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EP1727513A1 - Hair coloring agent containing indigoid vat dyes - Google Patents

Hair coloring agent containing indigoid vat dyes

Info

Publication number
EP1727513A1
EP1727513A1 EP04821834A EP04821834A EP1727513A1 EP 1727513 A1 EP1727513 A1 EP 1727513A1 EP 04821834 A EP04821834 A EP 04821834A EP 04821834 A EP04821834 A EP 04821834A EP 1727513 A1 EP1727513 A1 EP 1727513A1
Authority
EP
European Patent Office
Prior art keywords
polyquaternium
amino
acid
hair
alkaline medium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04821834A
Other languages
German (de)
French (fr)
Inventor
Manuela Javet
Catherine MÜLLER
Anita Roulin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Deutschland GmbH
Original Assignee
Wella GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wella GmbH filed Critical Wella GmbH
Publication of EP1727513A1 publication Critical patent/EP1727513A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4913—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid
    • A61K8/492—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid having condensed rings, e.g. indol
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34—Alcohols
    • A61K8/345—Alcohols containing more than one hydroxy group
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/35—Ketones, e.g. benzophenone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/10—Preparations for permanently dyeing the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/54—Polymers characterized by specific structures/properties
    • A61K2800/542—Polymers characterized by specific structures/properties characterized by the charge
    • A61K2800/5426—Polymers characterized by specific structures/properties characterized by the charge cationic

Definitions

  • the present invention relates to an agent and method for dyeing hair, in particular human hair, using so-called indigo vat dyes.
  • vat dyes are widely used in the dyeing of cellulosic fiber materials; on the other hand, they are only used very rarely for animal fibers, such as wool or hair, since these do not survive the required very high pH of around 13 without drastic damage.
  • very aggressive reducing agents such as sodium dithionite (hydrosulfite) or sodium bisulfite, are usually used. For these reasons, vat dyeing has practically not been successful even with animal fibers.
  • vat dyes such as, for example, indigo
  • indigo vat dyes
  • dyeing with vat dyes can also be carried out under physiologically tolerable conditions if cationic compounds are added to the dye mixture and the pH is adjusted accordingly before the dyeing.
  • cationic compounds are added to the dye mixture and the pH is adjusted accordingly before the dyeing.
  • lightening is possible, with partial or complete decolorization of the natural hair pigment melanin during the final oxidation step.
  • the present application therefore relates to an agent for coloring hair, which is characterized in that it contains at least one indigoid vat dye, at least one cationic compound and as a reducing agent at least one compound which forms an endiol in the alkaline medium.
  • Another object of the present application is a ready-to-use agent for dyeing hair, which is characterized in that it contains an indigoid vat dye which is reduced in the presence of a cationic compound with an endiol-forming compound in an alkaline medium, and one pH of 4 to 11.
  • Indigoid vat dyes for the purposes of the invention include in particular indigo and indirubin (CI 75790) and indigo derivatives, such as, for example, 6,6'-dibromoindigo, ⁇ . ⁇ 'J'-tetrabromoindigo, 4,4', 7,7'-tetrachloroindigo, Thioindigo, 6,6'-dichloro-4,4'-dimethylthioindigo, 5,5'-dichloro-7,7'-dimethylthioindigo, 4,4 ', 7,7'-tetramethylthioindigo and mixtures thereof call.
  • Other suitable vat dyes from this group can also be found in the Color Index (C.I.), third edition, 1971, published by the Society of Dyers and Colorists in the sections vat and sulfur dyes (vat dyes / sulfur dyes).
  • the indigoid vat dyes are used in a total amount of 0.01 to 10% by weight, preferably 0.1 to 2% by weight.
  • endiols endiolates
  • reducing agents such as, for example, monohydroxyacetone, dihydroxyacetone, acetoin, glutaroin, adipoin, glycol aldehyde, benzoin, 2,3-dihydroxyacrylaldehyde and cycopentadiolone, with acetoin, monohydroxyacetone and dihydroxyacetone being particularly preferred.
  • Alkalizing agents for the reduction step are sodium or potassium hydroxide, or alkali salts of aromatic mono-hydroxy or polyhydroxy compounds, such as sodium or potassium phenolate or sodium or potassium cresolate.
  • the pH value for the reduction step is generally 10 to 13.
  • the reducing agents are either in an equimolar amount or in an up to 50-fold molar excess, based on the vat. dye used, a 3 to ⁇ -fold molar excess is particularly preferred.
  • organic solvents can be used in the reduction in a concentration of 0.1 to 80 percent by weight, preferably between 5 and 50 percent by weight.
  • the organic solvents should form a homogeneous phase with water.
  • organic solvents such as ethanol, n-propanol, isopropanol, n-butanol, glycols, such as, for example, ethylene glycol, propylene glycol, lactones, lactams, acid amides of lower carboxylic acids, ureas and sulfones are suitable and sulfoxides in question. Mixtures of these solvents can also be used.
  • cationic compounds preferably cationic polymers, such as, for example, Polyquaternium-2, Polyquatemium-4, Polyquaternium-5, Polyquatemium-6, Polyquatemium-7, Polyquatemium-10, Polyquatemium -11, polyquaternium-15, polyquaternium-16, polyquaternium-17, polyquaternium-18, polyquaternium-19, polyquaternium-20, polyquaternium-22, polyquaternium-24, polyquaternium-27, polyquaternium-28, polyquaternium-29, polyquaternium-31 , Polyquaternium-35, Polyquaternium-36, Polyquaternium-37, Polyquaternium-39, Polyquaternium-44, Polyquaternium-46, Polyquaternium-47, Polyquaternium-51, Polyquaternium-55, Polyquaternium-57, Hydroxypropylguar-hydroxypropyltrimethylernonium chloride, -hydroxypropyltrimethyl
  • Polyquaternium-4 are particularly preferred (Hydroxyethyl cellulose-dimethyldiallylammonium chloride copolymer), polyquaternium-7 (dimethyldiallylammonium chloride-acrylamide copolymer) and polyquaternium-22 (acrylic acid-diallyldimethylammonium chloride copolymer).
  • the cationic compounds are used in a total amount of 0.001 to 5 percent by weight, in particular 0.1 to 1 percent by weight.
  • ammonium ions for example in the form of aqueous ammonia or ammonium salts.
  • amines such as, for example, glucamines, aminomethylpropanol, monoethanolamine or triethanolamine
  • inorganic bases for example ammonium carbonate, ammonium hydrogen carbonate or ammonium carbonate.
  • the strongly alkaline pH of the color composition is adjusted to a physiologically tolerable value of 4 to 11, preferably 6 to 10.
  • Buffer systems or inorganic or organic acids for example lactic acid, citric acid, tartaric acid, glycolic acid, acetic acid, phosphoric acid, ammonium sulfate, ammonium chloride or cetyl lactate, can be used, for example, to set the desired pH.
  • oxidation dye precursors can also be added to the colorant according to the invention after the reduction step.
  • suitable oxidation dye precursors are the following developer substances and coupler substances and self-coupling compounds: (i) Developer substances: 1,4-diamino-benzene (p-phenylenediamine), 1,4-diamino-2-methyl-benzene (p -Toluenediamine), 1,4-diamino-2,6-dimethyl-benzene, 1,4-diamino-3,5-diethyl-benzene, 1,4-diamino-2,5-dimethyl-benzene, 1,4- Diamino-2,3-dimethyl-benzene, 2-chloro-1,4-diaminobenzene, 1,4-diamino-2- (thiophene-2-yl) benzene, 1,4-diamino-2- (thiophene-3- yl) benzene, 1,4-d
  • Coupler substances N- (3-dimethylamino-phenyl) urea, 2,6-diamino-pyridine, 2-amino-4 - [(2-hydroxyethyl) amino] -anisoI, 2,4-diamino-1- fluoro-5-methyl-benzene, 2,4-diamino-1-methoxy-5-methyl-benzene, 2,4-diamino-1-ethoxy-5-methyl-benzene, 2,4-diamino-1- (2nd -hydroxy-ethoxy) -5-methyl-benzene, 2,4-di [(2-hydroxyethyl) amino] -1, 5-dimethoxy-benzene, 2,3-diamino-6-methoxy-pyridine, 3-amino- 6-methoxy-2- (methylamino) pyridine, 2,6-diamino-3,5-dimethoxy-pyridine, 3,5-diamino-2,6-ddiamin
  • the total amount of the oxidation dye precursors contained in the agent according to the invention can be about 0.01 to 12 percent by weight, in particular about 0.2 to 6 percent by weight.
  • customary natural and / or synthetic direct dyes for example so-called plant dyes such as henna, triphenylmethane dyes, aromatic nitro dyes, azo dyes, quinones, can also be used. dyes, cationic or anionic dyes contained in the colorant.
  • Suitable synthetic dyes are: 1,4-bis [(2-hydroxyethyl) amino] -2-nitrobenzene, 1- (2-hydroxyethyl) amino-2-nitro-4- [di (2-hydroxyethyl) -amino] -benzene (HC Blue No. 2), 1 -amino-3-methyl-4 - [(2-hydroxyethyl) -amino] -6-nitrobenzene (HC Violet No. 1), 4- [ethyl- ( 2-hydroxyethyl) amino] -1 - [(2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Blue No.
  • the total amount of direct dyes in the agent according to the invention can be about 0.01 to 7 percent by weight, preferably about 0.2 to 4 percent by weight.
  • antioxidants such as, for example, ascorbic acid, thioglycolic acid or sodium sulfite, and complexing agents for heavy metals, for example ethylenediaminetetraacetate or nitriloacetic acid, can be present in the agent according to the invention in an amount of up to about 0.1% by weight.
  • Perfume oils can be contained in the color carrier composition according to the invention in an amount of up to about 1 percent by weight.
  • the hair colorant described above may optionally contain other additives customary for hair colorants, such as thickeners, for example homopolymers of acrylic acid, vegetable gums, cellulose and Starch derivatives, algal polyasaccharides, amphiphilic associative thickeners, furthermore preservatives;
  • Antioxidants for example sodium sulfite, thioglycolic acid or ascorbic acid; complexing; Solvents such as water, or, as already described, lower aliphatic alcohols, for example aliphatic alcohols having 1 to 4 carbon atoms such as ethanol, propanol and isopropanol, or glycols such as glycerol and 1,2-propylene glycol, or also sorbitol and wetting agents or emulsifiers, from the classes of anionic, cationic, amphoteric or nonionic surface-active substances and also plasticizers; Vaseline; Contain silicone oils, paraffin oil, polysorbates and fatty acids as well as care
  • the agent according to the invention is preferably packaged in the form of an aqueous or aqueous-alcoholic preparation, for example as a thickened solution, as an emulsion, as a cream, as an aerosol foam or as a gel.
  • the reduced colorant preparation should be stabilized in the reduced form as far as possible and protected against atmospheric oxygen. This can be achieved by suitable packaging, protective gas and the addition of protective and / or stabilizing substances or esterification (so-called leuco vat dye esters made with chlorosulfuric acid).
  • Protective or stabilizing compounds are for example cationic compounds, for example polymers, surfactants or metal ions such as zinc.
  • valve openings can be used to "inject" a relatively liquid dye mixture under the plastic hood and then distribute and massage in as well as possible from the outside. It is also possible to use a plastic hood with small holes through which an aerosol foam can be used with the help of a filling nozzle apply to the hair under the cover and then spread by massaging.
  • the coloring After an exposure time of about 1 to 60 minutes, preferably 5 to 30 minutes, at about 1 ⁇ to 60 ° C., preferably 20 to 4 ⁇ ° C., the coloring is “developed” oxidatively.
  • oxidizing agents for developing the coloring in particular hydrogen peroxide or its addition compounds to urea, melamine or sodium borate in the form of a 1 to 12 percent, preferably a 1, 6 to 6 percent, aqueous solution into consideration.
  • the mixing ratio of colorant to oxidizing agent is dependent on the concentration of the oxidizing agent and is in the Rule about ⁇ : 1 to 1: 2, preferably 1: 1, the content of oxidizing agent in the resulting mixture of colorant and oxidizing agent preferably being about 0, ⁇ to 8 percent by weight, in particular 1 to 4 percent by weight act until the dye is back in its insoluble pigment form (in de r usually about 2 to ⁇ minutes) and is wash-stable on the hair.
  • the exposure time of the oxidizing agent can be extended depending on the desired degree of lightening. If brightening of the natural pigment by more than two stages is desired, persulfates or mixtures of persulfates and hydrogen peroxide or their addition compounds can also be used. In this case, alkaline persulfate / peroxide preparations are preferably used.
  • the hair is rinsed with water and dried. If necessary, the hair can also be washed with a shampoo and possibly rinsed with an acidic conditioner. The hair is then dried.
  • 10 g of the mixture thus obtained are then applied to medium blonde natural hair.
  • the hair is then covered with a plastic hood or plastic wrap.
  • an additional 10 g of a 6% aqueous hydrogen peroxide emulsion are massaged in and left to act for 2 minutes.
  • the hair is then rinsed out with water, washed with a shampoo, then rinsed with an acid conditioner and then dried.
  • the hair gets an even blue-black color.
  • the hair gets a deep blue, even color.
  • the above substances are mixed and left under argon at 40 ° C for 2 hours.
  • the pH is then adjusted to 9.6 with 4.0 g of ammonia (2 ⁇ % aqueous solution) and 4.0 g of lactic acid (90% aqueous solution).
  • 1 ⁇ g of the mixture thus obtained are applied to bleached natural hair.
  • the hair is then covered with a plastic hood or plastic wrap.
  • an additional 1 ⁇ g of a 6% aqueous hydrogen peroxide emulsion is massaged in and left to act for 2 minutes.
  • the hair is then rinsed out with water, then rinsed with an acid conditioner and then dried.
  • the hair gets an even red-violet color.
  • the above substances are mixed and left under argon at 40 ° C for 2 hours.
  • the pH is then adjusted to 9.6 with 4.0 g ammonia (2 ⁇ % aqueous solution) and 4.0 g lactic acid (90% aqueous solution) and the oxidative dye precursors (1.5 g 1-hydroxyethyl 4,5-diamino-pyrazole sulfate, 0.8 g of 4-amino-2-hydroxytoluene and 0.1 g of 2,6-diamino-3 - ((pyridin-3-yl) azo) pyridine) were added.
  • the above substances are mixed and left under argon at 40 ° C for 2 hours.
  • the pH is then adjusted to 9.6 with 4.0 g of ammonia (2 ⁇ % aqueous solution) and 4.0 g of lactic acid (90% aqueous solution).
  • 10 g of the mixture thus obtained are applied to bleached natural hair.
  • the hair is then covered with a plastic hood or plastic wrap.
  • an additional 10 g of a 6% aqueous hydrogen peroxide emulsion are massaged in and left to act for 2 minutes.
  • rinse the hair with water, then rinse with an acid Conditioner and finally it dries.
  • the hair gets an even pink color.

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  • Life Sciences & Earth Sciences (AREA)
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Abstract

The invention relates to an agent for coloring hair containing at least one indigoid vat dye, at least one cationic compound and, as a reducing agent, at least one compound that forms an enediol in the alkaline medium. The invention also relates to a method for coloring hair while using this agent with a physiologically compatible pH value followed by a reoxidation of the vat dye.

Description

B e s c h r e i b u n g Description
Haarfärbemittel mit indigoiden KüpenfarbstoffenHair dye with indigo vat dyes
Die vorliegende Erfindung betrifft ein Mittel und Verfahren zum Färben von Haaren, insbesondere menschlichen Haaren mit sogenannten indigoiden Küpenfarbstoffen.The present invention relates to an agent and method for dyeing hair, in particular human hair, using so-called indigo vat dyes.
Indigoide Küpenfarbstoffe finden zwar eine weite Verwendung bei der Färbung von cellulosischen Fasermaterialien; für tierische Fasern, wie zum Beispiel Wolle oder Haare werden sie hingegen nur sehr selten angewandt, da diese den erforderlichen sehr hohen pH-Wert von ca. 13 nicht ohne drastische Schädigung überstehen. Zudem werden meist sehr aggressive Reduktionsmittel, wie beispielsweise Natriumdithionit (Hydrosulfit) oder Natriumhydrogensulfite, verwendet. Aus diesen Gründen hat sich die Küpenfärberei auch bei tierischen Fasern bis jetzt praktisch nicht durchgesetzt.Indigo vat dyes are widely used in the dyeing of cellulosic fiber materials; on the other hand, they are only used very rarely for animal fibers, such as wool or hair, since these do not survive the required very high pH of around 13 without drastic damage. In addition, very aggressive reducing agents, such as sodium dithionite (hydrosulfite) or sodium bisulfite, are usually used. For these reasons, vat dyeing has practically not been successful even with animal fibers.
Es wurden bereits Versuche unternommen, die Hydrosulfite vor allem auch wegen der hohen Abwasserbelastung als Verküpungsmittel in der Textilfärberei durch andere Reduktionsmittel abzulösen. In der EP 0 357 548 A1 wurden als geeigneter Ersatz Endiole empfohlen, die im Alkalischen die Farbstoffe praktisch wie Dithionit reduzieren, aber eine weitaus bessere Umweltverträglichkeit aufweisen. Diese Verfahren lassen sich aber weiterhin nur auf cellulosichen Fasern und nicht auf Keratinfasern anwenden, da immer noch ein pH-Wert von ca. 13 bei der Färbung erforderlich ist. Alternativ wurde in der DE 44 27 888 A1 für die Haarfärbung die Reduktion von Küpenfarbstoffen mit Laserlicht vorgeschlagen. Dieses Verfahren ist jedoch wegen der Verwendung von Laserstrahlung in der Praxis nur schwer anwendbar.Attempts have already been made to replace the hydrosulfites as a coupling agent in textile dyeing with other reducing agents, especially because of the high wastewater load. In EP 0 357 548 A1, endiols were recommended as a suitable substitute, which practically reduce the dyes in alkaline as dithionite, but have a far better environmental compatibility. However, these processes can still only be used on cellulosic fibers and not on keratin fibers, since a pH value of approx. 13 is still required for the dyeing. Alternatively, the reduction of vat dyes with laser light was used in DE 44 27 888 A1 for hair coloring proposed. However, this method is difficult to use in practice because of the use of laser radiation.
Es bestand daher weiterhin die Aufgabe, ein Verfahren zur Verfügung zu stellen, dass eine einfache und schonende Färbung von Haaren mit Küpenfarbstoffen ermöglicht.There was therefore still the task of making available a process that enables simple and gentle coloring of hair with vat dyes.
Überraschenderweise wurde nunmehr gefunden, dass man Färbungen mit Küpenfarbstoffen (wie zum Beispiel Indigo) auch unter physiologisch verträglichen Bedingungen durchführen kann, wenn man der Färbemischung kationische Verbindungen zusetzt und der pH-Wert vor der Färbung entsprechend eingestellt wird. Man erhält auf diese Weise intensive gleichmäßige Haarfärbungen bei gleichzeitiger größtmöglicher Schonung der Haare. Außerdem ist hierbei ein sogenanntes Hellerfärben, unter teilweiser oder vollständiger Entfärbung des natürlichen Haarpigments Melanin während des abschließenden Oxidationsschrittes möglich.Surprisingly, it has now been found that dyeing with vat dyes (such as, for example, indigo) can also be carried out under physiologically tolerable conditions if cationic compounds are added to the dye mixture and the pH is adjusted accordingly before the dyeing. In this way, intensive, even hair colorations are obtained with the greatest possible protection of the hair. In addition, so-called lightening is possible, with partial or complete decolorization of the natural hair pigment melanin during the final oxidation step.
Gegenstand der vorliegenden Anmeldung ist daher ein Mittel zur Färbung von Haaren, welches dadurch gekennzeichnet ist, dass es mindestens einen indigoiden Küpenfarbstoff, mindestens eine kationische Verbindung und als Reduktionsmittel mindestens eine im alkalischen Medium ein Endiol bildende Verbindung enthält.The present application therefore relates to an agent for coloring hair, which is characterized in that it contains at least one indigoid vat dye, at least one cationic compound and as a reducing agent at least one compound which forms an endiol in the alkaline medium.
Ein weiterer Gegenstand der vorliegenden Anmeldung ist ein gebrauchsfertiges Mittel zur Färbung von Haaren, welches dadurch gekennzeichnet ist, dass es einen in Gegenwart einer kationischen Verbindung mit einer im alkalischen Medium ein Endiol bildenden Verbindung reduzierten indigoiden Küpenfarbstoff enthält und einen pH-Wert von 4 bis 11 aufweist.Another object of the present application is a ready-to-use agent for dyeing hair, which is characterized in that it contains an indigoid vat dye which is reduced in the presence of a cationic compound with an endiol-forming compound in an alkaline medium, and one pH of 4 to 11.
Unter indigoiden Küpenfarbstoffen im Sinne der Erfindung sind insbesondere Indigo und Indirubin (C. I. 75790) sowie Indigoderivate, wie zum Beispiel 6,6'-Dibromindigo, δ.δ' J'-Tetrabromindigo, 4,4',7,7'-Tetrachlorindigo, Thioindigo, 6,6'Dichlor-4,4'-dimethyl-thioindigo, 5,5'-Dichlor-7,7'-dimethyl-thioindigo, 4,4',7,7'-Tetramethyl-thioindigo und deren Mischungen zu nennen. Weitere geeignete Küpenfarbstoffe aus dieser Gruppe finden sich auch im Colour Index (C. I. ), Dritte Auflage, 1971 , publiziert von der Society of Dyers and Colourists in den Abschnitten Küpen- und Schwefelfarbsoffe (vat dyes/sulphur dyes).Indigoid vat dyes for the purposes of the invention include in particular indigo and indirubin (CI 75790) and indigo derivatives, such as, for example, 6,6'-dibromoindigo, δ.δ 'J'-tetrabromoindigo, 4,4', 7,7'-tetrachloroindigo, Thioindigo, 6,6'-dichloro-4,4'-dimethylthioindigo, 5,5'-dichloro-7,7'-dimethylthioindigo, 4,4 ', 7,7'-tetramethylthioindigo and mixtures thereof call. Other suitable vat dyes from this group can also be found in the Color Index (C.I.), third edition, 1971, published by the Society of Dyers and Colorists in the sections vat and sulfur dyes (vat dyes / sulfur dyes).
Die indigoiden Küpenfarbstoffe werden in einer Gesamtmenge von 0,01 bis 10 Gew%, vorzugsweise 0,1 bis 2 Gew.% eingesetzt.The indigoid vat dyes are used in a total amount of 0.01 to 10% by weight, preferably 0.1 to 2% by weight.
Als Reduktionsmittel werden im alkalischen Medium Endiole (Endiolate) bildende Verbindungen eingesetzt, wie zum Beispiel Monohydroxyaceton, Dihydroxyaceton, Acetoin, Glutaroin, Adipoin, Glykolaldehyd, Benzoin, 2,3-Dihydroxyacrylaldehyd und Cycopentadiolon, wobei Acetoin, Monohydroxyaceton und Dihydroxyaceton besonders bevorzugt sind.Compounds forming endiols (endiolates) are used as reducing agents in the alkaline medium, such as, for example, monohydroxyacetone, dihydroxyacetone, acetoin, glutaroin, adipoin, glycol aldehyde, benzoin, 2,3-dihydroxyacrylaldehyde and cycopentadiolone, with acetoin, monohydroxyacetone and dihydroxyacetone being particularly preferred.
Als Alkalisierungsmittel für den Reduktionsschritt werden Natrium- oder Kaliumhydroxyd, oder Alkalisalze von aromatischen Monoydroxy- oder Polyhydroxyverbindungen, wie zum Beispiel Natrium- oder Kalium- phenolat oder Natrium- oder Kaliumkresolat eingesetzt. Der pH-Wert liegt für den Reduktionsschritt im Allgemeinen bei 10 bis 13.Alkalizing agents for the reduction step are sodium or potassium hydroxide, or alkali salts of aromatic mono-hydroxy or polyhydroxy compounds, such as sodium or potassium phenolate or sodium or potassium cresolate. The pH value for the reduction step is generally 10 to 13.
Die Reduktionsmittel werden entweder in einer äquimolaren Menge oder in einem bis zu 50fachen molarem Überschuss -bezogen auf den Küpen- farbstoff- angewandt, besonders bevorzugt wird ein 3- bis δfacher molarer Überschuss.The reducing agents are either in an equimolar amount or in an up to 50-fold molar excess, based on the vat. dye used, a 3 to δ-fold molar excess is particularly preferred.
Außerdem können bei der Reduktion organische Lösungsmittel zur Anwendung kommen in einer Konzentration von 0,1 bis 80 Gewichtsprozent, vorzugsweise zwischen 5 und 50 Gewichtsprozent. Die organischen Lösungsmittel sollten mit Wasser eine homogene Phase bilden. Es kommen sowohl protische als auch aprotische, organische Lösungsmittel in Frage, wie zum Beispiel Ethanol, n-Propanol, Iso- propanol, n-Butanol, Glykole, wie zum Beispiel Ethylenglykol, Propylenglykol, Lactone, Lactame, Säureamide niedriger Carbonsäuren, Harnstoffe und Sulfone und Sulfoxide in Frage. Es können ebenfalls Mischungen dieser Lösungsmittel zum Einsatz kommen.In addition, organic solvents can be used in the reduction in a concentration of 0.1 to 80 percent by weight, preferably between 5 and 50 percent by weight. The organic solvents should form a homogeneous phase with water. Both protic and aprotic, organic solvents, such as ethanol, n-propanol, isopropanol, n-butanol, glycols, such as, for example, ethylene glycol, propylene glycol, lactones, lactams, acid amides of lower carboxylic acids, ureas and sulfones are suitable and sulfoxides in question. Mixtures of these solvents can also be used.
Zur Beschleunigung der Reduktion und zur Verbesserung des Aufziehens des Farbstoffes auf die Faser werden kationische Verbindungen, vorzugsweise kationische Polymere, wie zum Beispiel Polyquaternium-2, Polyquatemium-4, Polyquaternium-5, Polyquatemium-6, Polyquatemium-7, Polyquatemium-10, Polyquatemium-11 , Polyquaternium-15, Polyquatemium-16, Polyquaternium-17, Polyquatemium-18, Polyquaternium-19, Polyquaternium-20, Polyquaternium-22, Polyquaternium-24, Polyquaternium-27, Polyquaternium-28, Polyquaternium-29, Polyquatemium-31 , Polyquaternium-35, Polyquaternium-36, Polyquaternium-37, Polyquaternium-39, Polyquaternium-44, Polyquaternium-46, Polyquatemium-47, Polyquaternium-51 , Polyquaternium-55, Polyquaternium-57, Hydroxypropylguar-hydroxypropyltrimethylammoniumchlorid, Quaternium-80, Guar-hydroxypropyltrimethylammonium-chlorid oder deren Mischungen eingesetzt. Besonders bevorzugt sind Polyquaternium-4 (Hydroxyethylcellulose-dimethyldiallylammoniumchlorid-Copolymer), Polyquatemium-7 (Dimethyldiallylammoniumchlorid-acrylamid-Copolymer) und Polyquatemium-22 (Acrylsäure-Diallyldimethylammoniumchlorid- Copolymer), verwendet.To accelerate the reduction and to improve the absorption of the dye on the fiber, cationic compounds, preferably cationic polymers, such as, for example, Polyquaternium-2, Polyquatemium-4, Polyquaternium-5, Polyquatemium-6, Polyquatemium-7, Polyquatemium-10, Polyquatemium -11, polyquaternium-15, polyquaternium-16, polyquaternium-17, polyquaternium-18, polyquaternium-19, polyquaternium-20, polyquaternium-22, polyquaternium-24, polyquaternium-27, polyquaternium-28, polyquaternium-29, polyquaternium-31 , Polyquaternium-35, Polyquaternium-36, Polyquaternium-37, Polyquaternium-39, Polyquaternium-44, Polyquaternium-46, Polyquaternium-47, Polyquaternium-51, Polyquaternium-55, Polyquaternium-57, Hydroxypropylguar-hydroxypropyltrimethylernonium chloride, -hydroxypropyltrimethylammonium chloride or mixtures thereof. Polyquaternium-4 are particularly preferred (Hydroxyethyl cellulose-dimethyldiallylammonium chloride copolymer), polyquaternium-7 (dimethyldiallylammonium chloride-acrylamide copolymer) and polyquaternium-22 (acrylic acid-diallyldimethylammonium chloride copolymer).
Die kationischen Verbindungen werden in einer Gesamtmenge von 0,001 bis 5 Gewichtsprozent, insbesondere von 0,1 bis 1 Gewichtsprozent, eingesetzt.The cationic compounds are used in a total amount of 0.001 to 5 percent by weight, in particular 0.1 to 1 percent by weight.
Bei der im Anschluss an den Reduktionsschritt erfolgenden Färbung hat es sich als günstig erwiesen, Ammonium-Ionen zuzusetzen, beispielsweise in Form von wäßrigem Ammoniak oder Ammoniumsalzen. Es können aber auch Amine, wie zum Beispiel Glucamine, Aminomethyl- propanol, Monoethanolamin oder Triethanolamin, anorganische Basen, beispielsweise Ammoniumcarbonat, Ammoniumhydrogencarbonat oder Ammoniumcarbonat, zugesetzt werden.In the dyeing that follows the reduction step, it has proven to be advantageous to add ammonium ions, for example in the form of aqueous ammonia or ammonium salts. However, it is also possible to add amines, such as, for example, glucamines, aminomethylpropanol, monoethanolamine or triethanolamine, inorganic bases, for example ammonium carbonate, ammonium hydrogen carbonate or ammonium carbonate.
Der stark alkalische pH-Wert der Farbmasse wird nach der Reduktion mit einer Säure oder einer hydrolisierenden Substanz, bespielsweise einem Salz oder einem Ester auf einen physiologisch verträglichen Wert von 4 bis 11, vorzugsweise 6 bis 10, eingestellt. Für die Einstellung des gewünschten pH-Wertes können beispielsweise Puffersysteme oder anorganische oder organische Säuren, zum Beispiel Milchsäure, Zitronensäure, Weinsäure, Glykolsäure, Essigsäure, Phosphorsäure, Ammoniumsulfat, Ammoniumchlorid oder Cetyllactat, verwendet werden.After reduction with an acid or a hydrolyzing substance, for example a salt or an ester, the strongly alkaline pH of the color composition is adjusted to a physiologically tolerable value of 4 to 11, preferably 6 to 10. Buffer systems or inorganic or organic acids, for example lactic acid, citric acid, tartaric acid, glycolic acid, acetic acid, phosphoric acid, ammonium sulfate, ammonium chloride or cetyl lactate, can be used, for example, to set the desired pH.
Dem erfindungsgemäßen Färbemittel können nach dem Reduktionsschritt auch übliche Oxidationsfarbstoffvorstufen zugesetzt werden. Als geeignete Oxidationsfarbstoffvorstufen können beispielsweise die folgenden Entwicklersubstanzen und Kupplersubstanzen und mit sich selbst kuppelnden Verbindungen genannt werden: (i) Entwicklersubstanzen: 1 ,4-Diamino-benzol (p-Phenylendiamin), 1 ,4-Diamino-2-methyl-benzol (p-Toluylendiamin), 1 ,4-Diamino-2,6- dimethyl-benzol, 1 ,4-Diamino-3,5-diethyl-benzol, 1 ,4-Diamino-2,5- dimethyl-benzol, 1 ,4-Diamino-2,3-dimethyl-benzol, 2-Chlor-1 ,4- diaminobenzol, 1 ,4-Diamino-2-(thiophen-2-yl)benzol, 1 ,4-Diamino-2- (thiophen-3-yl)benzol, 1 ,4-Diamino-2-(pyridin-3-yl)benzol, 2,5-Diamino- biphenyl, 1 ,4-Diamino-2-methoxymethyl-benzol, 1 ,4-Diamino-2- aminomethyl-benzol, 1 ,4-Diamino-2-hydroxymethyl-benzol, 1 ,4-Diamino-2- (2-hydroxyethoxy)-benzol, 2-(2-(Acetylamino)ethoxy)-1 ,4-diamino-benzol, 4-Phenylamino-anilin, 4-Dimethylamino-anilin, 4-Diethylamino-anilin, 4-Dipropylamino-anilin, 4-[Ethyl(2-hydroxyethyl)amino]-anilin, 4-[Di(2-hydroxyethyl)amino]-anilin, 4-[Di(2-hydroxyethyl)amino]-2-methyl- anilin, 4-[(2-Methoxyethyl)amino]-anilin, 4-[(3-Hydroxypropyl)amino]-anilin, 4-[(2,3-Dihydroxypropyl)amino]-anilin, 1 ,4-Diamino-2-(2-hydroxyethyl)- benzol, 1 ,4:Diamino-2-(1-methylethyl)-benzol, 1 ,3-Bis[(4-aminophenyl)(2- hydroxyethyl)amino]-2-propanol, 1,4-Bis[(4-Aminophenyl)amino]-butan, 1 ,8-Bis(2,5-diaminophenoxy)-3,6-dioxaoctan, 4-Amino-phenol, 4-Amino-3- methyl-phenol, 4-Amino-3-(hydroxymethyl)-phenol, 4-Amino-3-fluor- phenol, 4-Methylamino-phenol, 4-Amino-2-(aminomethyl)-phenol, 4-Amino-2-(hydroxymethyl)-phenol, 4-Amino-2-fluor-phenol, 4-Amino-2- [(2-hydroxyethyl)-amino]methyl-phenol, 4-Amino-2-methyl-phenol, 4-Amino-2-(methoxymethyl)-phenol, 4-Amino-2-(2-hydroxyethyl)-phenol, 5-Amino-salicylsäure, 2,5-Diamino-pyridin, 2,4,5,6-Tetraamino-pyrimidin, 2,5,6-Triamino-4-(1 H)-pyrimidon, 4,5-Diamino-1-(2-hydroxyethyl)-1 H- pyrazol, 4,5-Diamino-1-(1-methylethyl)-1 H-pyrazol, 4,5-Diamino-1-[(4- methylphenyl)methyl]-1 H-pyrazol, 1 -[(4-Chlorphenyl)methyl]-4,5-diamino- 1 H-pyrazol, 4,5-Diamino-1-methyl-1 H-pyrazol, 2-Amino-phenol, 2-Amino-6-methyl-phenol, 2-Amino-5-methyl-phenol, allein oder im Gemisch miteinander.Conventional oxidation dye precursors can also be added to the colorant according to the invention after the reduction step. Examples of suitable oxidation dye precursors are the following developer substances and coupler substances and self-coupling compounds: (i) Developer substances: 1,4-diamino-benzene (p-phenylenediamine), 1,4-diamino-2-methyl-benzene (p -Toluenediamine), 1,4-diamino-2,6-dimethyl-benzene, 1,4-diamino-3,5-diethyl-benzene, 1,4-diamino-2,5-dimethyl-benzene, 1,4- Diamino-2,3-dimethyl-benzene, 2-chloro-1,4-diaminobenzene, 1,4-diamino-2- (thiophene-2-yl) benzene, 1,4-diamino-2- (thiophene-3- yl) benzene, 1,4-diamino-2- (pyridin-3-yl) benzene, 2,5-diamino-biphenyl, 1,4-diamino-2-methoxymethyl-benzene, 1,4-diamino-2-aminomethyl -benzene, 1,4-diamino-2-hydroxymethyl-benzene, 1,4-diamino-2- (2-hydroxyethoxy) benzene, 2- (2- (acetylamino) ethoxy) -1,4-diamino-benzene, 4-phenylamino-aniline, 4-dimethylamino-aniline, 4-diethylamino-aniline, 4-dipropylamino-aniline, 4- [ethyl (2-hydroxyethyl) amino] aniline, 4- [di (2-hydroxyethyl) amino] - aniline, 4- [di (2-hydroxyethyl) amino] -2-me thylaniline, 4 - [(2-methoxyethyl) amino] aniline, 4 - [(3-hydroxypropyl) amino] aniline, 4 - [(2,3-dihydroxypropyl) amino] aniline, 1,4-diamino -2- (2-hydroxyethyl) benzene, 1,4: diamino-2- (1-methylethyl) benzene, 1,3-bis [(4-aminophenyl) (2-hydroxyethyl) amino] -2-propanol, 1,4-bis [(4-aminophenyl) amino] butane, 1,8-bis (2,5-diaminophenoxy) -3,6-dioxaoctane, 4-amino-phenol, 4-amino-3-methyl-phenol , 4-amino-3- (hydroxymethyl) phenol, 4-amino-3-fluorophenol, 4-methylamino-phenol, 4-amino-2- (aminomethyl) phenol, 4-amino-2- (hydroxymethyl) -phenol, 4-amino-2-fluorophenol, 4-amino-2- [(2-hydroxyethyl) amino] methylphenol, 4-amino-2-methylphenol, 4-amino-2- (methoxymethyl ) phenol, 4-amino-2- (2-hydroxyethyl) phenol, 5-amino salicylic acid, 2,5-diamino-pyridine, 2,4,5,6-tetraamino-pyrimidine, 2,5,6- Triamino-4- (1 H) -pyrimidone, 4,5-diamino-1- (2-hydroxyethyl) -1 H-pyrazole, 4,5-diamino-1- (1-methylethyl) -1 H-pyrazole, 4 , 5-diamino-1 - [(4- methylphenyl) methyl] -1 H-pyrazole, 1 - [(4-chlorophenyl) methyl] -4,5-diamino-1 H-pyrazole, 4,5-diamino-1-methyl-1 H-pyrazole, 2-amino -phenol, 2-amino-6-methyl-phenol, 2-amino-5-methyl-phenol, alone or in a mixture with one another.
(ii) Kupplersubstanzen: N-(3-Dimethylamino-phenyl)-hamstoff, 2,6-Diamino-pyridin, 2-Amino-4-[(2-hydroxyethyl)amino]-anisoI, 2,4-Diamino-1-fluor-5-methyl-benzol, 2,4-Diamino-1-methoxy-5-methyl- benzol, 2,4-Diamino-1-ethoxy-5-methyl-benzol, 2,4-Diamino-1-(2-hydroxy- ethoxy)-5-methyl-benzol, 2,4-Di[(2-hydroxyethyl)amino]-1 ,5-dimethoxy- benzol, 2,3-Diamino-6-methoxy-pyridin, 3-Amino-6-methoxy-2- (methylamino)-pyridin, 2,6-Diamino-3,5-dimethoxy-pyridin, 3,5-Diamino- 2,6-dimethoxy-pyridin, 1 ,3-Diamino-benzol, 2,4-Diamino-1-(2-hydroxy- ethoxy)-benzol, 1 ,3-Diamino-4-(2,3-dihydroxypropoxy)-benzol, 2,4-Diamino-1 ,5-di(2-hydroxyethoxy)-benzol, 1 -(2-Aminoethoxy)-2,4- diamino-benzol, 2-Amino-1-(2-hydroxyethoxy)-4-methylamino-benzol, 2,4-Diaminophenoxy-essigsäure, 3-[Di(2-hydroxyethyl)amino]-anilin, 4-Amino-2-di[(2-hydroxyethyl)amino]-1 -ethoxy-benzol, 5-Methyl-2-(1 - methylethyl)-phenol, 3-[(2-Hydroxyethyl)amino]-anilin, 3-[(2-Aminoethyl)- aminoj-anilin, 1 ,3-Di(2,4-diaminophenoxy)-propan, Di(2,4-diamino- phenoxy)-methan, 1 ,3-Diamino-2,4-dimethoxy-benzol, 2,6-Bis(2-hydroxy- ethyl)amino-toluol, 4-Hydroxyindol, 3-Dimethylamino-phenol, 3-Diethylamino-phenol, 5-Amino-2-methyl-phenol, 5-Amino-4-fluor-2- methyl-phenol, 5-Amino-4-methoxy-2-methyl-phenol, 5-Amino-4-ethoxy-2- methyl-phenol, 3-Amino-2,4-dichlor-phenol, 5-Amino-2,4-dichlor-phenol, 3-Amino-2-methyl-phenol, 3-Amino-2-chlor-6-methyl-phenol, 3-Amino- phenol, 2-[(3-Hydroxyphenyl)amino]-acetamid, 5-[(2-Hydroxyethyl)amino]- 4-methoxy-2-methyl-phenol, 5-[(2-Hydroxyethyl)amino]-2-methyl-phenol, 3-[(2-Hydroxyethyl)amino]-phenol, 3-[(2-Methoxyethyl)amino]-phenol, 5-Amino-2-ethyl-phenol, 5-Amino-2-methoxy-phenol, 2-(4-Amino-2- hydroxyphenoxy)-ethanol, 5-[(3-Hydroxypropyl)amino]-2-methyl-phenol, 3-[(2,3-Dihydroxypropyl)amino]-2-methyl-phenol, 3-[(2-Hydroxyethyl)- amino]-2-methyl-phenol, 2-Amino-3-hydroxy-pyridin, 5-Amino-4-chlor-2- methyl-phenol, 1-Naphthol, 2-Methyl-1-naphthol, 1 ,5-Dihydroxy- naphthalin, 1 ,7-Dihydroxy-naphthalin, 2,3-Dihydroxy-naphthalin, 2,7-Dihydroxy-naphthalin, 2-Methyl-1-naphthol-acetat, 1 ,3-Dihydroxy- benzol, 1-Chlor-2,4-dihydroxy-benzol, 2-Chlor-1 ,3-dihydroxy-benzol, 1 ,2-Dichlor-3,5-dihydroxy-4-methyl-benzol, 1 ,5-Dichlor-2,4-dihydroxy- benzol, 1 ,3-Dihydroxy-2-methyl-benzol, 3,4-Methylendioxy-phenol, 3,4-Methylendioxy-anilin, 5-[(2-Hydroxyethyl)amino]-1 ,3-benzodioxol, 6-Brom-1-hydroxy-3,4-methylendioxy-benzol, 3,4-Diamino-benzoesäure, 3,4-Dihydro-6-hydroxy-1 ,4(2H)-benzoxazin, 6-Amino-3,4-dihydro-1 ,4(2H)- benzoxazin, 3-Methyl-1-phenyl-5-pyrazolon, 5,6-Dihydroxy-indol, 5,6-Dihydroxy-indolin, 5-Hydroxy-indol, 6-Hydroxy-indol, 7-Hydroxy-indol, 2,3-lndolindion, allein oder im Gemisch miteinander. (iii) Mit sich selbst kuppelnde Verbindungen: 2-Amino-5-methylphenol, 2-Amino-6-methylphenol, 2-Amino-5-ethoxyphenol oder 2-Propyl- amino-5-aminopyridin.(ii) Coupler substances: N- (3-dimethylamino-phenyl) urea, 2,6-diamino-pyridine, 2-amino-4 - [(2-hydroxyethyl) amino] -anisoI, 2,4-diamino-1- fluoro-5-methyl-benzene, 2,4-diamino-1-methoxy-5-methyl-benzene, 2,4-diamino-1-ethoxy-5-methyl-benzene, 2,4-diamino-1- (2nd -hydroxy-ethoxy) -5-methyl-benzene, 2,4-di [(2-hydroxyethyl) amino] -1, 5-dimethoxy-benzene, 2,3-diamino-6-methoxy-pyridine, 3-amino- 6-methoxy-2- (methylamino) pyridine, 2,6-diamino-3,5-dimethoxy-pyridine, 3,5-diamino-2,6-dimethoxy-pyridine, 1, 3-diamino-benzene, 2, 4-diamino-1- (2-hydroxyethoxy) benzene, 1,3-diamino-4- (2,3-dihydroxypropoxy) benzene, 2,4-diamino-1,5-di (2-hydroxyethoxy) -benzene, 1 - (2-aminoethoxy) -2,4-diamino-benzene, 2-amino-1- (2-hydroxyethoxy) -4-methylamino-benzene, 2,4-diaminophenoxy-acetic acid, 3- [di ( 2-hydroxyethyl) amino] aniline, 4-amino-2-di [(2-hydroxyethyl) amino] -1-ethoxy-benzene, 5-methyl-2- (1-methylethyl) phenol, 3 - [(2nd -Hydroxyethyl) amino] aniline, 3 - [(2-aminoethyl) aminoj-aniline, 1,3-di (2,4-diaminophenoxy) propane, di ( 2,4-diaminophenoxy) methane, 1,3-diamino-2,4-dimethoxy-benzene, 2,6-bis (2-hydroxyethyl) aminotoluene, 4-hydroxyindole, 3-dimethylamino-phenol , 3-diethylamino-phenol, 5-amino-2-methylphenol, 5-amino-4-fluoro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5-amino-4 -ethoxy-2-methylphenol, 3-amino-2,4-dichlorophenol, 5-amino-2,4-dichlorophenol, 3-amino-2-methylphenol, 3-amino-2-chloro -6-methylphenol, 3-aminophenol, 2 - [(3-hydroxyphenyl) amino] acetamide, 5 - [(2-hydroxyethyl) amino] - 4-methoxy-2-methylphenol, 5- [ (2-hydroxyethyl) amino] -2-methylphenol, 3 - [(2-hydroxyethyl) amino] phenol, 3 - [(2-methoxyethyl) amino] phenol, 5-amino-2-ethylphenol, 5-amino-2-methoxyphenol, 2- (4-amino-2-hydroxyphenoxy) ethanol, 5 - [(3-hydroxypropyl) amino] -2-methylphenol , 3 - [(2,3-dihydroxypropyl) amino] -2-methylphenol, 3 - [(2-hydroxyethyl) amino] -2-methylphenol, 2-amino-3-hydroxy-pyridine, 5- Amino-4-chloro-2-methylphenol, 1-naphthol, 2-methyl-1-naphthol, 1, 5-dihydroxy-naphthalene, 1, 7-dihydroxy-naphthalene, 2,3-dihydroxy-naphthalene, 2, 7-dihydroxy-naphthalene, 2-methyl-1-naphthol acetate, 1, 3-dihydroxy-benzene, 1-chloro-2,4-dihydroxy-benzene, 2-chloro-1, 3-dihydroxy-benzene, 1, 2-dichloro-3,5-dihydroxy-4-methylbenzene, 1,5-dichloro-2,4-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 3,4-methylenedioxyphenol, 3,4-methylenedioxy-aniline, 5 - [(2-hydroxyethyl) amino] -1, 3-benzodioxole, 6-bromo-1-hydroxy-3,4-methylenedioxy-benzene, 3,4-diamino-benzoic acid, 3 , 4-dihydro-6-hydroxy-1, 4 (2H) -benzoxazine, 6-amino-3,4-dihydro-1, 4 (2H) - benzoxazine, 3-methyl-1-phenyl-5-pyrazolone, 5 , 6-dihydroxy-indole, 5,6-dihydroxy-indoline, 5-hydroxy-indole, 6-hydr oxy-indole, 7-hydroxy-indole, 2,3-indole indione, alone or as a mixture with one another. (iii) Self-coupling compounds: 2-amino-5-methylphenol, 2-amino-6-methylphenol, 2-amino-5-ethoxyphenol or 2-propylamino-5-aminopyridine.
Die Gesamtmenge der in dem erfindungsgemäßen Mittel enthaltenen Oxidationsfarbstoffvorstufen können etwa 0,01 bis 12 Gewichtsprozent, insbesondere etwa 0,2 bis 6 Gewichtsprozent betragen.The total amount of the oxidation dye precursors contained in the agent according to the invention can be about 0.01 to 12 percent by weight, in particular about 0.2 to 6 percent by weight.
Zur Erzielung bestimmter Farbnuancen können ferner auch übliche natürliche und/oder synthetische direktziehende Farbstoffe, beispielsweise sogenannte Pflanzenfarbstoffe wie zum Beispiel Henna, Triphenyl- methanfarbstoffe, aromatische Nitrofarbstoffe, Azofarbstofte, Chinon- farbstoffe, kationische oder anionische Farbstoffe, in dem Färbemittel enthalten sein.In order to achieve certain color shades, customary natural and / or synthetic direct dyes, for example so-called plant dyes such as henna, triphenylmethane dyes, aromatic nitro dyes, azo dyes, quinones, can also be used. dyes, cationic or anionic dyes contained in the colorant.
Als geeignete synthetische Farbstoffe können beispielsweise genannt werden: 1 ,4-Bis[(2-hydroxyethyl)amino]-2-nitrobenzol, 1-(2-Hydroxyethyl)- amino-2-nitro-4-[di(2-hydroxyethyl)-amino]-benzol (HC Blue No. 2), 1 -Amino-3-methyl-4-[(2-hydroxyethyl)-amino]-6-nitrobenzol (HC Violet No. 1 ), 4-[Ethyl-(2-hydroxyethyl)amino]-1-[(2-hydroxyethyl)amino]-2-nitro- benzol-hydrochlorid (HC Blue No. 12), 4-[Di(2-hydroxyethyl)amino]-1-[(2- methoxyethyl)amino]-2-nitrobenzol (HC Blue No. 11 ), 1-[(2,3-Dihydroxy- propyl)amino]-4-[methyl-(2-hydroxy-ethyl)-amino]-2-nitrobenzol (HC Blue No. 10), 1-[(2,3-Dihydroxypropyl)-amino]-4-[ethyl-(2-hydroxyethyl)amino]- 2-nitrobenzol-hydrochlorid (HC Blue No. 9), 1-(3-Hydroxypropylamino)-4- [di(2-hydroxyethyl)amino]-2-nitrobenzol (HC Violet No. 2), 1-Methylamino- 4-[methyl-(2,3-dihydroxy-propyl)amino]-2-nitrobenzol (HC Blue No. 6), 2-((4-Amino-2-nitrophenyl)-amino)-5-dimethylamino-benzoesäure (HC Blue No. 13), 1-Amino-4-[(2-hydroxyethyl)amino]-2-nitrobenzol (HC Red No. 7), 2-Amino-4,6-dinitro-phenol, 4-Amino-2-nitro- diphenylamin (HC Red No. 1 ), 1-Amino-4-[di(2-hydroxyethyl)amino]-2- nitrobenzol-hydrochlorid (HC Red No. 13), 1-Amino-5-chlor-4-[(2- hydroxyethyl)amino]-2-nitrobenzol, 4-Amino-1-[(2-hydroxyethyl)amino]-2- nitrobenzol (HC Red No. 3), 4-Amino-3-nitrophenol, 4-[(2-Hydroxyethyl)- amino]-3-nitrophenol, 1-[(2-Aminoethyl)amino]-4-(2-hydroxyethoxy)-2- nitrobenzol (HC Orange No. 2), 4-(2,3-Dihydroxy-propoxy)-1-[(2-hydroxy- ethyl)amino]-2-nitrobenzol (HC Orange No. 3), 1-Amino-5-chlor-4-[(2,3- dihydroxypropyl)amino]-2-nitrobenzol (HC Red No. 10), 5-Chlor-1 ,4- [di(2,3-dihydroxypropyl)amino]-2-nitrobenzol (HC Red No. 11), 2-[(2-Hydroxyethyl)amino]-4,6-dinitro-phenol, 4-Ethylamino-3-nitro- benzoesäure, 2-[(4-Amino-2-nitrophenyl)-amino]-benzoesäure, 2-Chlor-6- ethylamino-4-nitrophenol, 2-Amino-6-chlor-4-nitrophenol, 4-[(3-Hydroxy- propyl)amino]-3-nitrophenol, 2,5-Diamino-6-nitropyridin, 1 ,2,3,4-Tetra- hydro-6-nitrochinoxalin, 7-Amino-3,4-dihydro-6-nitro-2H-1,4-benzoxazin (HC Red No. 14), 1-Amino-2-[(2-hydroxyethyl)amino]-5-nitrobenzol (HC Yellow No. 5), 1-(2-Hydroxy-ethoxy)-2-[(2-hydroxyethyl)-amino]-5- nitrobenzol (HC Yellow No. 4), 1-[(2-Hydroxyethyl)amino]-2-nitrobenzol (HC Yellow No. 2), 2-[(2-Hydroxy-ethyl)-amino]-1-methoxy-5-nitrobenzol. 2-Amino-3-nitrophenol, 1-(2-Hydroxyethoxy)-3-methylamino-4-nitrobenzol, 2,3-(Dihydroxy-propoxy)-3-methyl-amino-4-nitrobenzol, 2-[(2-Hydroxy- ethyl)amino]-5-nitrophenol (HC Yellow No. 11), 3-[(2-Aminoethyl)-amino]- 1-methoxy-4-nitrobenzol-hydrochlorid (HC Yellow No.9), 1-[(2-Ureido- ethyl)amino]-4-nitrobenzol, 4-[(2,3-Di-hydroxypropyl)amino]-3-nitro-1- trifluormethyl-benzol (HC Yellow No. 6), 1-Chlor-2,4-bis[(2-hydroxyethyl)- amino]-5-nitrobenzol (HC Yellow No. 10), 4-[(2-Hydroxy-ethyl)amino]-3- nitro-1 -methylbenzol, 1 -Chlor-4-[(2-hydroxy-ethyl)amino]-3-nitrobenzol (HC Yellow No. 12), 4-[(2-Hydroxyethyl)-amino]-3-nitro-1-trifluormethyl-benzol (HC Yellow No. 13), 4-[(2-Hydroxy-ethyl)amino]-3-nitro-benzonitril (HC Yellow No. 14), 4-[(2-Hydroxyethyl)-amino]-3-nitro-benzamid (HC Yellow No. 15), 1.4-Di[(2,3-dihydroxy-propyl)amino]-9.10- anthrachinon, 1 -[(2-Hydroxy-ethyl)amino]-4-methyl-amino-9,10- anthrachinon (CI61505, Disperse Blue No. 3), 2-[(2-Amino-ethyl)amino]- 9,10-anthrachinon (HC Orange No. 5), 1-Hydroxy-4-[(4~methyl-2- sulfophenyl)amino]-9,10-anthrachinon, 1-[(3-Aminopropyl)-amino]-4- methylamino-9,10-anthrachinon (HC Blue No. 8),1-[(3-Amino-propyl)- amino]-9,10-anthrachinon (HC Red No. 8), 1 ,4-Diamino-2-methoxy-9,10- anthrachinon (CI62015, Disperse Red No. 11, Solvent Violet No. 26), 1 ,4-Dihydroxy-5,8-bis[(2-hydroxyethyl)amino]-9,10-anthrachinon (CI62500, Disperse Blue No. 7, Solvent Blue No. 69), 9-(Dimethylamino)-benzo[a]- phenoxazin-7-ium-chlorid (CI51175; Basic Blue No. 6), Di[4-(diethyl- amino)phenyl][4-(ethylamino)naphthyl]-carbenium-chlorid (CI42595; Basic Blue No. 7), 3,7-Di(dimethylamino)-phenothiazin-5-ium-chlorid (CI52015; Basic Blue No. 9), Di[4-(dimethyl-amino)phenyl][4-(phenylamino)naphthyl]- carbenium-chlorid (CI44045; Basic Blue No. 26), 2-[(4-(Ethyl(2-hydroxy- ethyl)amino)phenyl)azo]-6-methoxy-3-methyl-benzothiazolium-methylsulfat (CI11154; Basic Blue No. 41), 8-Amino-2-brom-5-hydroxy-4-imino-6-[(3- (trimethylammonio)phenyl)-amino]-1(4H)-naphthalinon-chlorid (CI56059; Basic Blue No. 99), Bis[4-(dimethyl-amino)phenyl][4-(methyl-amino)phenyl]- carbenium-chlorid (CI42535; Basic Violet No. 1), Tris[4-(dimethylamino)- phenyljcarbenium-chlorid (CI42555; Basic Violet No. 3), 2-[3,6- (Diethylamino)-dibenzopyranium-9-yl]-benzoesäure-chlorid (CI45170; Basic Violet No. 10), Di(4-aminophenyl)-(4-amino-3-methyl- phenyl)carbenium-chlorid (CI42510; Basic Violet No. 14), 1 ,3-Bis[(2,4- diamino-5-methylphenyl)azo]-3-methylbenzol (CI21010; Basic Brown No. 4), 1-[(4-Aminophenyl)azo]-7-(trimethylammonio)-2-naphthol-chlorid (Cl 12250; Basic Brown No. 16), 1-[(4-Amino-2-nitrophenyl)azo]-7- (trimethylammonio)-2-naphthol-chlorid (Basic Brown No. 17), 1 -[(4-Amino- 3-nitrophenyl)azo]-7-(trimethyl-ammonio)-2-naphthol-chlorid (Cl 12251 ; Basic Brown No. 17), 3,7-Diamino-2,8-dimethyl-5-phenyl-phenazinium- chlorid (CI50240; Basic Red No. 2), 1 ,4-Dimethyl-5-[(4-(dimethylamino)- phenyl)-azo]-1 ,2.4-triazolium-chlorid (CI11055; Basic Red No. 22), 2-Hydroxy-1-[(2-methoxy-phenyl)azo]-7-(trimethylammonio)-naphthalin- chlorid (Cl 12245; Basic Red No. 76), 2-[2-((2,4-Dimethoxy-phenyl)- amino)ethenyl]-1 ,3,3-trimethyl-3H-indol-1-ium-chlorid (CI48055; Basic Yellow No. 11), 3-Methyl-1-phenyl-4-[(3-(trimethylammonio)-phenyl)azo]- pyrazol-5-on-chlorid (CI12719; Basic Yellow No. 57), Bis[4-(diethylamino)- phenyl]phenylcarbenium-hydrogensulfat(1 :1) (CI42040; Basic Green No. 1 ), 1 -[Di(2-hydroxyethyl)-amino]-3-methyl-4-[(4-nitro-phenyl)azo]-benzol (CI11210, Disperse Red No. 17), 4-[(4-Aminophenyl)-azo]-1-[di(2- hydroxyethyl)amino]-3-methyl-benzol (HC Yellow No. 7), 2,6-Diamino-3- [(pyridin-3-yl)azo]-pyridin, 6-Hydroxy-5-[(4-sulfophenyl)azo]-2- naphthalinsulfonsäure-dinatriumsalz (Cl 15985; Food Yellow No. 3; FD&C Yellow No. 6), 2,4-Dinitro-1-naphthol-7-sulfonsäure-dinatriumsalz (CI10316; Acid Yellow No. 1 ; Food Yellow No. 1), 2-(lndan-1 ,3-dion-2- yl)chinolin-x,x-sulfonsäure (Gemisch aus Mono- und Disulfonsäure) (CI47005;D&C Yellow No. 10; Food Yellow No. 13; Acid Yellow No. 3), 5-Hydroxy-1-(4-sulfophenyl)-4-[(4-sulfophenyl)-azo]pyrazol-3-carbonsäure- trinatriumsalz (CM 9140; Food Yellow No. 4; Acid Yellow No. 23), 9-(2- Carboxyphenyl)-6-hydroxy-3H-xanthen-3-on (CI45350; Acid Yellow No. 73; D&C Yellow No. 8), 5-[(2,4-Dinitrophenyl)-amino]-2-phenylamino- benzolsulfonsäure-natriumsalz (Cl 10385; Acid Orange No. 3), 4-[(2,4- Dihydroxyphenyl)azo]-benzolsulfonsäure-mononatriumsalz (Cl 14270; Acid Orange No. 6), 4-[(2-Hydroxynaphth-1-yl)azo]-benzolsulfonsäure- natriumsalz (CM 5510; Acid Orange No. 7), 4-[(2,4-Dihydroxy-3-[(2,4- dimethylphenyl)azo]phenyl)azo]-benzol-sulfonsäure-natriumsalz (CI20170; Acid Orange No. 24), 4-Hydroxy-3-[(4-sulfonaphth-1-yl)azo]-1-naphthalin- sulfonsäure-dinatriumsalz (CI14720; Acid Red No. 14), 6-Hydroxy-5-[(4- sulfonaphth-1-yl)azo]-2, 4-naphthalin-disulfonsäure-trinatriumsalz (Cl 16255; Ponceau 4R; Acid Red No. 18), 3-Hydroxy-4-[(4-sulfonaphth-1- yl)azo]-2,7-naphthalin-disulfonsäure-trinatriumsalz (CM 6185; Acid Red No. 27), 8-Amino-1-hydroxy-2-(phenylazo)-3,6-naphthalin-disulfonsäure- dinatriumsalz (CI17200; Acid Red No. 33), 5-(Acetylamino)-4-hydroxy-3- [(2-methylphenyl)azo]-2,7-naphthalin-disulfonsäure-dinatriumsalz (CM 8065; Acid Red No. 35), 2-(3-Hydroxy-2,4,5,7-tetraiod-dibenzopyran-6- on-9-yl)-benzoesäure-dinatriumsalz (CI45430;Acid Red No. 51), N-[6-(Diethylamino)-9-(2,4-disulfophenyl)-3H-xanthen-3-yliden]-N- ethylethanammonium-hydroxid, inneres Salz, Natriumsalz (CI45100; Acid Red No. 52), 8-[(4-(Phenylazo)-phenyl)azo]-7-naphthol-1 ,3-disulfonsäure- dinatriumsalz (CI27290; Acid Red No. 73), dihydroxyspiro-[isobenzofuran-1(3H),9'-[9H]xanthen]-3-on-dinatriumsalz (CI45380; Acid Red No. 87), 2, I4, )5, I7,-Tetrabrom-4,5>6,7-tetrachlor-3, J6'- dihydroxyspiropsobenzofuran-I ßH Θ'fθHjxanthenj-S-on-dinatriumsalz (CI45410; Acid Red No. 92),3,,6'-Dihydroxy-4')5,-diiodospiro[isobenzofuran- 1(3H),9'(9H)-xanthen]-3-on-dinatriumsalz (CI45425; Acid Red No. 95), (2-Sulfophenyl)di[4-(ethyl((4-sulfophenyl)methyl)amino)phenyl]-carbenium- dinatriumsalz, betain (CI42090; Acid Blue No. 9; FD&C Blue No. 1), 1 ,4-Bis[(2-sulfo-4-methylphenyl)amino]-9,10-anthrachinon-dinatriumsalz (Cl 61570; Acid Green No. 25), Bis[4-(dimethylamino)phenyl]-(3,7-disulfo- 2-hydroxy-naphth-1-yl)carbenium-inneres Salz, mononatriumsalz (CI44090; Food Green No. 4; Acid Green No. 50), Bis[4-(diethylamino)- phenyl](2,4-disulfophenyl)carbenium-inneres salz, Natriumsalz (2:1) (CI42045; Food Blue No. 3; Acid Blue No. 1), Bis[4-(diethylamino)phenyl](5- hydroxy-2,4-disulfophenyl)carbenium-inneres salz, Calciumsalz (2:1) (CI42051 ; Acid Blue No. 3), 1-Amino-4-(cyclohexylamino)-9,10- anthrachinon-2-sulfon-säure-natriumsalz (CI62045; Acid Blue No. 62), 2-(1 ,3-Dihydro-3-oxo-5-sulfo-2H-indol-2-yliden)-2,3-dihydro-3-oxo-1 H-indol- 5-sulfonsäure-dinatriumsalz (CI73015; Acid Blue No. 74), 9-(2-Carboxy- phenyl)-3-[(2-methylphenyl)amino]-6-[(2-methyl-4-sulfophenyl)amino]- xanthylium-inneres Salz, mononatriumsalz (CI45190; Acid Violet No. 9), 1-Hydroxy-4-[(4-methyl-2-sulfophenyl)amino]-9,10-anthrachinon- natriumsalz (CI60730; D&C Violett No. 2; Acid Violet No. 43), Bis[3-nitro-4- [(4-phenylamino)-3-sulfo-phenylamino]-phenyl]-sulfon (Cl 10410; Acid Brown No. 13), 5-Amino-4-hydroxy-6-[(4-nitrophenyl)azo]-3-(phenylazo)- 2,7-naphthalin-disulfonsäure-dinatriumsalz (CI20470; Acid Black No. 1), 3- Hydroxy-4-[(2-hydroxynaphth-1-yl)azo]-7-nitro-1-naphthalin-sulfonsäure- chromkomplex (3:2) (CM 5711 ; Acid Black No. 52), 3-[(2,4-Dimethyl-5- sulfophenyl)azo]-4-hydroxy-1-naphthalin-sulfonsäure-dinatriumsalz (CI14700; Food Red No. 1; FD&C Red No. 4), 4-(Acetylamino)-δ-hydroxy- 6-[(7-sulfo-4-[(4-sulfophenyl)azo]naphth-1-yl)azo]-1 ,7-naphthalin- disulfonsäure-tetranatriumsalz (CI28440; Food Black No. 1) und 3-Hydroxy-4-(3-methyl-δ-oxo-1-phenyl-4,δ-dihydro-1H-pyrazol-4-ylazo)- naphthalin-1-sulfonsäure-natriumsalz, Chrom-Komplex (Acid Red No. 19δ), alleine oder in Kombination miteinander.Examples of suitable synthetic dyes are: 1,4-bis [(2-hydroxyethyl) amino] -2-nitrobenzene, 1- (2-hydroxyethyl) amino-2-nitro-4- [di (2-hydroxyethyl) -amino] -benzene (HC Blue No. 2), 1 -amino-3-methyl-4 - [(2-hydroxyethyl) -amino] -6-nitrobenzene (HC Violet No. 1), 4- [ethyl- ( 2-hydroxyethyl) amino] -1 - [(2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Blue No. 12), 4- [di (2-hydroxyethyl) amino] -1 - [(2nd - methoxyethyl) amino] -2-nitrobenzene (HC Blue No. 11), 1 - [(2,3-dihydroxypropyl) amino] -4- [methyl- (2-hydroxyethyl) amino] -2- nitrobenzene (HC Blue No. 10), 1 - [(2,3-dihydroxypropyl) amino] -4- [ethyl- (2-hydroxyethyl) amino] - 2-nitrobenzene hydrochloride (HC Blue No. 9), 1 - (3-hydroxypropylamino) -4- [di (2-hydroxyethyl) amino] -2-nitrobenzene (HC Violet No. 2), 1-methylamino- 4- [methyl- (2,3-dihydroxy-propyl) amino] -2-nitrobenzene (HC Blue No. 6), 2 - ((4-amino-2-nitrophenyl) amino) -5-dimethylamino-benzoic acid (HC Blue No. 13), 1-amino-4 - [(2nd -hydroxyethyl) amino] -2-nitrobenzene (HC Red No. 7), 2-amino-4,6-dinitro-phenol, 4-amino-2-nitro-diphenylamine (HC Red No. 1), 1-amino-4- [di (2-hydroxyethyl) amino] -2- nitrobenzene hydrochloride (HC Red No. 13), 1-amino-5-chloro-4 - [(2-hydroxyethyl) amino] -2-nitrobenzene, 4-amino-1 - [(2-hydroxyethyl) amino] -2 - nitrobenzene (HC Red No. 3), 4-amino-3-nitrophenol, 4 - [(2-hydroxyethyl) - amino] -3-nitrophenol, 1 - [(2-aminoethyl) amino] -4- (2- hydroxyethoxy) -2-nitrobenzene (HC Orange No. 2), 4- (2,3-dihydroxy-propoxy) -1 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Orange No. 3), 1-Amino-5-chloro-4 - [(2,3-dihydroxypropyl) amino] -2-nitrobenzene (HC Red No. 10), 5-chloro-1,4, 4- [di (2,3-dihydroxypropyl) amino ] -2-nitrobenzene (HC Red No. 11), 2 - [(2-hydroxyethyl) amino] -4,6-dinitro-phenol, 4-ethylamino-3-nitrobenzoic acid, 2 - [(4-amino- 2-nitrophenyl) amino] benzoic acid, 2-chloro-6- ethylamino-4-nitrophenol, 2-amino-6-chloro-4-nitrophenol, 4 - [(3-hydroxypropyl) amino] -3-nitrophenol, 2,5-diamino-6-nitropyridine, 1, 2,3 , 4-Tetrahydro-6-nitroquinoxaline, 7-amino-3,4-dihydro-6-nitro-2H-1,4-benzoxazine (HC Red No. 14), 1-amino-2 - [(2- hydroxyethyl) amino] -5-nitrobenzene (HC Yellow No. 5), 1- (2-hydroxyethoxy) -2 - [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow No. 4), 1 - [(2-Hydroxyethyl) amino] -2-nitrobenzene (HC Yellow No. 2), 2 - [(2-hydroxyethyl) amino] -1-methoxy-5-nitrobenzene. 2-amino-3-nitrophenol, 1- (2-hydroxyethoxy) -3-methylamino-4-nitrobenzene, 2,3- (dihydroxy-propoxy) -3-methylamino-4-nitrobenzene, 2 - [(2- Hydroxyethyl) amino] -5-nitrophenol (HC Yellow No. 11), 3 - [(2-aminoethyl) amino] - 1-methoxy-4-nitrobenzene hydrochloride (HC Yellow No.9), 1- [ (2-ureido-ethyl) amino] -4-nitrobenzene, 4 - [(2,3-di-hydroxypropyl) amino] -3-nitro-1-trifluoromethyl-benzene (HC Yellow No. 6), 1-chloro 2,4-bis [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow No. 10), 4 - [(2-hydroxyethyl) amino] -3-nitro-1-methylbenzene, 1-chlorine -4 - [(2-hydroxy-ethyl) amino] -3-nitrobenzene (HC Yellow No. 12), 4 - [(2-hydroxyethyl) amino] -3-nitro-1-trifluoromethyl-benzene (HC Yellow No 13), 4 - [(2-hydroxyethyl) amino] -3-nitro-benzonitrile (HC Yellow No. 14), 4 - [(2-hydroxyethyl) amino] -3-nitro-benzamide (HC Yellow No. 15), 1,4-di [(2,3-dihydroxy-propyl) amino] -9.10- anthraquinone, 1 - [(2-hydroxyethyl) amino] -4-methylamino-9,10-anthraquinone ( CI61505, Disperse Blue No. 3), 2 - [(2-amino-ethyl) amino] - 9,10-anthraquinone (HC Orange No. 5), 1-Hydroxy-4 - [(4 ~ methyl-2-sulfophenyl) amino] -9,10-anthraquinone, 1 - [(3-aminopropyl) amino] -4-methylamino-9,10-anthraquinone ( HC Blue No. 8), 1 - [(3-aminopropyl) amino] -9,10-anthraquinone (HC Red No. 8), 1, 4-diamino-2-methoxy-9,10-anthraquinone ( CI62015, Disperse Red No. 11, Solvent Violet No. 26), 1,4-dihydroxy-5,8-bis [(2-hydroxyethyl) amino] -9,10-anthraquinone (CI62500, Disperse Blue No. 7, solvent Blue No. 69), 9- (dimethylamino) benzo [a] - phenoxazin-7-ium chloride (CI51175; Basic Blue No. 6), Di [4- (diethyl- amino) phenyl] [4- (ethylamino) naphthyl] carbenium chloride (CI42595; Basic Blue No. 7), 3,7-di (dimethylamino) phenothiazine-5-ium chloride (CI52015; Basic Blue No. 9 ), Di [4- (dimethylamino) phenyl] [4- (phenylamino) naphthyl] carbenium chloride (CI44045; Basic Blue No. 26), 2 - [(4- (ethyl (2-hydroxyethyl) amino) phenyl) azo] -6-methoxy-3-methyl-benzothiazolium-methyl sulfate (CI11154; Basic Blue No. 41), 8-amino-2-bromo-5-hydroxy-4-imino-6 - [(3- (trimethylammonio) phenyl) amino] -1 (4H) -naphthalenone chloride (CI56059; Basic Blue No. 99), bis [4- (dimethylamino) phenyl] [4- (methylamino) phenyl] carbenium -chloride (CI42535; Basic Violet No. 1), tris [4- (dimethylamino) - phenyljcarbenium chloride (CI42555; Basic Violet No. 3), 2- [3,6- (diethylamino) -dibenzopyranium-9-yl] -benzoic acid chloride (CI45170; Basic Violet No. 10), di (4-aminophenyl) - (4-amino-3-methylphenyl) carbenium chloride (CI42510; Basic Violet No. 14), 1, 3-bis [(2,4-diamino-5-methylphenyl) azo] -3-methylbenzene (CI21010; Basic Brown No. 4), 1 - [(4-aminophe nyl) azo] -7- (trimethylammonio) -2-naphthol chloride (Cl 12250; Basic Brown No. 16), 1 - [(4-Amino-2-nitrophenyl) azo] -7- (trimethylammonio) -2-naphthol chloride (Basic Brown No. 17), 1 - [(4-amino-3-nitrophenyl) azo ] -7- (trimethyl-ammonio) -2-naphthol chloride (Cl 12251; Basic Brown No. 17), 3,7-diamino-2,8-dimethyl-5-phenyl-phenazinium chloride (CI50240; Basic Red No. 2), 1,4-dimethyl-5 - [(4- (dimethylamino) - phenyl) -azo] -1, 2,4-triazolium chloride (CI11055; Basic Red No. 22), 2-hydroxy-1- [(2-methoxyphenyl) azo] -7- (trimethylammonio) naphthalene chloride (Cl 12245; Basic Red No. 76), 2- [2 - ((2,4-dimethoxyphenyl) amino) ethenyl ] -1,3,3-trimethyl-3H-indole-1-ium chloride (CI48055; Basic Yellow No. 11), 3-methyl-1-phenyl-4 - [(3- (trimethylammonio) phenyl) azo ] - pyrazol-5-one chloride (CI12719; Basic Yellow No. 57), bis [4- (diethylamino) - phenyl] phenylcarbenium hydrogen sulfate (1: 1) (CI42040; Basic Green No. 1), 1 - [ Di (2-hydroxyethyl) amino] -3-methyl-4 - [(4-nitro-phenyl) azo] benzene (CI11210, Disperse Red No. 17), 4 - [(4-aminophenyl) -azo] - 1- [di (2- hydroxyethyl) amino] -3-methyl-benzene (HC Yellow No. 7), 2,6-diamino-3- [(pyridin-3-yl) azo] pyridine, 6-hydroxy-5 - [(4-sulfophenyl ) azo] -2- naphthalenesulfonic acid disodium salt (Cl 15985; Food Yellow No. 3; FD&C Yellow No. 6), 2,4-dinitro-1-naphthol-7-sulfonic acid disodium salt (CI10316; Acid Yellow No. 1; Food Yellow No. 1), 2- (Indan-1, 3-dion-2-yl) quinoline-x, x-sulfonic acid (mixture of mono- and disulfonic acid) (CI47005; D&C Yellow No. 10; Food Yellow No. 13; Acid Yellow No. 3), 5-Hydroxy-1- (4-sulfophenyl) -4 - [(4-sulfophenyl) -azo] pyrazole-3-carboxylic acid trisodium salt (CM 9140; Food Yellow No. 4; Acid Yellow No. 23), 9- (2-carboxyphenyl) -6-hydroxy-3H-xanthene-3-one (CI45350; Acid Yellow No. 73; D&C Yellow No. 8), 5 - [(2,4-dinitrophenyl ) -amino] -2-phenylamino-benzenesulfonic acid sodium salt (Cl 10385; Acid Orange No. 3), 4 - [(2,4-Dihydroxyphenyl) azo] -benzenesulfonic acid monosodium salt (Cl 14270; Acid Orange No. 6), 4 - [(2-hydroxynaphth-1-yl) azo] benzenesulfonic acid sodium salt (CM 5510; Acid Or ange No. 7), 4 - [(2,4-Dihydroxy-3 - [(2,4-dimethylphenyl) azo] phenyl) azo] benzene sulfonic acid sodium salt (CI20170; Acid Orange No. 24), 4-hydroxy-3 - [(4-sulfonaphth-1-yl) azo] -1-naphthalenesulfonic acid disodium salt (CI14720; Acid Red No. 14), 6-hydroxy-5 - [(4-sulfonaphth-1-yl) azo] - 2, 4-naphthalene-disulfonic acid, trisodium salt (Cl 16255; Ponceau 4R; Acid Red No. 18), 3-hydroxy-4 - [(4-sulfonaphth-1-yl) azo] -2,7-naphthalene-disulfonic acid- trisodium salt (CM 6185; Acid Red No. 27), 8-amino-1-hydroxy-2- (phenylazo) -3,6-naphthalenedisulfonic acid disodium salt (CI17200; Acid Red No. 33), 5- (acetylamino) -4-hydroxy-3- [(2-methylphenyl) azo] -2,7-naphthalene-disulfonic acid disodium salt (CM 8065; Acid Red No. 35), 2- (3-hydroxy-2,4,5,7 -tetraiododibenzopyran-6- on-9-yl) -benzoic acid disodium salt (CI45430; Acid Red No. 51), N- [6- (diethylamino) -9- (2,4-disulfophenyl) -3H-xanthene- 3-ylidene] -N-ethylethanammonium hydroxide, inner salt, sodium salt (CI45100; Acid Red No. 52), 8 - [(4- (phenylazo) phenyl) azo] -7-naphthol-1, 3-disulphonic disodium salt (CI27290; Acid Red No. 73), dihydroxyspiro- [isobenzofuran-1 (3H), 9 '- [9H] xanthene] -3-one disodium salt (CI45380; Acid Red No. 87), 2 , I 4 , ) 5 , I 7 , -Tetrabrom-4, 5> 6,7-tetrachloro-3, J-I 6'dihydroxyspiropsobenzofuran ßH Θ'fθHjxanthenj-S-one disodium salt (CI45410; Acid Red No. 92), 3,,) 6'-dihydroxy-4 '5, -diiodospiro [isobenzofuran-1 (3H), 9 '(9H) -xanthene] -3-one-disodium salt (CI45425; Acid Red No. 95), (2-sulfophenyl) di [4- (ethyl ((4-sulfophenyl ) methyl) amino) phenyl] carbenium disodium salt, betaine (CI42090; Acid Blue No. 9; FD&C Blue No. 1), 1, 4-bis [(2-sulfo-4-methylphenyl) amino] -9.10 -anthraquinone disodium salt (Cl 61570; Acid Green No. 25), bis [4- (dimethylamino) phenyl] - (3,7-disulfo-2-hydroxy-naphth-1-yl) carbenium inner salt, monosodium salt (CI44090 ; Food Green No. 4; Acid Green No. 50), bis [4- (diethylamino) phenyl] (2,4-disulfophenyl) carbenium inner salt, sodium salt (2: 1) (CI42045; Food Blue No. 3 Acid Blue No. 1), bis [4- (diethylamino) phenyl] (5-hydroxy-2,4-disulfophenyl) carbenium inner salt, Cal calcium salt (2: 1) (CI42051; Acid Blue No. 3), 1-Amino-4- (cyclohexylamino) -9,10-anthraquinone-2-sulfonic acid sodium salt (CI62045; Acid Blue No. 62), 2- (1, 3-dihydro-3-oxo-5 -sulfo-2H-indol-2-ylidene) -2,3-dihydro-3-oxo-1 H-indole-5-sulfonic acid disodium salt (CI73015; Acid Blue No. 74), 9- (2-carboxyphenyl ) -3 - [(2-methylphenyl) amino] -6 - [(2-methyl-4-sulfophenyl) amino] - xanthylium inner salt, monosodium salt (CI45190; Acid Violet No. 9), 1-hydroxy-4- [(4-methyl-2-sulfophenyl) amino] -9,10-anthraquinone sodium salt (CI60730; D&C Violet No. 2; Acid Violet No. 43), bis [3-nitro-4- [(4-phenylamino) -3-sulfo-phenylamino] phenyl] sulfone (Cl 10410; Acid Brown No. 13), 5-amino-4-hydroxy-6 - [(4-nitrophenyl) azo] -3- (phenylazo) - 2, 7-naphthalene-disulfonic acid disodium salt (CI20470; Acid Black No. 1), 3-hydroxy-4 - [(2-hydroxynaphth-1-yl) azo] -7-nitro-1-naphthalene-sulfonic acid-chromium complex (3: 2) (CM 5711; Acid Black No. 52), 3 - [(2,4-dimethyl-5-sulfophenyl) azo] -4-hydroxy-1-naphthalenesulfonic acid disodium salt (CI14700; Food Red No. 1; FD&C Red No. 4), 4- (acetylamino) -δ-hydroxy-6 - [(7-sulfo-4 - [(4-sulfophenyl) azo] naphth-1-yl) azo] -1, 7-naphthalenedisulfonic acid tetrasodium salt (CI28440; Food Black No. 1) and 3-hydroxy-4- (3-methyl-δ-oxo-1-phenyl-4, δ-dihydro-1H-pyrazole -4-ylazo) - naphthalene-1-sulfonic acid sodium salt, chromium complex (Acid Red No. 19δ), alone or in combination with each other.
Die Gesamtmenge der direktziehenden Farbstoffe kann in dem erfindungsgemässen Mittel etwa 0,01 bis 7 Gewichtsprozent betragen, vorzugsweise etwa 0,2 bis 4 Gewichtsprozent.The total amount of direct dyes in the agent according to the invention can be about 0.01 to 7 percent by weight, preferably about 0.2 to 4 percent by weight.
Weitere zur Haarfärbung bekannte und übliche Farbstoffe, die in dem erfindungsgemässen Färbemittel enthalten sein können, sind unter anderem in E. Sagarin, "Cosmetics, Science and Technology", Interscience Publishers Inc., New York (19δ7), Seiten δ03 ff. sowie H. Janistyn, "Handbuch der Kosmetika und Riechstoffe", Band 3 (1973), Seiten 388 ff. und K. Schrader „Grundlagen und Rezepturen der Kosmetika", 2. Auflage (1989), Seiten 782-81 δ beschrieben.Further dyes known and customary for hair dyeing, which may be present in the colorant according to the invention, are described, inter alia, in E. Sagarin, "Cosmetics, Science and Technology", Interscience Publishers Inc., New York (19δ7), pages δ03 ff Janistyn, "Handbook of Cosmetics and Fragrances", Volume 3 (1973), pages 388 ff. And K. Schrader "Fundamentals and Recipes of Cosmetics", 2nd edition (1989), pages 782-81 δ.
Darüberhinaus können in dem erfindungsgemäßen Mittel Antioxidantien wie zum Beispiel Ascorbinsäure, Thioglykolsäure oder Natriumsulfit, sowie Komplexbildner für Schwermetalle, beispielsweise Ethylendiamino- tetraacetat oder Nitriloessigsäure, in einer Menge von bis zu etwa 0,δ Gewichtsprozent enthalten sein. Parfümöle können in der erfindungsgemäßen Farbträgermasse in einer Menge von bis zu etwa 1 Gewichtsprozent enthalten sein. Selbstverständlich kann das vorstehend beschriebene Haarfärbemittel gegebenenfalls weitere, für Haarfärbemittel übliche Zusätze, wie zum Beispiel Verdickungsmittel, beispielsweise Homopolymere der Acrylsäure, Pflanzen Gums, Cellulose- und Stärkederivate, Algenpolyasaccharide, amphiphile Assoziatiwerdicker, desweiteren Konservierungsstoffe; Antioxidantien, beispielsweise Natriumsulfit, Thioglykolsäure oder Ascorbinsäure; Komplexbildner; Lösungsmittel wie Wasser, oder wie bereits beschrieben niedere aliphatische Alkohole, beispielsweise aliphatische Alkohole mit 1 bis 4 Kohlenstoffatomen wie Ethanol, Propanol und Isopropanol, oder Glykole wie Glycerin und 1 ,2-Propylenglykol, oder auch Sorbitol und Netzmittel oder Emulgatoren, aus den Klassen der anionischen, kationischen, amphoteren oder nichtionogenen oberflächenaktiven Substanzen und weiterhin Weichmacher; Vaseline; Silikonöle, Paraffinöl, Polysorbate und Fettsäuren sowie außerdem Pflegestoffe, wie kationische Polymere oder Harze, Lanolinderivate, Cholesterin, Vitamine, Pantothensäure und Betain, Salze, wie Natriumchlorid oder Natriumsulfat, enthalten. Die erwähnten Bestandteile werden in den für solche Zwecke üblichen Mengen verwendet, zum Beispiel die Netzmittel und Emulgatoren in Konzentrationen von 0,1 bis 30 Gewichtsprozent und die Pflegestoffe in einer Konzentration von 0,1 bis 5,0 Gewichtsprozent.In addition, antioxidants such as, for example, ascorbic acid, thioglycolic acid or sodium sulfite, and complexing agents for heavy metals, for example ethylenediaminetetraacetate or nitriloacetic acid, can be present in the agent according to the invention in an amount of up to about 0.1% by weight. Perfume oils can be contained in the color carrier composition according to the invention in an amount of up to about 1 percent by weight. Of course, the hair colorant described above may optionally contain other additives customary for hair colorants, such as thickeners, for example homopolymers of acrylic acid, vegetable gums, cellulose and Starch derivatives, algal polyasaccharides, amphiphilic associative thickeners, furthermore preservatives; Antioxidants, for example sodium sulfite, thioglycolic acid or ascorbic acid; complexing; Solvents such as water, or, as already described, lower aliphatic alcohols, for example aliphatic alcohols having 1 to 4 carbon atoms such as ethanol, propanol and isopropanol, or glycols such as glycerol and 1,2-propylene glycol, or also sorbitol and wetting agents or emulsifiers, from the classes of anionic, cationic, amphoteric or nonionic surface-active substances and also plasticizers; Vaseline; Contain silicone oils, paraffin oil, polysorbates and fatty acids as well as care substances such as cationic polymers or resins, lanolin derivatives, cholesterol, vitamins, pantothenic acid and betaine, salts such as sodium chloride or sodium sulfate. The constituents mentioned are used in the amounts customary for such purposes, for example the wetting agents and emulsifiers in concentrations of 0.1 to 30 percent by weight and the care substances in a concentration of 0.1 to 5.0 percent by weight.
Das erfindungsgemäße Mittel wird vorzugsweise in Form einer wäßrigen oder wäßrig-alkoholischen Zubereitung, beispielsweise als verdickte Lösung, als Emulsion, als Creme, als Aerosol-Schaum oder als Gel, konfektioniert.The agent according to the invention is preferably packaged in the form of an aqueous or aqueous-alcoholic preparation, for example as a thickened solution, as an emulsion, as a cream, as an aerosol foam or as a gel.
Die reduzierte Färbemittelzubereitung ist möglichst in der reduzierten Form zu stabilisieren und vor Luftsauerstoff zu schützen. Dies kann durch geeignete Verpackung, Schutzgas und Zusatz von schützenden und/oder stabilisierenden Substanzen oder Veresterung (sogenannte Leukoküpen- farbstoffester hergestellt mit Chloroschwefelsäure) erreicht werden. Schützende oder stabilisierende Verbindungen sind zum Beispiel kationische Verbindungen, beispielsweise Polymere, Tenside oder Metallionen wie zum Beispiel Zink.The reduced colorant preparation should be stabilized in the reduced form as far as possible and protected against atmospheric oxygen. This can be achieved by suitable packaging, protective gas and the addition of protective and / or stabilizing substances or esterification (so-called leuco vat dye esters made with chlorosulfuric acid). Protective or stabilizing compounds are for example cationic compounds, for example polymers, surfactants or metal ions such as zinc.
Zur Erzielung einer gleichmäßigen intensiven Färbung auf den Haaren ist es von Vorteil, die reduzierte Farbstofform auch während des Färbeprozesses vor Luftsauerstoff zu schützten. Dies kann beispielsweise dadurch geschehen, dass man eine Plastikkappe mit über die ganze Fläche verteilten Ventilöffnungen über das feuchte Haar stülpt. Über die etwa 5 bis 10 Ventile kann man so eine relativ flüssige Färbemischung unter die Plastikhaube „spritzen" und dann von aussen möglichst gut verteilen und einmassieren. Ebenfalls ist die Verwendung einer Plastikhaube mit kleinen Löchern möglich, durch die man mit Hilfe einer Einfülldüse einen Aerosolschaum unter die Abdeckung auf die Haare aufträgt und anschließend durch Massieren verteilt.In order to achieve a uniform, intensive dyeing on the hair, it is advantageous to protect the reduced dye form from atmospheric oxygen even during the dyeing process. This can be done, for example, by putting a plastic cap with valve openings over the entire surface over damp hair. About 5 to 10 valves can be used to "inject" a relatively liquid dye mixture under the plastic hood and then distribute and massage in as well as possible from the outside. It is also possible to use a plastic hood with small holes through which an aerosol foam can be used with the help of a filling nozzle apply to the hair under the cover and then spread by massaging.
Nach einer Einwirkungszeit von etwa 1 bis 60 Minuten, vorzugsweise 5 bis 30 Minuten, bei etwa 1δ bis 60 °C, vorzugsweise 20 bis 4δ °C, wird die Färbung oxidativ „entwickelt". Hierzu kommen als Oxidationsmittel zur Entwicklung der Färbung neben einfacher Luftoxidation insbesondere Wasserstoffperoxid oder dessen Additionsverbindungen an Harnstoff, Melamin oder Natriumborat in Form einer 1- bis 12prozentigen, vorzugsweise einer 1 ,δ- bis 6prozentigen, wäßrigen Lösung in Betracht. Das Mischungsverhältnis von Färbemittel zu Oxidationsmittel ist abhängig von der Konzentration des Oxidationsmittels und beträgt in der Regel etwa δ:1 bis 1 :2, vorzugsweise 1:1 , wobei der Gehalt an Oxidationsmittel in der erhaltenen Mischung aus Färbemittel und Oxidationsmittel vorzugsweise etwa 0,δ bis 8 Gewichtsprozent, insbesondere 1 bis 4 Gewichtsprozent, beträgt. Man läßt das Oxidationsmittel solange einwirken bis der Farbstoff wieder in seiner unlöslichen Pigmentform vorliegt (in der Regel etwa 2 bis δ Minuten) und so waschstabil am Haar fixiert ist. Man kann allerdings die Einwirkzeit des Oxidationsmittels je nach gewünschtem Aufhellungsgrad verlängern. Werden Aufellungen des Naturpigments um mehr als zwei Stufen gewünscht können auch Persulfate oder Mischungen aus Persulfaten und Wasserstoffperoxid oder dessen Additionsverbindungen verwendet werden. Vorzugsweise werden in diesem Fall alkalische Persulfat/Peroxid-Zubereitungen verwendet.After an exposure time of about 1 to 60 minutes, preferably 5 to 30 minutes, at about 1δ to 60 ° C., preferably 20 to 4δ ° C., the coloring is “developed” oxidatively. In addition to simple air oxidation, there are oxidizing agents for developing the coloring in particular hydrogen peroxide or its addition compounds to urea, melamine or sodium borate in the form of a 1 to 12 percent, preferably a 1, 6 to 6 percent, aqueous solution into consideration. The mixing ratio of colorant to oxidizing agent is dependent on the concentration of the oxidizing agent and is in the Rule about δ: 1 to 1: 2, preferably 1: 1, the content of oxidizing agent in the resulting mixture of colorant and oxidizing agent preferably being about 0, δ to 8 percent by weight, in particular 1 to 4 percent by weight act until the dye is back in its insoluble pigment form (in de r usually about 2 to δ minutes) and is wash-stable on the hair. However, the exposure time of the oxidizing agent can be extended depending on the desired degree of lightening. If brightening of the natural pigment by more than two stages is desired, persulfates or mixtures of persulfates and hydrogen peroxide or their addition compounds can also be used. In this case, alkaline persulfate / peroxide preparations are preferably used.
Im Anschluss an den Färbevorgang spült man das Haar mit Wasser aus und trocknet sie. Gegebenenfalls kann das Haar zusätzlich mit einem Shampoo gewaschen und eventuell mit einem sauer eingestellten Konditioner nachgespült werden. Anschließend wird das Haar getrocknet.After the dyeing process, the hair is rinsed with water and dried. If necessary, the hair can also be washed with a shampoo and possibly rinsed with an acidic conditioner. The hair is then dried.
Die nachfolgenden Beispiele sollen den Gegenstand der Erfindung näher erläutern ohne diesen hierauf zu beschränken.The following examples are intended to explain the subject matter of the invention in more detail without restricting it thereto.
B e i s p i e l eExample
Beispiel 1 : FärbemischungExample 1: Coloring mix
10,0 g Propylenglykol 1 ,0 g Indigo 1 ,0 g Acetoin 12,0 g Natriumhydroxyd (10%ige wäßrige Lösung) 3,0 g Polyquaternium-7 (8%ige wäßrige Lösung) 6δ,0 g Wasser Die vorgenannten Substanzen werden gemischt und unter Argon 2 Stunden lang bei 40 °C stehen gelassen. Anschließend wird der pH-Wert mit 4,0 g Ammoniak (2δ%ige wäßrige Lösung) und 4,0 g Milchsäure (90%ige wäßrige Lösung) auf 9,6 eingestellt.10.0 g propylene glycol 1.0 g indigo 1.0 g acetoin 12.0 g sodium hydroxide (10% aqueous solution) 3.0 g polyquaternium-7 (8% aqueous solution) 6.0 g water The above substances are mixed and left under argon at 40 ° C for 2 hours. The pH is then adjusted to 9.6 with 4.0 g of ammonia (2δ% aqueous solution) and 4.0 g of lactic acid (90% aqueous solution).
10 g des so erhaltenen Gemisches werden anschließend auf mittelblonde Naturhaare aufgetragen. Das Haar wird sodann mit einer Plastikhaube oder Plastikfolie abgedeckt. Nach einer Einwirkungszeit von 30 Minuten bei 40 °C werden zusätzlich 10 g einer 6%igen wäßrigen Wasserstoff- peroxyd-Emulsion einmassiert und 2 Minuten lang einwirken gelassen. Anschließend spült man das Haar mit Wasser aus, wäscht es mit einem Shampoo, spült sodann mit einem sauren Konditioner und trocknet es abschließend.10 g of the mixture thus obtained are then applied to medium blonde natural hair. The hair is then covered with a plastic hood or plastic wrap. After an exposure time of 30 minutes at 40 ° C., an additional 10 g of a 6% aqueous hydrogen peroxide emulsion are massaged in and left to act for 2 minutes. The hair is then rinsed out with water, washed with a shampoo, then rinsed with an acid conditioner and then dried.
Das Haar erhält eine gleichmäßige blauschwarze Färbung.The hair gets an even blue-black color.
Beispiel 2: FärbemischungExample 2: Coloring mix
20,00 g Propylenglykol 1 ,00 g Indigo 1 ,00 g Acetoin 12,00 g Natriumhydroxyd (10%ige wäßrige Lösung) 0,2δ g Polyquaternium-4 57,75 g Wasser20.00 g propylene glycol 1.00 g indigo 1.00 g acetoin 12.00 g sodium hydroxide (10% aqueous solution) 0.2δ g polyquaternium-4 57.75 g water
Die vorgenannten Substanzen werden gemischt und unter Argon 2 Stunden lang bei 40 °C stehen gelassen. Anschließend wird der pH-Wert mit 4,0 g Ammoniak (25%ige wäßrige Lösung) und 4,0 g Milchsäure (90%ige wäßrige Lösung) auf 9,6 eingestellt.The above substances are mixed and left under argon at 40 ° C for 2 hours. Then the pH adjusted to 9.6 with 4.0 g ammonia (25% aqueous solution) and 4.0 g lactic acid (90% aqueous solution).
10 g der so erhaltenen Mischung werden mit δ g einer Creme aus10 g of the mixture thus obtained are made with δ g of a cream
10,0 g Laurylethersulfat (28%ige wäßrige Lösung) 11 ,0 g Cetylstearylalkohol ad 100,0 g Wasser10.0 g lauryl ether sulfate (28% aqueous solution) 11.0 g cetylstearyl alcohol ad 100.0 g water
verrührt und die Färbecreme auf eine gebleichte Haarsträhne aufgetragen. Man lässt 30 Minuten lang bei 40 °C unter Sauerstoffausschluss einwirken. Anschließend werden zusätzlich 1δ g einer 6 %igen Wasserstoffperoxyd-Emulsion einmassiert. Man läßt 2 lang Minuten einwirken und spült das Haar sodann mit Wasser aus. Nach erneutem Spülen mit einem sauren Konditioner wird das Haar getrocknet.stirred and the coloring cream applied to a bleached strand of hair. Allow to act for 30 minutes at 40 ° C with exclusion of oxygen. Then an additional 1δ g of a 6% hydrogen peroxide emulsion is massaged in. Allow to act for 2 minutes and then rinse the hair with water. After rinsing again with an acid conditioner, the hair is dried.
Das Haar erhält eine tiefblaue gleichmäßige Färbung.The hair gets a deep blue, even color.
Beispiel 3: FärbemischungExample 3: Coloring mix
10,00 g Propylenglykol 1 ,00 g Indigo 12,00 g Natriumhydroxyd (10%ige wäßrige Lösung) 1 ,00 g Hydroxyaceton 0,6δ g Polyquaternium-16 (40%ige wäßrige Lösung) 67,3δ g Wasser Die vorgenannten Substanzen werden gemischt und unter Argon 2 Stunden lang bei 40 °C stehen gelassen. Anschließend wird der pH-Wert mit 4,0 g Ammoniak (2δ%ige wäßrige Lösung) und 4,0 g Milchsäure (90%ige wäßrige Lösung) auf 9,6 eingestellt.10.00 g propylene glycol 1.00 g indigo 12.00 g sodium hydroxide (10% aqueous solution) 1.00 g hydroxyacetone 0.6δ g polyquaternium-16 (40% aqueous solution) 67.3δ g water The above substances are mixed and left under argon at 40 ° C for 2 hours. The pH is then adjusted to 9.6 with 4.0 g of ammonia (2δ% aqueous solution) and 4.0 g of lactic acid (90% aqueous solution).
20 g des so erhaltenen Gemisches werden auf hellbraune Naturhaare aufgetragen. Das Haar wird sodann mit einer Plastikhaube oder Plastikfolie abgedeckt. Nach einer Einwirkungszeit von 30 Minuten bei 40 °C werden zusätzlich 20 g einer 6%igen wäßrigen Wasserstoffperoxyd-Emulsion einmassiert und 2 Minuten lang einwirken gelassen. Anschließend spült man das Haar mit Wasser aus, spült sodann mit einem sauren Konditioner und trocknet es abschließend. Das Haar erhält eine gleichmäßige blauschwarze Färbung.20 g of the mixture thus obtained are applied to light brown natural hair. The hair is then covered with a plastic hood or plastic wrap. After an exposure time of 30 minutes at 40 ° C., an additional 20 g of a 6% aqueous hydrogen peroxide emulsion are massaged in and left to act for 2 minutes. The hair is then rinsed out with water, then rinsed with an acid conditioner and then dried. The hair gets an even blue-black color.
Beispiel 4: FärbemischungExample 4: Coloring mix
10,0 g Propylenglykol 1 ,0 g Indirubin 12,0 g Natriumhydroxyd (10%ige wäßrige Lösung) 3,0 g Polyquaternium-7 (8%ige wäßrige Lösung) 1 ,0 g Acetoin 6δ,0 g Wasser10.0 g propylene glycol 1.0 g indirubin 12.0 g sodium hydroxide (10% aqueous solution) 3.0 g polyquaternium-7 (8% aqueous solution) 1.0 g acetoin 6δ.0 g water
Die vorgenannten Substanzen werden gemischt und unter Argon 2 Stunden lang bei 40 °C stehen gelassen. Anschließend wird der pH-Wert mit 4,0 g Ammoniak (2δ%ige wäßrige Lösung) und 4,0 g Milchsäure (90%ige wäßrige Lösung) auf 9,6 eingestellt. 1δ g des so erhaltenen Gemisches werden auf gebleichte Naturhaare aufgetragen. Das Haar wird sodann mit einer Plastikhaube oder Plastikfolie abgedeckt. Nach einer Einwirkungszeit von 30 Minuten bei 40 °C werden zusätzlich 1δ g einer 6%igen wäßrigen Wasserstoffperoxyd-Emulsion einmassiert und 2 Minuten lang einwirken gelassen. Anschließend spült man das Haar mit Wasser aus, spült sodann mit einem sauren Konditioner und trocknet es abschließend. Das Haar erhält eine gleichmäßige rotviolette Färbung.The above substances are mixed and left under argon at 40 ° C for 2 hours. The pH is then adjusted to 9.6 with 4.0 g of ammonia (2δ% aqueous solution) and 4.0 g of lactic acid (90% aqueous solution). 1δ g of the mixture thus obtained are applied to bleached natural hair. The hair is then covered with a plastic hood or plastic wrap. After an exposure time of 30 minutes at 40 ° C., an additional 1δ g of a 6% aqueous hydrogen peroxide emulsion is massaged in and left to act for 2 minutes. The hair is then rinsed out with water, then rinsed with an acid conditioner and then dried. The hair gets an even red-violet color.
Beispiel 5: FärbemischungExample 5: Coloring mix
10,0 g Propylenglykol 1 ,0 g Indigo 12,0 g Natriumhydroxyd (10%ige wäßrige Lösung) 3,0 g Polyquatemium-7 (8%ige wäßrige Lösung) 1 ,0 g Acetoin 62,6 g Wasser10.0 g propylene glycol 1.0 g indigo 12.0 g sodium hydroxide (10% aqueous solution) 3.0 g polyquaternium-7 (8% aqueous solution) 1.0 g acetoin 62.6 g water
Die vorgenannten Substanzen werden gemischt und unter Argon 2 Stunden lang bei 40 °C stehen gelassen. Anschließend werden der pH- Wert mit 4,0 g Ammoniak (2δ%ige wäßrige Lösung) und 4,0 g Milchsäure (90%ige wäßrige Lösung) auf 9,6 eingestellt und die oxidativen Farbstoffvorstufen (1 ,5 g 1-Hydroxyethyl-4,5-diamino-pyrazol-Sulfat; 0,8 g 4-Amino-2-hydroxytoluol und 0,1 g 2,6-Diamino-3-((pyridin-3- yl)azo)pyridin) zugegeben.The above substances are mixed and left under argon at 40 ° C for 2 hours. The pH is then adjusted to 9.6 with 4.0 g ammonia (2δ% aqueous solution) and 4.0 g lactic acid (90% aqueous solution) and the oxidative dye precursors (1.5 g 1-hydroxyethyl 4,5-diamino-pyrazole sulfate, 0.8 g of 4-amino-2-hydroxytoluene and 0.1 g of 2,6-diamino-3 - ((pyridin-3-yl) azo) pyridine) were added.
20 g des so erhaltenen Gemisches werden anschließend auf dunkelblonde Naturhaare aufgetragen. Das Haar wird sodann mit einer Plastikhaube oder Plastikfolie abgedeckt. Nach einer Einwirkungszeit von 1δ Minuten bei 40 °C werden zusätzlich 30 g einer 6%igen wäßrigen Wasserstoffperoxyd-Emulsion einmassiert und 10 Minuten lang einwirken gelassen. Anschließend spült man das Haar mit Wasser aus, spült sodann mit einem sauren Konditioner und trocknet es abschließend. Das Haar erhält eine gleichmäßige rotbraune Färbung.20 g of the mixture thus obtained are then applied to dark blonde natural hair. The hair is then with a Plastic hood or plastic film covered. After an exposure time of 1δ minutes at 40 ° C., an additional 30 g of a 6% aqueous hydrogen peroxide emulsion are massaged in and left to act for 10 minutes. The hair is then rinsed out with water, then rinsed with an acid conditioner and then dried. The hair gets an even red-brown color.
Beispiel 6: FärbemischungExample 6: Coloring mix
10,0 g Propylenglykol 1 ,0 g 6,6'-Dibrom-indigo 12,0 g Natriumhydroxyd (10%ige wäßrige Lösung) 3,0 g Polyquaternium-7 (8%ige wäßrige Lösung) 1 ,0 g Acetoin 6δ,0 g Wasser10.0 g propylene glycol 1, 0 g 6,6'-dibromo-indigo 12.0 g sodium hydroxide (10% aqueous solution) 3.0 g polyquaternium-7 (8% aqueous solution) 1, 0 g acetoin 6δ, 0 g water
Die vorgenannten Substanzen werden gemischt und unter Argon 2 Stunden lang bei 40 °C stehen gelassen. Anschließend wird der pH-Wert mit 4,0 g Ammoniak (2δ%ige wäßrige Lösung) und 4,0 g Milchsäure (90%ige wäßrige Lösung) auf 9,6 eingestellt.The above substances are mixed and left under argon at 40 ° C for 2 hours. The pH is then adjusted to 9.6 with 4.0 g of ammonia (2δ% aqueous solution) and 4.0 g of lactic acid (90% aqueous solution).
10 g des so erhaltenen Gemisches werden auf gebleichte Naturhaare aufgetragen. Das Haar wird sodann mit einer Plastikhaube oder Plastikfolie abgedeckt. Nach einer Einwirkungszeit von 30 Minuten bei 40 °C werden zusätzlich 10 g einer 6%igen wäßrigen Wasserstoffperoxyd-Emulsion einmassiert und 2 Minuten lang einwirken gelassen. Anschließend spült man das Haar mit Wasser aus, spült sodann mit einem sauren Konditioner und trocknet es abschließend. Das Haar erhält eine gleichmäßige rosa Färbung.10 g of the mixture thus obtained are applied to bleached natural hair. The hair is then covered with a plastic hood or plastic wrap. After an exposure time of 30 minutes at 40 ° C., an additional 10 g of a 6% aqueous hydrogen peroxide emulsion are massaged in and left to act for 2 minutes. Then rinse the hair with water, then rinse with an acid Conditioner and finally it dries. The hair gets an even pink color.
Alle in der vorliegenden Anmeldung genannten Prozentangaben stellen, soweit nicht anders angegeben, Gewichtsprozente dar. Unless stated otherwise, all percentages given in the present application represent percentages by weight.

Claims

P a t e n t a n s p r ü c h e Patent claims
1. Mittel zur Färbung von Haaren, dadurch gekennzeichnet, dass es mindestens einen indigoiden Küpenfarbstoff, mindestens eine kationische Verbindung und als Reduktionsmittel mindestens eine im alkalischen Medium ein Endiol bildende Verbindung enthält.1. Agent for dyeing hair, characterized in that it contains at least one indigoid vat dye, at least one cationic compound and as a reducing agent at least one compound forming an endiol in the alkaline medium.
2. Gebrauchsfertiges Mittel zur Färbung von Haaren, dadurch gekennzeichnet, dass es einen in Gegenwart einer kationischen Verbindung mit einer im alkalischen Medium ein Endiol bildenden Verbindung reduzierten indigoiden Küpenfarbstoff enthält und einen pH- Wert von 4 bis 11 aufweist.2. Ready-to-use agent for dyeing hair, characterized in that it contains an indigoid vat dye reduced in the presence of a cationic compound with an endiol-forming compound in an alkaline medium and has a pH of 4 to 11.
3. Mittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die im alkalischen Medium ein Endiol bildende Verbindung ausgewählt ist aus Monohydroxyaceton, Dihydroxyaceton, Acetoin, Glutaroin, Adipoin, Glykolaldehyd, Benzoin, 2,3-Dihydroxyacrylaldehyd und Cycopentadiolon.3. Composition according to claim 1 or 2, characterized in that the compound forming an endiol in the alkaline medium is selected from monohydroxyacetone, dihydroxyacetone, acetoin, glutaroin, adipoin, glycol aldehyde, benzoin, 2,3-dihydroxyacrylaldehyde and cycopentadiolone.
4. Mittel nach einem der Ansprüche 1 bis 3 dadurch gekennzeichnet, dass die im alkalischen Medium ein Endiol bildende Verbindung bezogen auf den Küpenfarbstoff in einer äquimolaren Menge oder einem bis zu δOfachen Überschuss enthalten ist.4. Composition according to one of claims 1 to 3, characterized in that the compound which forms an endiol in the alkaline medium, based on the vat dye, is present in an equimolar amount or in an up to δO fold excess.
δ. Mittel nach einem der Ansprüche 1 bis 4 dadurch gekennzeichnet, dass der Küpenfarbstoff ausgewählt ist aus Indigo, Indirubin, 6,6'-Dibromindigo, 5,5',7,7'-Tetrabromindigo, 4,4',7,7'-Tetrachlorindigo, Thioindigo, 6,6'Dichlor-4,4'-dimethyl-thioindigo, δ. Agent according to one of claims 1 to 4, characterized in that the vat dye is selected from indigo, indirubin, 6,6'-dibromoindigo, 5,5 ', 7,7'-tetrabromoindigo, 4,4', 7,7'- Tetrachlorindigo, thioindigo, 6,6'-dichloro-4,4'-dimethyl-thioindigo,
5,δ'-Dichlor-7,7'-dimethyl- thioindigo, 4,4',7,7'-Tetramethyl-thioindigo und deren Mischungen. 5, δ'-dichloro-7,7'-dimethylthioindigo, 4,4 ', 7,7'-tetramethylthioindigo and mixtures thereof.
6. Mittel nach einem der Ansprüche 1 bis 5 dadurch gekennzeichnet, dass der Küpenfarbstoff in einer Menge von 0,01 bis 10 Gewichtsprozent eingesetzt wird.6. Agent according to one of claims 1 to 5, characterized in that the vat dye is used in an amount of 0.01 to 10 percent by weight.
7. Mittel nach einem der Ansprüche 1 bis 6 dadurch gekennzeichnet, dass die kationische Verbindung ein kationisches Polymer ist.7. Composition according to one of claims 1 to 6, characterized in that the cationic compound is a cationic polymer.
8. Mittel nach Anspruch 7, dadurch gekennzeichnet, dass das kationische Polymer ausgewählt ist aus Polyquaternium-2, Polyquaternium-4, Polyquatemium-δ, Polyquaternium-6, Polyquaternium-7, Polyquaternium-10, Polyquaternium-11 , Polyquaternium-1δ, Polyquaternium-16, Polyquaternium-17, Polyquaternium-18, Polyquatemium-19, Polyquatemium-20, Polyquatemium-22, Polyquatemium-24, Polyquatemium-27, Polyquatemium-28, Polyquaternium-29, Polyquatemium-31 , Polyquaternium-3δ, Polyquaternium-36, Polyquaternium-37, Polyquaternium-39, Polyquaternium-44, Polyquaternium-46, Polyquatemium-47, Polyquaternium-δ1 , Polyquaternium-δδ, Polyquaternium-δ7, Hydroxypropylguar-hydroxypropyl- trimethylammoniumchlorid, Guar-hydroxypropyltrimethylammoniumchlorid, Quaternium-80 und deren Mischungen8. Composition according to claim 7, characterized in that the cationic polymer is selected from polyquaternium-2, polyquaternium-4, polyquaternium-δ, polyquaternium-6, polyquaternium-7, polyquaternium-10, polyquaternium-11, polyquaternium-1δ, polyquaternium -16, polyquaternium-17, polyquaternium-18, polyquaternium-19, polyquaternium-20, polyquaternium-22, polyquaternium-24, polyquaternium-27, polyquaternium-28, polyquaternium-29, polyquaternium-31, polyquaternium-3δ, polyquaternium-36 , Polyquaternium-37, Polyquaternium-39, Polyquaternium-44, Polyquaternium-46, Polyquaternium-47, Polyquaternium-δ1, Polyquaternium-δδ, Polyquaternium-δ7, Hydroxypropylguar-hydroxypropyl-trimethylammonium chloride, Guar-hydroxypropyltrimethylammonium mixtures, quaternary mixtures thereof
9. Mittel nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die kationische Verbindung in einer Menge von 0,001 bis δ Gewichtsprozent enthalten ist. 9. Composition according to one of claims 1 to 8, characterized in that the cationic compound is contained in an amount of 0.001 to δ weight percent.
10. Mittel nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass es zusätzlich Entwicklersubstanzen und/oder Kupplersubstanzen und/oder natürliche oder synthetische direktziehende Farbstoffe enthält.10. Agent according to one of claims 1 to 9, characterized in that it additionally contains developer substances and / or coupler substances and / or natural or synthetic direct dyes.
11. Verwendung von in Gegenwart von kationischen Verbindungen im stark alkalischen Medium (pH 10-13) mit im alkalischen Medium Endiole bildenden Verbindungen vorreduzierten indigoiden Küpenfarbstoffen (Leukoküpenfarbstoffen) zur Färbung von Haaren bei einem pH-Wert von 4 bis 11.11. Use of indigoid vat dyes (leuco vat dyes) pre-reduced in the presence of cationic compounds in a strongly alkaline medium (pH 10-13) with compounds forming endiols in the alkaline medium for dyeing hair at a pH of 4 to 11.
12. Verfahren zum Färben von Haaren, bei dem in Gegenwart von kationischen Verbindungen im stark alkalischen Medium (pH = 10-13) mit im alkalischen Medium Endiole bildenden Verbindungen vorreduzierte indigoide Küpenfarbstoffe bei einem physiologisch verträglichen pH-Wert (pH = 4-11) auf das Haar aufgetragen werden und nach einer Einwirkungszeit von 1 bis 60 Minuten bei 1δ bis 60 °C mit Luftsauerstoff oder einem Oxidationsmittel zu einem unlöslichen Pigment zurückoxidiert werden.12. Process for dyeing hair, in which, in the presence of cationic compounds in a strongly alkaline medium (pH = 10-13), with indigoid vat dyes pre-reduced with compounds forming endiols in the alkaline medium, at a physiologically tolerable pH value (pH = 4-11) applied to the hair and after an exposure time of 1 to 60 minutes at 1δ to 60 ° C with oxygen or an oxidizing agent back oxidized to an insoluble pigment.
13. Verfahren nach Anspruch 12, dadurch gekennzeichnet, dass das Oxidationsmittel ausgewählt ist aus Wasserstoffperoxid oder dessen Additionsverbindungen an Harnstoff, Melamin und Natriumborat, Persulfaten und deren Mischungen. 13. The method according to claim 12, characterized in that the oxidizing agent is selected from hydrogen peroxide or its addition compounds to urea, melamine and sodium borate, persulfates and mixtures thereof.
EP04821834A 2004-03-26 2004-11-24 Hair coloring agent containing indigoid vat dyes Withdrawn EP1727513A1 (en)

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DE102004014763A DE102004014763A1 (en) 2004-03-26 2004-03-26 Hair dyes with indigoid vat dyes
PCT/EP2004/013306 WO2005094763A1 (en) 2004-03-26 2004-11-24 Hair coloring agent containing indigoid vat dyes

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FR2954120B1 (en) * 2009-12-18 2012-02-24 Oreal COSMETIC COMPOSITION COMPRISING A PARTICULAR INDIGOID COMPOUND AND A PARTICULAR ORGANIC COMPOUND, AND ITS USE IN COLORING.
FR2949333B1 (en) * 2009-09-02 2013-01-04 Oreal COMPOSITION COMPRISING A HYDROPHOBIC COLOR, A MINERAL BASE AND A PARTICULAR COMPOUND (I), AND ITS USE IN COLORING
JP2013503928A (en) * 2009-09-02 2013-02-04 ロレアル Composition containing a hydrophobic dye, a specific inorganic alkaline agent and/or an organic alkaline agent, a specific compound (I) and a specific organic compound (II), and use thereof in dyeing
DE102010041974A1 (en) * 2010-10-05 2012-04-05 Henkel Ag & Co. Kgaa Nourishing plant hair color
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FR3014315B1 (en) * 2013-12-06 2017-01-27 Oreal PROCESS FOR COLORING KERATINIC MATERIALS FROM INDIGOFERE (S) PLANT POWDER (S) AND ALKALINE AGENT (S)
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DE102004014763A1 (en) 2005-10-06
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JP2007530464A (en) 2007-11-01

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