = C [-C5-alkyl, phenyl and in which the radicals C and B can be nonionically substituted, for example by halogen such as F, Cl, Br, by Q-Q-alkyl or NO2, the alkyl radicals not being further substituted.
Das Verfahren wird im einzelnen so durchgeführt, dass man den Farbstoff (I), der in üblicher Weise durch Kupplung hergestellt wurde, in Form der freien Säure isoliert - zweckmässigerweise bei pH-Werten unter 3 - insbesondere bei pH-Werten zwischen 2 und 0,5, anschliessend möglichst weitgehend von anorganischen Salzen befreit - beispielsweise durch Waschen mit Wasser-und dann in Form der feuchten Paste oder als getrockneten Farbstoff in wässrigem Medium in Gegenwart der angegebenen Menge Trialkanolamin mit Verbindungen, des 6-wertigen Chroms, insbesondere Natriumbichromat, und Reduktionsmitteln, insbesondere Traubenzucker, bei ca. 80-105 °C chromiert. The process is carried out in detail so that the dye (I), which was prepared in the usual manner by coupling, is isolated in the form of the free acid - expediently at pH values below 3 - in particular at pH values between 2 and 0, 5, then as far as possible freed from inorganic salts - for example by washing with water and then in the form of the moist paste or as a dried dye in an aqueous medium in the presence of the specified amount of trialkanolamine with compounds, the 6-valent chromium, in particular sodium bichromate, and reducing agents , especially dextrose, chromed at approx. 80-105 ° C.
Das Verfahren ermöglicht im allgemeinen eine praktisch vollständige Chromierung und führt zu Farbstoffen die praktisch frei von nicht komplex-gebundenem Chrom sind. The process generally enables virtually complete chromating and leads to dyes which are practically free of chromium which is not bound to the complex.
Die Farbstoffe werden vorzugsweise in Form ihrer Alkalisalze, insbesondere Natriumsalze, isoliert, die aus den Lösungen in kristalliner Form ausfallen. Um die Ausfällung als Alkalisalz möglichst vollständig zu gestalten, kann man dem Chromierungsgemisch Alkalihydroxide, insbesondere Natronlauge und/oder Alkalisalze, insbesondere Natriumchlorid, zusetzen. The dyes are preferably isolated in the form of their alkali metal salts, in particular sodium salts, which precipitate out of the solutions in crystalline form. In order to make the precipitation as alkali salt as complete as possible, alkali metal hydroxides, in particular sodium hydroxide solution and / or alkali metal salts, in particular sodium chloride, can be added to the chromating mixture.
Die Chromierungsreaktion wird im allgemeinen in Gegenwart der etwa l-20fachen Menge Wasser, bezogen auf Farbstoff, durchgeführt. Vorzugsweise verwendet man die 3fache bis lOfache Menge Wasser. The chromating reaction is generally carried out in the presence of about 1-20 times the amount of water, based on the dye. Preferably 3 to 10 times the amount of water is used.
3 3rd
639 116 639 116
Bei den 1:2-Cr-Komplexen kann es sich selbstverständlich Farbstoff The 1: 2 Cr complexes can of course be a dye
Farbton um a) symmetrische und unsymmetrische auf Basis von 2 Mol (1) handeln, d.h. solche aus 2 identischen oder nichtidentischen Farbstoffen (I), oder aber b) um unsymmetrische Komplexe auf Basis von 1 Mol (I) und 1 Mol eines beliebigen chromierbaren Farbstoffs, wie sie in der Literatur in grosser Zahl beschrieben sind. Hue to be a) symmetrical and asymmetrical based on 2 moles (1), i.e. those of 2 identical or non-identical dyes (I), or b) unsymmetrical complexes based on 1 mol (I) and 1 mol of any chromable dye, as described in large numbers in the literature.
Die erhaltenen Farbstoffe eignen sich zum Färben und Bedrucken von natürlichen und synthetischen Fasermaterialien aus Polyamiden sowie insbesondere auch zum Färben von Kunststoffen und Lacken sowie zum Färben von Leder. The dyes obtained are suitable for dyeing and printing natural and synthetic fiber materials made from polyamides and in particular also for dyeing plastics and lacquers and for dyeing leather.
Beispiel 1 example 1
1 Mol Anthranilsäure wird in üblicher Weise diazotiert und auf 1 Mol l-PhenyI-3-methyl-pyrazolon-5 gekuppelt. Anschliessend wird der Ansatz auf 95-100 °C erwärmt, mit Salzsäure auf pH 0,5 gestellt, abgesaugt und mit 1.380 ml Wasser gewaschen. 1 mol of anthranilic acid is diazotized in a conventional manner and coupled to 1 mol of 1-phenylene-3-methyl-pyrazolone-5. The mixture is then heated to 95-100 ° C, adjusted to pH 0.5 with hydrochloric acid, suction filtered and washed with 1,380 ml of water.
1 Mol = 775,9 g ausgewaschene Kupplungspaste (Farbstoffgehalt 41,5%) werden in 2.000 ml Wasser und 447 g Tri-äthanolamin verrührt und auf 95-100 °C erwärmt (bei 70-80 °C entsteht eine klare Lösung). Unter Rühren lässt man in 30 Minuten eine Lösung, bestehend aus 74,5 g NaiCr;07.2 H20, 50 g Traubenzucker und 400 ml Wasser, zutropfen und rührt 90 Minuten bei 95 °C nach. Dann kühlt man den Ansatz auf 90-95 °C ab und tropft im Verlaufe von 2 Stunden eine Lösung, bestehend aus 330 g Kochsalz, 132,5 g Natronlauge 40%ig und 1.650 ml Wasser, zu. Der Farbstoff fällt in kristalliner Form aus. Man saugt ab und wäscht in üb- 30 licher Weise mit Wasser von 90-95 °C auf der Nutsche. Gegebenenfalls kann man auch mit l%iger Natronlauge waschen. Nach dem Trocknen bei 100 °C im Vakuum erhält man einen Farbstoff, der sich zum Färben von Folienlacken in gelben Farbtönen gut eignet. 1 mol = 775.9 g of washed coupling paste (dye content 41.5%) are stirred in 2,000 ml of water and 447 g of triethanolamine and heated to 95-100 ° C (at 70-80 ° C a clear solution is formed). A solution consisting of 74.5 g of NaiCr; 07.2 H20, 50 g of glucose and 400 ml of water is added dropwise with stirring in 30 minutes and stirring is continued at 95 ° C. for 90 minutes. The mixture is then cooled to 90-95 ° C. and a solution consisting of 330 g of sodium chloride, 132.5 g of 40% sodium hydroxide solution and 1,650 ml of water is added dropwise over the course of 2 hours. The dye precipitates in a crystalline form. It is suctioned off and washed in the usual way with water at 90-95 ° C. on the suction filter. If necessary, you can also wash with 1% sodium hydroxide solution. After drying at 100 ° C in a vacuum, a dye is obtained which is well suited for dyeing film varnishes in yellow shades.
COOH COOH
Ù" Ù "
N N
HO HO
yir yir
Ù Ù
CH, CH,
gelb yellow
C2«5 C2 «5
COOH fi\-N - N COOH fi \ -N - N
Ò- O-
gelb yellow
Cl Cl
25 25th
COOH COOH
Ô- O-
CH, CH,
Cl gelb Cl yellow
35 35
Beispiel 2 Example 2
1 Mol Farbstoff Anthranilsäure -> I-(2'-Chlorphenyl)-3-methylpyrazolon-5 = 564,1 g Paste mit einem Farbstoffgehalt von 63,2%, salzarm und in saurer Form, hergestellt analog Beispiel 1, werden in einer Mischung von 655 g Wasser und 298 g Triäthanolamin bei 70-80 °C gelöst. Dann erwärmt man auf 100 °C und lässt unter Rühren eine Lösung, bestehend aus 74,5 g Na2Cr207.2 H20,50 g Traubenzucker und 440 ml Wasser, in 30 Minuten bei 100 °C zutropfen und rührt 90 Minuten bei dieser Temperatur nach. Nach der Chromierung kühlt man auf 50 °C, saugt den kristallin ausgefallenen Farbstoff ab und trocknet ihn bei 70 °C im Vakuum. Man erhält ein braunes Pulver, das Wolle aus organischen sauren Bade in gelben Tönen färbt. 1 mol of dye anthranilic acid -> I- (2'-chlorophenyl) -3-methylpyrazolone-5 = 564.1 g paste with a dye content of 63.2%, low in salt and in acid form, prepared analogously to Example 1, are mixed of 655 g of water and 298 g of triethanolamine at 70-80 ° C. The mixture is then heated to 100 ° C. and a solution consisting of 74.5 g of Na2Cr207.2 H20.50 g of glucose and 440 ml of water is added dropwise at 100 ° C. in 30 minutes, and the mixture is stirred at this temperature for 90 minutes. After chroming, the mixture is cooled to 50 ° C., the crystalline dye which has precipitated is filtered off and dried at 70 ° C. in vacuo. A brown powder is obtained which dyes wool from organic acid baths in yellow tones.
Nach dem Verfahren der Beispiele 1 und 2 lassen sich aus den in der Tabelle angeführten Farbstoffen die symmetrischen l:2-Cr-Komplexe mit den angegebenen Farbtönen herstellen: Using the procedure of Examples 1 and 2, the symmetrical 1: 2-Cr complexes with the specified shades can be prepared from the dyes listed in the table:
COOH COOH
òr* ■ " jt"™2 òr * ■ "jt" ™ 2
HO HO
% %
gelb yellow
50 50
(Ôr "N (Ôr "N
HO £ HO £
gelb yellow
55 55
c c
Claims (2)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2801035A DE2801035C2 (en) | 1978-01-11 | 1978-01-11 | Process for the preparation of 1: 2 Cr complex dyes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH639116A5 true CH639116A5 (en) | 1983-10-31 |
Family
ID=6029304
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH26579A CH639116A5 (en) | 1978-01-11 | 1979-01-11 | METHOD FOR PRODUCING 1: 2 CR COMPLEXES OF DYES, SULFOGROUP-FREE. |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS54101834A (en) |
| BE (1) | BE873383A (en) |
| CH (1) | CH639116A5 (en) |
| DE (1) | DE2801035C2 (en) |
| FR (1) | FR2414528A1 (en) |
| GB (1) | GB2013231B (en) |
| IT (1) | IT7919161A0 (en) |
| NL (1) | NL7900039A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3222966A1 (en) * | 1982-06-19 | 1983-12-22 | Bayer Ag, 5090 Leverkusen | METHOD FOR THE PRODUCTION OF CHROME COMPLEXES FROM AZO- OR AZOMETHINE DYES |
| US5019132A (en) * | 1989-11-28 | 1991-05-28 | Ciba-Geigy Corporation | Process for the preparation of concentrated 1:2 metal complex dye preparations |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA612466A (en) * | 1961-01-10 | E.I. Du Pont De Nemours And Company | Chromation of azo dyes | |
| US1693448A (en) * | 1926-06-15 | 1928-11-27 | Grasselli Dyestuff Corp | Production of metallic compounds of dyestuffs |
| DE929567C (en) * | 1952-11-07 | 1956-04-12 | Bayer Ag | Process for the production of chromium-containing dyes |
| CH343559A (en) * | 1955-10-28 | 1959-12-31 | Ciba Geigy | Process for the production of chromium-containing dyes |
| FR2224527B1 (en) * | 1973-04-04 | 1976-09-10 | Ugine Kuhlmann | |
| DE2444736C2 (en) * | 1974-09-19 | 1984-01-05 | Bayer Ag, 5090 Leverkusen | Concentrated solutions of 1: 2 azo and azomethine chromium complex dyes and process for their preparation |
-
1978
- 1978-01-11 DE DE2801035A patent/DE2801035C2/en not_active Expired
-
1979
- 1979-01-03 NL NL7900039A patent/NL7900039A/en not_active Application Discontinuation
- 1979-01-08 GB GB7900579A patent/GB2013231B/en not_active Expired
- 1979-01-09 JP JP46379A patent/JPS54101834A/en active Pending
- 1979-01-09 IT IT7919161A patent/IT7919161A0/en unknown
- 1979-01-10 FR FR7900532A patent/FR2414528A1/en active Pending
- 1979-01-10 BE BE0/192821A patent/BE873383A/en unknown
- 1979-01-11 CH CH26579A patent/CH639116A5/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| BE873383A (en) | 1979-07-10 |
| DE2801035A1 (en) | 1979-07-12 |
| GB2013231A (en) | 1979-08-08 |
| NL7900039A (en) | 1979-07-13 |
| IT7919161A0 (en) | 1979-01-09 |
| GB2013231B (en) | 1982-05-06 |
| DE2801035C2 (en) | 1984-08-16 |
| JPS54101834A (en) | 1979-08-10 |
| FR2414528A1 (en) | 1979-08-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CH634091A5 (en) | METHOD FOR PRODUCING AN AMINO ACID DYE SALT. | |
| CH639116A5 (en) | METHOD FOR PRODUCING 1: 2 CR COMPLEXES OF DYES, SULFOGROUP-FREE. | |
| DE2704364C2 (en) | ||
| DE1569603C3 (en) | Process for the preparation of oxazine dyes | |
| DE1104090B (en) | Process for the preparation of copper complex compounds of azo dyes | |
| DE2507120C2 (en) | Asymmetric 1 to 2 chromium complex compounds, processes for their preparation and their use | |
| DE2835493C2 (en) | Chromium complex dyes | |
| DE2104624A1 (en) | Basic azo dye, its manufacture and use | |
| DE1544469B1 (en) | Process for the preparation of pyridazinazo dyes, new pyridazinazo dyes and their use | |
| DE951750C (en) | Process for the production of brown, chromium-containing azo dyes | |
| DE1644219C3 (en) | 2 to 1 metal complex monoazo dyes Process for their preparation and their use | |
| DE882451C (en) | Process for the production of metal-containing azo dyes | |
| DE2500550A1 (en) | NEW CHROME COMPLEX DYES, THEIR PRODUCTION AND USE | |
| DE848980C (en) | Process for the production of new azo dyes | |
| EP0112281B1 (en) | Assymmetrical 1:2 chromium complex dyestuffs containing one azo and one azomethine compound | |
| DE956864C (en) | Process for the production of metal-containing azo dyes | |
| DE960753C (en) | Process for the preparation of metal-containing monoazo dyes | |
| DE1544469C (en) | Process for the production of pyridazinazo dyes, new pyndazinazo dyes and their use | |
| DE923736C (en) | Process for the production of metal-containing azo dyes | |
| DE2501039A1 (en) | NEW CHROME COMPLEX DYES, THEIR PRODUCTION AND USE | |
| EP0166687B1 (en) | Complex iron compounds of azo dyes prepared from naphthyl amino sulfonic acids, resorcin and nitro-amino phenol | |
| DE1444568C (en) | Azo metal complex dyes and process for their preparation | |
| DE3116295C2 (en) | Process for the preparation of copper complex azo dyes | |
| EP0126378A1 (en) | Preparation process of acid nitro dyes | |
| DE950226C (en) | Process for the preparation of disazo dyes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PL | Patent ceased |