DE4128490A1 - New cationic thiazole azo dyestuff cpds. - used on polyacrylonitrile or paper or keratinous material, prepd. from methyl amino carbo-methoxy-thiazolyl-acetate and tert. aniline - Google Patents

New cationic thiazole azo dyestuff cpds. - used on polyacrylonitrile or paper or keratinous material, prepd. from methyl amino carbo-methoxy-thiazolyl-acetate and tert. aniline

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Publication number
DE4128490A1
DE4128490A1 DE19914128490 DE4128490A DE4128490A1 DE 4128490 A1 DE4128490 A1 DE 4128490A1 DE 19914128490 DE19914128490 DE 19914128490 DE 4128490 A DE4128490 A DE 4128490A DE 4128490 A1 DE4128490 A1 DE 4128490A1
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Prior art keywords
polyacrylonitrile
colouring
paper
aniline
prepd
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DE19914128490
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German (de)
Inventor
Horst Dipl Chem Noack
Gerhard Prof Dr Mann
Bernd Dr Noll
Herbert Dr Weinelt
Regina Dipl Chem Muehlberg
Dieter Dr Sicker
Holger Dipl Chem Hartenstein
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Chemie GmbH Bitterfeld Wolfen
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Chemie GmbH Bitterfeld Wolfen
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Priority to DE19914128490 priority Critical patent/DE4128490A1/en
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    • 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
    • C09B44/00—Azo dyes containing onium groups
    • C09B44/02—Azo dyes containing onium groups containing ammonium groups not directly attached to an azo group
    • C09B44/04—Azo dyes containing onium groups containing ammonium groups not directly attached to an azo group from coupling components containing amino as the only directing group
    • 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
    • C09B44/00—Azo dyes containing onium groups
    • C09B44/10—Azo dyes containing onium groups containing cyclammonium groups attached to an azo group by a carbon atom of the ring system
    • C09B44/20—Thiazoles or hydrogenated thiazoles
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/28—Colorants ; Pigments or opacifying agents

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Coloring (AREA)

Abstract

New cationic thiazole azo dyestuffs are of the formulae (I) and (II), A = a gp. derived from an N,N-di-substd. aniline C6H5-NR1R2, R1 = Me, Et or benzyl, R2 = Me, Et or -CH2CH2N(R5)(R6)(R7), R5-7 = Me, Et or beta-methoxyethyl, An- = a Cl, methosulphate, ZnCl4 or BF4 anion. USE/ADVANTAGE - (I) are claimed for colouring polyacrylonitrile spinning compsns., and (I) and (II) for colouring paper. They are also useful for colouring keratin materials esp. in hair dyes, and (II) are also suitable for colouring polyacrylonitrile. They give red to reddish-blue hues with good fastness to washing and are readily soluble in DMF. The 2-aminothiazole dicarboxylate ester used as starting material for (I) and (II) can be prepd. easily and contain ester gps. which are stable enough to remain intact during dyestuff synthesis. In an example, 23 g. (III) were diazotised with nitrosylsulphuric acid in concn. H2SO4 and coupled with 12.1 g. dimethylaniline. The dyestuff was isolated (yield ca. 45 g.), then methylated and worked up. This gave ca. 47 g. dyestuff, which dyed polyacrylonitrile in reddish-blue hues with good fastness.

Description

Die Erfindung betrifft neue kationische Thiazolazofarbstoffe, die zum Färben von Polyacrylnitrilfasern, Papier und Keratinmaterialien verwendet werden können.The invention relates to new cationic thiazole azo dyes for dyeing of polyacrylonitrile fibers, paper and keratin materials can.

Aus der Patentliteratur sind eine Vielzahl kationischer Thiazolazofarbstoffe bekannt. Zu deren Herstellung werden 2-Aminothiazol und in 4- und 5-Stellung durch nichtionogene Reste substituierte 2-Aminothiazole eingesetzt. Die Kupp­ lung der daraus hergestellten Diazoverbindungen erfolgt mit tertiären aromati­ schen Aminen, 2-substituierten Indolen und weiteren CH-aciden Kupplungskompo­ nenten. Durch Alkylierung der Kupplungsprodukte, bevorzugt mit Dimethylsulfat als Alkylierungsmittel werden die quaternären Farbsalze erhalten. Aus dieser Gruppe der Cyclammoniumfarbstoffe sind besonders die roten und blauen Farbstof­ fe von technischem Interesse.A large number of cationic thiazoleazo dyes are from the patent literature known. For their preparation, 2-aminothiazole and in the 4- and 5-position 2-aminothiazoles substituted by nonionogenic radicals. The dome The diazo compounds produced therefrom are treated with tertiary aromati 's amines, 2-substituted indoles and other CH-acidic coupling compo nenten. By alkylation of the coupling products, preferably with dimethyl sulfate the quaternary color salts are obtained as alkylating agents. From this The group of cyclammonium dyes are especially the red and blue dyes of technical interest.

So werden gemäß US-PS 28 83 373 und DE-OS 21 42 565 durch Methylierung der Azokörper aus 2-Aminothiazol und tertiären aromatischen Aminen wertvolle blaue Farbstoffe für das Färben von Polyacrylnitrilfasern erhalten.So are according to US-PS 28 83 373 and DE-OS 21 42 565 by methylation of the azo body from 2-aminothiazole and tertiary aromatic amines valuable blue dyes obtained for dyeing polyacrylonitrile fibers.

Kationische Azofarbstoffe aus 2-Aminothiazolen mit Carbonsäureestergruppen in 4- bzw. 5-Stellung sind u. a. in der CH-PS 4 53 529, DE-OS 22 48 738 und DE-OS 21 47 809 beschrieben.Cationic azo dyes from 2-aminothiazoles with carboxylic ester groups in 4- or 5-position are u. a. in CH-PS 4 53 529, DE-OS 22 48 738 and DE-OS 21 47 809.

Nach CH-PS 4 53 529 ergeben 2-Aminothiazol-4-methyl-5-carbonsäureethylester und 2-Aminothiazol-4-phenyl-5-carbonsäureethylester nach Kupplung mit Dimethyl­ anilin und Alkylierung blaue Farbstoffe und mit 2-Methyl-indol als Kupplungs­ komponente rote Farbstoffe, die auf Polyacrylnitrilfasern eine hohe Lichtecht­ heit besitzen.According to CH-PS 4 53 529 give 2-aminothiazole-4-methyl-5-carboxylic acid ethyl ester and ethyl 2-aminothiazole-4-phenyl-5-carboxylate after coupling with dimethyl aniline and alkylation blue dyes and with 2-methyl-indole as a coupling component red dyes that have high lightfastness on polyacrylonitrile fibers possess.

Aus der DE-OS 28 22 913 ist zu entnehmen, daß biskationische Monoazofarbstoffe der FormelFrom DE-OS 28 22 913 it can be seen that biscationic monoazo dyes of the formula

R = CH₃- oder C₆H₅-
X = 0 oder NH
An = Cl- oder BF₄-
für die Spinnmassefärbung von Polyacrylnitril in violetten Farbtönen geeignet sind.R = CH₃- or C₆H₅-
X = 0 or NH
An = Cl - or BF₄ -
are suitable for spinning dyed polyacrylonitrile in violet shades.

Kationische Thiazolazofarbstoffe, die 2 Carbonsäureestergruppen verbunden mit dem Thiazolring enthalten, sind bisher aus der Literatur nicht bekannt.Cationic thiazole azo dyes that link 2 carboxylic ester groups containing with the thiazole ring are not yet known from the literature.

Die Aufgabe der Erfindung besteht darin, neue kationische Thiazolazofarbstoffe herzustellen, die am Thiazolring 2 Carbonsäureestergruppen direkt oder über Alkylreste verbrückt tragen und die für möglichst viele Anwendungsgebiete eingesetzt werden können.The object of the invention is to provide new cationic thiazoleazo dyes produce the 2 carboxylic acid ester groups directly or via the thiazole ring Wear alkyl residues bridged and for as many areas of application can be used.

Der Aufgabe der Erfindung entsprechend mußte der zur Anwendung kommende Di­ carbonsäureester des 2-Aminothiazols leicht herstellbar sein und ausreichend stabile Estergruppen enthalten, die unter den Bedingungen der Farbstoffsynthese intakt bleiben.According to the object of the invention, the Di used carboxylic acid esters of 2-aminothiazole can be easily prepared and sufficient contain stable ester groups under the conditions of dye synthesis stay intact.

Es wurde gefunden, daß neue kationische Thiazolazofarbstoffe entsprechend der Auf­ gabenstellung erhalten werden, wenn 2-Aminothiazol-4-carbomethoxy-5-essigsäure­ methylester als Diazokomponente mit tertiären aromatischen Aminen gekuppelt wird und die Kupplungsprodukte in bekannter Weise methyliert werden.It has been found that new cationic thiazoleazo dyes correspond to the On can be obtained when 2-aminothiazole-4-carbomethoxy-5-acetic acid methyl ester is coupled as a diazo component with tertiary aromatic amines and the coupling products are methylated in a known manner.

Die erfindungsgemäßen neuen Farbstoffe der allgemeinen FormelThe new dyes of the general formula according to the invention

in der
R₁ = den Methyl-, Ethyl- oder Benzylrest und
R₂ = Methyl- oder Ethylreste bedeuten,
R₃ und R₄ = für Methyl- oder Ethylgruppen steht, wobei R₃ und R₄ gleich oder verschieden sein kann,
R₅, R₆, R₇ = niederer Alkylreste bedeuten: z. B. CH₃-, C₂H₅- oder CH₂CH₂OCH₃ und
An- für das chlorid-, Methosulfat-, Tetrachlorzinkat- oder Tetrafluor­ boratanion steht, können zum Färben von Polyacrylnitrilmaterial, Papier und zur Haarfärbung verwendet werden.in the
R₁ = the methyl, ethyl or benzyl radical and
R₂ = methyl or ethyl radicals,
R₃ and R₄ = represents methyl or ethyl groups, where R₃ and R₄ can be the same or different,
R₅, R₆, R₇ = lower alkyl radicals mean: z. B. CH₃-, C₂H₅- or CH₂CH₂OCH₃ and
An - stands for the chloride, methosulfate, tetrachlorozincate or tetrafluoro borate anion, can be used for dyeing polyacrylonitrile material, paper and for dyeing hair.

Für die Spinnmassefärbung von Polyacrylnitril sind besonders die neuen Farb­ stoffe der Formel II und III geeignet. Sie zeichnen sich durch geringes Aus­ bluten in den Waschbädern und eine überraschende gute Löslichkeit in Dimethyl­ formamid aus.The new colors are particularly useful for the dyeing of polyacrylonitrile substances of formula II and III suitable. They are characterized by little loss bleed in the wash baths and surprisingly good solubility in dimethyl formamide.

Die erfindungsgemäßen neuen Farbstoffe der allgemeinen Formel I bis IV färben Polyacrylnitrilmaterialien in roten bis rötlich-blauen Tönen mit guten Allge­ meinechtheiten an.The novel dyes of the general formula I to IV dye Polyacrylonitrile materials in red to reddish-blue tones with good generality genuineness.

Die Erfindung soll an nachfolgenden Beispielen erläutert werden: The invention is illustrated by the following examples:  

Ausführungsbeispiel 1Embodiment 1

23 g 2-Aminothiazol-4-carbomethoxy-5-essigsäuremethylester werden in 50 ml Schwefelsäure (conz.) mit 50 ml Nitroxylschwefelsäure , welche 6,9 g Natrium­ nitrit entspricht, bei -5°C diazotiert. Zu der mit 500 g Eis verdünnten Di­ azolösung wird bei -5°C eine Lösung von 12,1 g Dimethylanilin in 50 ml Was­ ser und 10 ml Schwefelsäure (conz.) langsam hinzugesetzt. Nach ca. 2 h Nach­ rühren bei -5°C bis 0°C ist die Kupplung beendet. Durch Zugabe von Natrium­ acetat wird bis zur Bisulfatstufe abgestumpft. Der abgeschiedene Farbstoff wird abgesaugt und getrocknet. Es werden ca. 45 g Farbstoff erhalten.23 g of 2-aminothiazole-4-carbomethoxy-5-acetic acid methyl ester are dissolved in 50 ml Sulfuric acid (conc.) With 50 ml nitroxylsulfuric acid, which contains 6.9 g sodium corresponds to nitrite, diazotized at -5 ° C. To the Di. Diluted with 500 g ice azo solution at -5 ° C is a solution of 12.1 g of dimethylaniline in 50 ml water and 10 ml sulfuric acid (conc.) slowly added. After about 2 hours stirring at -5 ° C to 0 ° C the coupling is finished. By adding sodium acetate is blunted to the bisulfate level. The separated dye is suctioned off and dried. About 45 g of dye are obtained.

Zur Methylierung werden 45 g des obigen Farbstoffes in 500 ml Chlorbenzol (wasserfrei) eingetragen und nach Zusatz von 12,2 g Zinkoxyd bei 40°C mit 25 ml Dimethylsulfat tropfenweise versetzt, rührt 1 h nach und danach weite­ re 3 h bei 80-90°C. Der anfallende Farbstoff wird abgesaugt und in 800 ml Wasser eingetragen und mit Kochsalz und Zinkchloridlösung ausgefällt. Es wer­ den ca. 47 g Farbstoff erhalten. Der Farbstoff färbt Polyacrylnitril in rot­ stichig blauen Tönen mit guten Allgemeinechtheiten an.For methylation, 45 g of the above dye in 500 ml of chlorobenzene (anhydrous) entered and after adding 12.2 g of zinc oxide at 40 ° C with 25 ml of dimethyl sulfate are added dropwise, stirring is continued for 1 h and then wide re 3 h at 80-90 ° C. The resulting dye is suctioned off and in 800 ml Water entered and precipitated with table salt and zinc chloride solution. It who receive the approx. 47 g dye. The dye colors polyacrylonitrile in red tinged blue tones with good general fastness.

Ausführungsbeispiel 2 Embodiment 2

23 g 2-Aminothiazol-4-carbomethoxy-5-essigsäuremethylester werden im Beispiel 1 beschrieben diazotiert. Zu der mit 500 g Eis verdUnnten Diazotierung werden bei -5 bis 0°C 32 g N-Ethyl-N-phenylaminoethyl-trimethylammoniummethosulfat in 150 ml Wasser hinzugesetzt. Nach 2-3 h wird durch Zusatz von verdünnter Natronlauge auf pH 4 gestellt und der Farbstoff abgesaugt. Es werden 60 g 5 Farbstoff erhalten. Der Farbstoff färbt Papier in roten Tönen.23 g of 2-aminothiazole-4-carbomethoxy-5-acetic acid methyl ester are described in Example 1 described diazotized. To the diazotization diluted with 500 g of ice at -5 to 0 ° C 32 g of N-ethyl-N-phenylaminoethyl-trimethylammonium methosulfate added in 150 ml of water. After 2-3 h is diluted by adding Sodium hydroxide solution adjusted to pH 4 and the dye is suctioned off. There will be 60 g 5 dye obtained. The dye dyes paper in red tones.

Ausführungsbeispiel 3Embodiment 3

30 g des nach Beispiel 2 erhaltenen Farbstoffes werden in 120 ml Wasser mit 7 g Zinkoxyd verrührt und in ca. 15 min bei 30-35°C mit 15 g Dimethylsulfat hinzugesetzt. Nach ca. 1stündigem Nachrühren bei ca. 35°C wird auf 60°C erwärmt und ca. 30 min bei dieser Temperatur gerührt. Aus der mit 50 ml Wasser verdünnten Reaktionslösung wird der methylierte Farbstoff durch Zusatz von 20 g Kochsalz und 40 ml Zinkchloridlösung (12,5%ig) abgeschieden und getrocknet. Der Farbstoff ergibt auf Polyacrylnitril violette Nuancen mit guten Allgemein­ echtheiten. 30 g of the dye obtained in Example 2 are mixed in 120 ml of water 7 g of zinc oxide are stirred and in about 15 min at 30-35 ° C with 15 g of dimethyl sulfate added. After stirring for approx. 1 hour at approx. 35 ° C, the temperature increases to 60 ° C warmed and stirred for about 30 min at this temperature. From the with 50 ml of water diluted reaction solution is the methylated dye by adding 20 g of sodium chloride and 40 ml of zinc chloride solution (12.5%) separated and dried. The dye gives violet shades on polyacrylonitrile with good general authenticity.  

Ausführungsbeispiel 4Embodiment 4

23 g 2-Aminothiazol-4-carbomethoxy-5-essigsäuremethylester werden wie in Bei­ spiel 1 diazotiert und die Diazotierung in 500 ml Eis eingetragen.23 g of 2-aminothiazole-4-carbomethoxy-5-acetic acid methyl ester are as in Bei game 1 diazotized and the diazotization in 500 ml of ice.

Bei -5 bis 0°C werden zur Kupplung 13,4 g N,N′-Diethyl-N,N′-diphenylethylen­ diamin gelöst in 200 ml Wasser und 10 ml Schwefelsäure hinzugesetzt und ca. 2 h bei -5 bis 0°C gerührt. Danach wird mit Natronlauge (25%ig) bei 5-10°C auf pH 6-7 eingestellt und der Farbstoff angesaugt und mehrmals mit Wasser nachgewaschen.At -5 to 0 ° C for coupling 13.4 g of N, N'-diethyl-N, N'-diphenylethylene diamine dissolved in 200 ml water and 10 ml sulfuric acid and approx. Stirred at -5 to 0 ° C for 2 h. Then with sodium hydroxide solution (25%) at 5-10 ° C. adjusted to pH 6-7 and the dye sucked in and several times with water washed.

Der feuchte Preßkuchen wird in 150 ml Wasser mit 24,4 g Zinkoxyd verrührt und bei 35-40°C 48 ml Dimethylsulfat hinzugesetzt. Es wird 1 h bei dieser Temperatur gerührt und danach auf 60°C erwärmt, eine weitere Stunde gerührt und aus der mit 100 ml Wasser verdünnten Reaktionslösung der Farbstoff mit 80 ml Zinkchloridlösung und Kochsalz ausgefällt.The moist press cake is stirred in 150 ml of water with 24.4 g of zinc oxide and added 48 ml of dimethyl sulfate at 35-40 ° C. It will be 1 hour at this Stirred temperature and then heated to 60 ° C, stirred for a further hour and from the reaction solution diluted with 100 ml of water the dye with 80 ml of zinc chloride solution and table salt precipitated.

Es werden ca. 46 g Farbstoff erhalten. Der Farbstoff färbt Polyacrylnitril in violetten Tönen mit guten Allgemeinechtheiten an.About 46 g of dye are obtained. The dye colors polyacrylonitrile in violet tones with good general fastness properties.

Claims (5)

1. Neue kationische Thiazolazofarbstoffe, dadurch gekennzeichnet, daß diese der allgemeinen Formel in der A der Rest eines N,N-disubstituierten Anilins der Formel in der
R₁ = CH₃-, -C₂H₅ oder -CH₂C₆H₅
R₂ = CH₃-, -C₂H₅ oder bedeuten,
wobei R₅, R₆, R₇ = CH₃-, C₂H₅- oder -CH₂CH₂OCH₃-Reste darstellen, und
An- für das Chlorid-, Methosulfat-, Tetrachlorozinkat- und Tetrafluorboratanion steht, entsprechen.1. New cationic thiazoleazo dyes, characterized in that they have the general formula in which A is the residue of an N, N-disubstituted aniline of the formula in the
R₁ = CH₃-, -C₂H₅ or -CH₂C₆H₅
R₂ = CH₃-, -C₂H₅ or mean,
where R₅, R₆, R₇ = CH₃-, C₂H₅- or -CH₂CH₂OCH₃ radicals, and
An - represents the chloride, methosulfate, tetrachlorozincate and tetrafluoroborate anion. 2. Neue kationische Thiazolazofarbstoffe nach Anspruch 1, gekennzeichnet dadurch, daß der Rest A in Formel 1 in der Alkyl- für den Methyl- oder Ethylrest steht, bedeutet. 2. New cationic thiazoleazo dyes according to claim 1, characterized in that the radical A in formula 1 in which alkyl represents the methyl or ethyl radical means. 3. Neue kationische Thiazolazofarbstoffe, dadurch gekennzeichnet, daß diese der Formel in der
R₅, R₆, R₇ = CH₃, CH₂H₅- oder
-CH₂CH₂O-CH₃-Reste bedeuten und
An- für Chlorid-, Methosulfat-, Tetrachlorozinkat- und Tetrafluorboratanion steht,
entsprechen.3. New cationic thiazoleazo dyes, characterized in that they have the formula in the
R₅, R₆, R₇ = CH₃, CH₂H₅- or
-CH₂CH₂O-CH₃ radicals mean and
An - stands for chloride, methosulfate, tetrachlorozincate and tetrafluoroborate anion,
correspond. 4. Verwendung von Farbstoffen der Formel der Ansprüche 1 und 2 zum Färben von Polyacrylnitril in der Spinnmasse.4. Use of dyes of the formula of claims 1 and 2 for dyeing of polyacrylonitrile in the dope. 5. Verwendung der Verbindungen gemäß Anspruch 1 bis 3 zum Färben von Papier.5. Use of the compounds according to claims 1 to 3 for dyeing paper.
DE19914128490 1991-08-28 1991-08-28 New cationic thiazole azo dyestuff cpds. - used on polyacrylonitrile or paper or keratinous material, prepd. from methyl amino carbo-methoxy-thiazolyl-acetate and tert. aniline Withdrawn DE4128490A1 (en)

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4314787A1 (en) * 1993-05-05 1994-11-10 Oekologische Sanierungs Und En N-Benzylated triazoleazo dyes and preparation thereof
EP0757083A2 (en) * 1995-08-02 1997-02-05 Ciba SC Holding AG Cationic thiazolazo and benzothiazolazo dyestuffs
FR2822698A1 (en) * 2001-04-03 2002-10-04 Oreal NEW DYE COMPOSITION FOR DYEING KERATIN FIBERS COMPRISING A DICATIONIC MONOAZO DYE
FR2825703A1 (en) * 2001-06-11 2002-12-13 Oreal COMPOSITION FOR DYEING KERATINIC FIBERS COMPRISING A SPECIAL DICATION DIAZOIC DYE
FR2825624A1 (en) * 2001-06-12 2002-12-13 Oreal DYEING COMPOSITION OF HUMAN KERATINIC FIBERS WITH DIRECT DYES AND DICATIONIC COMPOUNDS
FR2825622A1 (en) * 2001-06-11 2002-12-13 Oreal COMPOSITION FOR DYEING KERATINIC FIBERS COMPRISING A SPECIAL DICATION DIAZOIC DYE
FR2825623A1 (en) * 2001-06-12 2002-12-13 Oreal DYEING COMPOSITION OF HUMAN KERATINIC FIBERS WITH OXIDATION DYES AND DICATIONIC COMPOUNDS
FR2825625A1 (en) * 2001-06-12 2002-12-13 Oreal USE OF DICATIONIC COMPOUNDS IN DYEING OF HUMAN KERATIN FIBERS AND COMPOSITIONS CONTAINING SAME
WO2005058840A2 (en) * 2003-12-19 2005-06-30 Ciba Specialty Chemicals Holding Inc. Method of coloring with capped diazotized compound and coupling component
FR2872035A1 (en) * 2004-06-23 2005-12-30 Oreal Use of polycationic compound as a direct dye in tinctorial compositions for dyeing keratinous fibers (preferably human keratinous fibers e.g. hair) or for the manufacture of the tinctorial composition
US7326259B2 (en) 2004-06-23 2008-02-05 L'oreal S.A. Use of polycationic compounds in the dyeing of keratinous fibres
US7582122B2 (en) 2005-08-26 2009-09-01 L'oreal S.A. Mixed cationic dyes comprising at least one anthraquinone chromophore and their use in methods of hair dyeing
WO2016083012A1 (en) * 2014-11-25 2016-06-02 Henkel Ag & Co. Kgaa Agents for dyeing keratin fibres, containing at least one dimeric, dicationic azo dye and at least one anionic and/or cationic surfactant
US9889321B2 (en) 2014-11-25 2018-02-13 Henkel Ag & Co. Kgaa Agents for dyeing keratin fibers, containing at least one dimeric, ring-bridged azo dye
US10226648B2 (en) 2014-11-25 2019-03-12 Henkel Ag & Co. Kgaa Agents for dyeing keratin fibres, containing at least one dimeric, dicationic azo dye and at least one non-ionic surfactant
US10226647B2 (en) 2014-11-25 2019-03-12 Henkel Ag & Co. Kgaa Agents for dyeing keratin fibers, containing at least one dimeric, dicationic azo dye and at least one anionic surfactant
US10406089B2 (en) 2014-11-25 2019-09-10 Henkel Ag & Co. Kgaa Agents for dyeing keratin fibres, containing at least one dimeric, dicationic azo dye with special substitution pattern

Cited By (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4314787A1 (en) * 1993-05-05 1994-11-10 Oekologische Sanierungs Und En N-Benzylated triazoleazo dyes and preparation thereof
EP0757083A2 (en) * 1995-08-02 1997-02-05 Ciba SC Holding AG Cationic thiazolazo and benzothiazolazo dyestuffs
EP0757083A3 (en) * 1995-08-02 2000-01-12 Ciba SC Holding AG Cationic thiazolazo and benzothiazolazo dyestuffs
US7060110B2 (en) 2001-04-03 2006-06-13 L'oreal Dyeing composition for dyeing keratinous fibres comprising a particular dicationic monoazo dye
WO2002080869A2 (en) * 2001-04-03 2002-10-17 L'oreal Novel dyeing composition for dyeing keratinous fibres comprising a particular dicationic monoazo dye
FR2822698A1 (en) * 2001-04-03 2002-10-04 Oreal NEW DYE COMPOSITION FOR DYEING KERATIN FIBERS COMPRISING A DICATIONIC MONOAZO DYE
WO2002080869A3 (en) * 2001-04-03 2004-02-19 Oreal Novel dyeing composition for dyeing keratinous fibres comprising a particular dicationic monoazo dye
FR2825703A1 (en) * 2001-06-11 2002-12-13 Oreal COMPOSITION FOR DYEING KERATINIC FIBERS COMPRISING A SPECIAL DICATION DIAZOIC DYE
WO2002100834A1 (en) * 2001-06-11 2002-12-19 L'oreal Dyeing composition for keratinous fibres comprising a particular dicationic diazo dye
FR2825622A1 (en) * 2001-06-11 2002-12-13 Oreal COMPOSITION FOR DYEING KERATINIC FIBERS COMPRISING A SPECIAL DICATION DIAZOIC DYE
US7001436B2 (en) 2001-06-11 2006-02-21 L'oreal S.A. Dyeing composition for keratinous fibres comprising a particular dicationic diazo dye
US7407516B2 (en) 2001-06-11 2008-08-05 L'oreal, S.A. Dyeing composition for keratinous fibers comprising a dicationic diazo dye
WO2002100369A2 (en) * 2001-06-11 2002-12-19 L'oreal Dyeing composition for keratinous fibres comprising a particular dicationic diazo dye
WO2002100369A3 (en) * 2001-06-11 2004-02-19 Oreal Dyeing composition for keratinous fibres comprising a particular dicationic diazo dye
FR2825624A1 (en) * 2001-06-12 2002-12-13 Oreal DYEING COMPOSITION OF HUMAN KERATINIC FIBERS WITH DIRECT DYES AND DICATIONIC COMPOUNDS
WO2002100366A3 (en) * 2001-06-12 2004-02-19 Oreal Dyeing composition for human keratinous fibres with oxidation dyes and dicationic compounds
WO2002100367A1 (en) * 2001-06-12 2002-12-19 L'oreal Dyeing composition for human keratinous fibres with direct dyes and dicationic compounds
WO2002100365A1 (en) * 2001-06-12 2002-12-19 L'oreal Use of dicationic compounds for dyeing human keratinous fibres and compositions containing same
WO2002100366A2 (en) * 2001-06-12 2002-12-19 L'oreal Dyeing composition for human keratinous fibres with oxidation dyes and dicationic compounds
FR2825625A1 (en) * 2001-06-12 2002-12-13 Oreal USE OF DICATIONIC COMPOUNDS IN DYEING OF HUMAN KERATIN FIBERS AND COMPOSITIONS CONTAINING SAME
US7261743B2 (en) 2001-06-12 2007-08-28 L'oreal Dicationic compounds for dyeing human keratin fibers, and compositions comprising them
US7189266B2 (en) 2001-06-12 2007-03-13 L'oreal, S.A. Dyeing composition for human keratinous fibres with direct dyes and dicationic compounds
FR2825623A1 (en) * 2001-06-12 2002-12-13 Oreal DYEING COMPOSITION OF HUMAN KERATINIC FIBERS WITH OXIDATION DYES AND DICATIONIC COMPOUNDS
US7172631B2 (en) 2001-06-12 2007-02-06 L'oreal S.A. Dyeing composition for human keratinous fibers with oxidation dyes and dicationic compounds
WO2005058840A2 (en) * 2003-12-19 2005-06-30 Ciba Specialty Chemicals Holding Inc. Method of coloring with capped diazotized compound and coupling component
WO2005058840A3 (en) * 2003-12-19 2005-08-11 Ciba Sc Holding Ag Method of coloring with capped diazotized compound and coupling component
EP1618865A1 (en) * 2004-06-23 2006-01-25 L'oreal Use of polycationic compounds for dyeing keratin fibres
FR2872035A1 (en) * 2004-06-23 2005-12-30 Oreal Use of polycationic compound as a direct dye in tinctorial compositions for dyeing keratinous fibers (preferably human keratinous fibers e.g. hair) or for the manufacture of the tinctorial composition
US7326259B2 (en) 2004-06-23 2008-02-05 L'oreal S.A. Use of polycationic compounds in the dyeing of keratinous fibres
US7582122B2 (en) 2005-08-26 2009-09-01 L'oreal S.A. Mixed cationic dyes comprising at least one anthraquinone chromophore and their use in methods of hair dyeing
WO2016083012A1 (en) * 2014-11-25 2016-06-02 Henkel Ag & Co. Kgaa Agents for dyeing keratin fibres, containing at least one dimeric, dicationic azo dye and at least one anionic and/or cationic surfactant
US9889321B2 (en) 2014-11-25 2018-02-13 Henkel Ag & Co. Kgaa Agents for dyeing keratin fibers, containing at least one dimeric, ring-bridged azo dye
US10226648B2 (en) 2014-11-25 2019-03-12 Henkel Ag & Co. Kgaa Agents for dyeing keratin fibres, containing at least one dimeric, dicationic azo dye and at least one non-ionic surfactant
US10226647B2 (en) 2014-11-25 2019-03-12 Henkel Ag & Co. Kgaa Agents for dyeing keratin fibers, containing at least one dimeric, dicationic azo dye and at least one anionic surfactant
US10406089B2 (en) 2014-11-25 2019-09-10 Henkel Ag & Co. Kgaa Agents for dyeing keratin fibres, containing at least one dimeric, dicationic azo dye with special substitution pattern
US10413498B2 (en) 2014-11-25 2019-09-17 Henkel Ag & Co. Kgaa Agents for dyeing keratin fibers, containing at least one dimeric, dicationic azo dye and at least one anionic and/or cationic surfactant

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