WO1992006670A1 - Hair colorant containing 1,4-bis-[(dihydroxyalkyl)amino]-anthrachinone and novel 1,4-bis-[(dihydroxyalkyl)amino)]-anthrachinones - Google Patents

Hair colorant containing 1,4-bis-[(dihydroxyalkyl)amino]-anthrachinone and novel 1,4-bis-[(dihydroxyalkyl)amino)]-anthrachinones Download PDF

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Publication number
WO1992006670A1
WO1992006670A1 PCT/EP1991/001836 EP9101836W WO9206670A1 WO 1992006670 A1 WO1992006670 A1 WO 1992006670A1 EP 9101836 W EP9101836 W EP 9101836W WO 9206670 A1 WO9206670 A1 WO 9206670A1
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WIPO (PCT)
Prior art keywords
amino
bis
hydroxyethyl
hair
dihydroxyalkyl
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Application number
PCT/EP1991/001836
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German (de)
French (fr)
Inventor
Isolde LÖWE
Thomas Clausen
Wolfgang R. Balzer
Original Assignee
Wella Aktiengesellschaft
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Publication of WO1992006670A1 publication Critical patent/WO1992006670A1/en

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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
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/35—Ketones, e.g. benzophenone
    • A61K8/355—Quinones
    • 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
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A61Q5/065—Preparations for temporary colouring the hair, e.g. direct dyes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/24—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings
    • C07C225/26—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings having amino groups bound to carbon atoms of quinone rings or of condensed ring systems containing quinone rings
    • C07C225/32—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings having amino groups bound to carbon atoms of quinone rings or of condensed ring systems containing quinone rings of condensed quinone ring systems formed by at least three rings
    • C07C225/34—Amino anthraquinones
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
    • C09B1/16—Amino-anthraquinones
    • C09B1/20—Preparation from starting materials already containing the anthracene nucleus
    • C09B1/26—Dyes with amino groups substituted by hydrocarbon radicals
    • C09B1/28—Dyes with amino groups substituted by hydrocarbon radicals substituted by alkyl, aralkyl or cyclo alkyl groups
    • C09B1/285—Dyes with no other substituents than the amino groups

Definitions

  • the present invention relates to agents for dyeing hair containing 1,4-bis- [ " (dihydroxyalkyl) aminoj-anthraquinone and new 1,4-bis- (dihydroxyalkyl) aminoj-anthraquinones.
  • dyes which are used for coloring human hair have to be harmless from a toxicological and dermatological point of view and enable coloring in the desired intensity. Furthermore, good light, permanent wave, Acid and rub fastness required. In any case, such hair coloring must remain stable over a period of at least 4 to 6 weeks without exposure to light, rubbing and chemical agents.
  • the known 1,4-bis (2'-hydroxyethyl) amino-anthraquinone (Disperse Blue 23) has sufficient water solubility, but cannot be satisfactory in terms of the toxicological properties. For example, this dye shows a mutagenic effect in the Amestest.
  • the object was therefore to provide hair colorants containing blue-coloring anthraquinone derivatives, the blue-coloring anthraquinone derivatives being said to have good water solubility in addition to good physiological compatibility.
  • the new blue-coloring anthraquinone derivatives should enable more intense blue colorations than the previously known blue-coloring anthraquinones or their commercially available mixtures such as Celliton Fast Blue FFR®.
  • R1 and R2 can be the same or different and independently of one another represent a straight-chain or branched C3- to C4-dihydroxyalkyl radical, the object is achieved in an outstanding manner.
  • the compounds of the general formula (I) are notable for good physiological tolerance and very good absorbency on the hair.
  • Hair dyeings carried out with the compounds of the general formula (I) are distinguished by a color-free shade of blue and have a significantly greater color intensity than hair dyeings which are customary with Disperse Blue 3, Disperse Blue 14 or Disperse Blue 23 or their used mixture, for example in the form of the commercial product Celliton Fast Blue FFR® (BASF AG, Ludwigshafen).
  • the shading of hair colors by using a single defined dye of the general formula (I) is easier to carry out and therefore much more advantageous than the use of mixtures such as Celliton Fast Blue FFR® or the use of several dyes of the same color.
  • the agents according to the invention the one which contains the 1,4-bis-j (2 ', 3'-dihydroxypropyl) amino-anthraquinone is preferred.
  • the dyes of the general formula (I) should be present in the agent according to the invention in a concentration of 0.01 to 1.0 percent by weight, preferably in a concentration of 0.01 to 0.4 percent by weight.
  • the hair coloring agent according to the invention relates both to an embodiment in which it is used without the addition of an oxidizing agent and to a further embodiment in which the addition of an oxidizing agent is required.
  • the former hair dye without addition of oxidizing agent is an agent which contains at least one dye of the general formula (I), or an agent which, in addition to at least one dye of the general formula (I), also contains one or more others directly contains dyes on the hair.
  • aromatic nitro dyes such as, for example, 2-amino-4-nitrophenol, 2-nitro-l, 4-diaminobenzene, 2-amino-5-nitrophenol, picraminic acid, 2-amino-5- (2'-hydroxyethyl) amino-nitrobenzene, 4- (2'-hydroxyethyl) amino-3-nitrophenol, 1- (2'-hydroxyethyl) amino-2-amino-4-nitrobenzene, 4- (2'-ureidoethyl) amino-nitrobenzene, 4- (2 ', 3'-dihydroxypropyl) amino-3-nitro-trifluoromethylbenzene, 1,4-bis-j (2'-hydroxyethyl, 2-amino-4-nitrophenol, 2-nitro-l, 4-di
  • the dyes of the general formula (I) should be present in this hair dye without addition of oxidizing agents in a concentration of about 0.01 to 1.0 percent by weight, preferably in a concentration of 0.01 to 0.4 percent by weight.
  • the total content of the dyes which are applied directly to the hair is in the range of about 0.01 to 3.0 percent by weight.
  • the preparation of the hair dye described here without the addition of oxidizing agents can be, for example, that of a solution, in particular an aqueous or aqueous-alcoholic solution. Preferred forms of preparation are furthermore those of a cream, a gel, an emulsion or that of a foam, it also being possible to spray them in a mixture with a propellant gas or by means of a pump.
  • the dyes of the general formula (I) should be present in this hair dye without adding any oxidizing agent in a concentration of about 0.01 to 1.0 percent by weight, preferably in a concentration of 0.01 to 0.4 percent by weight.
  • the total content of the dyes which are applied directly to the hair is in the range of about 0.01 to 3.0 percent by weight.
  • the pH of this colorant is in the range from 3 to 10.5, in particular at pH 7.5 to 9.5, the desired alkaline pH being set primarily with ammonia, but also with organic amines such as, for example, monoethanolamine or Triethanolamine can be made.
  • the use of the hair dye described here without the addition of an oxidizing agent is usually carried out by applying to the hair an amount sufficient for hair dyeing with which it remains in contact for about 5 to 30 minutes. It is then rinsed with water, if appropriate also with an aqueous solution of a weak organic acid, and dried.
  • a weak organic acid for example, acetic acid, citric acid, tartaric acid and the like can be used as the weak organic acid.
  • the hair dye described above without the addition of an oxidizing agent can be in the form of a hair dye with additional hair fixation, which contains at least one polymer or natural polymer that is commonly used in cosmetics. Such agents are generally referred to as tinting or color strengthening agents.
  • polymers known for this purpose in cosmetics are, for example, polyvinyl pyrrolidone, polyvinyl acetate, polyvinyl alcohol or polyacrylic compounds such as polyacrylic acid or polymethacrylic acid, basic polymers of the esters of polyacrylic acid or polymethracrylic acid with amino alcohols or their salts or quaternization products, polyacrylonitrile, Polyvinyl lactams and copolymers of these compounds, such as polyvinylpyrrolidone-vinyl acetate and the like, are mentioned.
  • Natural polymers such as chitosan (deacetylated chitin) or chitosan derivatives, can also be used for the purpose mentioned.
  • the polymers and natural polymers are contained in the hair colorant described above without any oxidizing agent in the amount of about 1 to 5 percent by weight customary for such agents.
  • the pH of the agent is in the range of about 6.0 to 9.0.
  • This hair dye with additional setting is used in a known and customary manner by moistening the hair with the setting agent, setting (inserting) the hair for the hairstyle and subsequent drying.
  • the hair colorant described above can, if required, without the addition of an oxidizing agent, further additives which are customary for hair coloring agents, such as, for example, care substances, wetting agents, thickeners, plasticizers, preservatives and perfume oils, and also other customary additives listed below for hair coloring agents with addition of an oxidizing agent (oxidizing hair dye) Additives included.
  • the subject matter of the present invention also includes a hair colorant in which the addition of an oxidizing agent is necessary (oxidation hair colorant).
  • it additionally contains at least one developer substance-coupler substance combination which requires oxidative development.
  • the oxidation hair dye according to the invention can contain at least one dye which is applied directly to the hair and which should be selected from: 2-amino-4-nitrophenol, 2-nitro-l, 4-diamino-benzene, 2-amino-5-nitrophenol, 2- Amino-4,6-dinitrophenol, 2-amino-5- (2'-hydroxyethyl) amino-3-nitrobenzene, 4- (2'-hydroxyethyl) amino-3-nitrotoluene, 4- (2'-ureido-ethyl) amino-nitrobenzene, Basic Violet 14 (CI 42 510), Basic Violet 2 (CI 42 520), Acid Brown 4 (CI 14 805), 1,4-diaminoanthraquinone and 1,4,5,8-tetra-aminoanthraquinone.
  • 2-amino-4-nitrophenol 2-nitro-l
  • 4-diamino-benzene 2-amino-5-nitrophenol
  • 2- Amino-4,6-dinitrophenol 2-a
  • the oxidation hair dye according to the invention can also contain self-coupling dye precursors, such as 2-amino-5-methylphenol and 6-amino-2-methylphenol.
  • aromatic p-diamines and p-aminophenols such as 1,4-diamino benzene, 2,5-diaminotoluene, 2,5-diaminobenzyl alcohol, 2- (2'- Hydroxyethyl) -1,4-diaminobenzene, 4-aminophenol, 4-amino-3-methylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-ethoxymethylphenol and tetraaminopyrimidine or similar compounds.
  • aromatic p-diamines and p-aminophenols such as 1,4-diamino benzene, 2,5-diaminotoluene, 2,5-diaminobenzyl alcohol, 2- (2'- Hydroxyethyl) -1,4-diaminobenzene, 4-aminophenol, 4-amino-3-methylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-
  • the oxidation hair dye according to the invention should contain the developer and coupler substances in an amount of 0.01 to 5 percent by weight, preferably in an amount of 0.1 to 3 percent by weight.
  • the coupler and developer substances mentioned can in each case be present individually or in a mixture with one another in the hair colorants according to the invention.
  • the developer substances are generally used in approximately equimolar amounts, based on the coupler substances. However, it is not a disadvantage if the developer substance is present in a certain excess or deficit in this regard.
  • the coupler and developer substances as well as the other color components can also be used in the form of the physiologically compatible acid addition salts, such as, for example, as hydrochloride or sulfate or - if they have aromatic hydroxyl groups - in the form of the salts with bases, for example as alkali phenolates.
  • physiologically compatible acid addition salts such as, for example, as hydrochloride or sulfate or - if they have aromatic hydroxyl groups - in the form of the salts with bases, for example as alkali phenolates.
  • the total amount of the developer substance-coupler substance combination contained in the oxidation hair colorant described here should be about 0.1 to 5.0 percent by weight, preferably 0.5 to 4.0 percent by weight.
  • the dyes of the general formula (I) should be present in the oxidation hair dye described above in a concentration of 0.01 to 1.0 percent by weight, preferably in a concentration of 0.01 to 0.4 percent by weight.
  • the cosmetic hair dye can also contain other cosmetic additives, for example antioxidants such as ascorbic acid, thioglycolic acid or sodium sulfite, perfume oils, complexing agents, wetting agents, emulsifiers, thickeners, care agents and others.
  • the oxidation hair colorants according to the invention can react weakly acidic, neutral or alkaline.
  • they have a pH in the alkaline range between 8.0 and 11.5, the setting preferably being made with ammonia.
  • organic amines for example monoethanolamine and triethanolamine, or else inorganic bases such as sodium hydroxide and potassium hydroxide can also be used.
  • the main oxidizing agents used to develop hair color are hydrogen peroxide and its addition compounds to urea, melanin or sodium borate in the form of 3 to 12%, preferably 6%, aqueous solutions.
  • the weight ratio between the hair dye and the oxidizing agent is 5: 1 to 1: 2, but preferably 1: 1. Larger amounts of oxidizing agent are used above all in the case of higher dye concentrations in the hair dye or when more bleaching of the hair is intended at the same time.
  • the form of preparation of the oxidizing hair dye can be the same as that of the previously described hair dye without the addition of an oxidizing agent, for example that of an aqueous or aqueous-alcoholic solution.
  • the preparation form is preferably that of a cream, a gel or that of an emulsion.
  • Usual additives in solutions, creams, emulsions or gels are, for example, solvents such as water, lower aliphatic alcohols, for example ethanol, propanol and isopropanol or glycols such as glycerol and 1,2-propylene glycol, furthermore wetting agents or emulsifiers from the classes of the anionic, cationic, amphoteric or nonionic surfactants such as fatty alcohol sulfates, ethoxylated fatty alcohol sulfates, alkylsulfonates, alkylbenzenesulfonates, alkyltrimethylammonium salts, alkylbetaines, oxyethylated fatty alcohols, oxyethylated nonylphenols, fatty acid alkanolamides, ethoxylated fatty acid ester, further Ver ⁇ thicker such as higher fatty alcohols, starch or cellulose derivatives, petroleum jelly, paraffin oil and fatty acids as well as
  • the components mentioned are used in the amounts customary for such purposes, for example the wetting agents and emulsifiers in concentrations of about 0.5 to 30 percent by weight, the thickeners in an amount of about 0.1 to 25 percent by weight and the care substances in a concentration of about 0.1 to 5.0 weight percent.
  • the oxidizing hair dye described above is mixed with an oxidizing agent immediately before use and an amount sufficient for the hair dyeing treatment, depending on the fullness of the hair, is generally about 60 to 200 g of this mixture on the hair.
  • the mixture is allowed to act on the hair at 15 to 50 ° C for about 10 to 45 minutes, preferably 30 minutes, then the hair is rinsed with water and dried. If necessary, this rinse is washed with a shampoo and possibly rinsed with a weak organic acid, such as citric acid or tartaric acid. The hair is then dried.
  • a weak organic acid such as citric acid or tartaric acid.
  • oxidation hair colorants according to the invention containing at least one 1,4-bis- (dihydroxyalkyl) amino] anthraquinone of the general formula (I) lead to hair colorations with excellent fastness properties and high color intensity, never in the hair colorants described here and compounds of the formula (I) which do not contain any oxidizing agent are toxicologically and dermatologically harmless, readily water-soluble and stain alone in a clear shade of blue.
  • the compounds of the general formula (I) are particularly suitable for shading intense black shades.
  • This application also relates to the 1,4-bis j (dihydroxyalkyl) amino] anthraquinone of the general formula (II)
  • R1 and R2 can be the same or different and independently of one another represent a straight-chain or branched C3- to C4-dihydroxyalkyl radical.
  • An example of the new 1,4-bis- (dihydroxyalkyl) aminoj -anthraquinones of the general formula (II) is 1,4-bis- (2 ', 3'-dihydroxypropyl) amino J-anthraquinone.
  • the new 1,4-bis- ((dihydroxyalkyl) aminoj-anthraquinones can be described according to, for example, in the textbook NN Woroshzow, Basics of the Synthesis of Intermediates and Dyes, Akademie Verlag, Berlin (1966), pages 481-482 to produce the described process, in which the industrially available 1,4-dihydroxyanthraquinone is first reduced to 1,4,5,8-tetrahydroanthraquinone in a alkaline aqueous solution using a conventional reducing agent, for example sodium dithionite
  • a conventional reducing agent for example sodium dithionite
  • the 1,4,5,8-tetrahydroanthraquinone is then treated under a protective gas atmosphere, for example under nitrogen, with a implemented aqueous solution of the corresponding amino-alkyldiol in the heat.
  • Oxygen is then passed into the reaction mixture to reoxidize the quinone system, causing the 1,4-bis- (d
  • the compounds of the general formula (II) are intensely blue-coloring anthraquinone dyes which, in addition to good water solubility, are also notable for their good physiological tolerance. Because of their properties, the compounds of the formula (II) are valuable blue-coloring hair dyes.
  • 1,4-dihydroxyanthraquinone 50 g are dissolved in 1,000 ml of 5 percent sodium hydroxide solution and reduced with 500 ml of 20 percent sodium dithionite solution. After slower 75.8 g of 3-aminopropane-1,2-diol in 30 ml of water are added and the mixture is heated to 100 ° C. under nitrogen for 8 hours. Then oxygen is introduced for 3 hours. The 1,4-bis ((2 ', 3'-dihydroxypropyl) aminoj-anthraquinone is then filtered off and washed with acetone. 38 g of deep blue crystals, corresponding to a yield of 47% of theory, with a decomposition melting point of 220 ° C obtained.
  • Bleached natural hair is treated with the above liquid hair dye at room temperature for 20 minutes. After rinsing the hair with water and then drying it, the hair is colored in a blonde-ash color.
  • Lauryl alcohol diglycol ether sulfate sodium salt 28 percent aqueous solution of methyl p-hydroxybenzoate ammonia, 25 percent aqueous solution of water
  • Example C Color fastener
  • White human hair is inserted with the color fixer solution and dried.
  • the hair is colored and set in a fashionable silver tone.
  • 50 g of the above oxidation hair dye in gel form are mixed with 50 g of a 6% hydrogen peroxide solution and applied to white human hair. After an exposure time of 30 minutes at 40 degrees Celsius, the hair is rinsed with water, if necessary shampooed and dried. The hair is dyed in a natural medium blonde shade with a slight ash effect.

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Abstract

The object of the present invention are hair colorants containing at least one 1,4-bis-[(dihydroxyalkyl)amino]-anthrachinone of the general formula (I) in which R?1 and R?2 may be the same or different and mutually independently be a straight-chained or branched C3?- to C6?-dihydroxyalkyl radical and the new 1,4-bis-[(dihydroxyalkyl)amino]-anthrachinones of the general formula (II). The compounds of the general formula (II) are well tolerated physiologically, dissolve readily in water and give a pale blue hue with great depth of colour. Their properties make them invaluable hair colorants which are also especially suitable for shading black hair colorants.

Description

B e s c h r e i b u n g Description
Mittel zum Färben von Haaren mit einem Gehalt an 1,4- Bis- ((dihydroxyalkyl)aminoj-anthrachinon sowie neue 1,4-Bis- |(dihydroxyalkyl)aminoj-anthrachinoneHair dye containing 1,4-bis- ((dihydroxyalkyl) aminoj-anthraquinone and new 1,4-bis- | (dihydroxyalkyl) aminoj-anthraquinones
Gegenstand der vorliegenden Erfindung sind Mittel zum Färben von Haaren mit einem Gehalt an 1,4-Bis- ["(dihy¬ droxyalkyl)aminoj-anthrachinon sowie neue 1,4-Bis- |(dihydroxyalkyl)aminoj-anthrachinone.The present invention relates to agents for dyeing hair containing 1,4-bis- [ " (dihydroxyalkyl) aminoj-anthraquinone and new 1,4-bis- (dihydroxyalkyl) aminoj-anthraquinones.
Zur Erzielung sehr dunkler, insbesondere schwarzer, Nuancen bei der Färbung von Haaren, ist es notwendig eine Reihe verschiedener Farbstoffe einzusetzen, um das einfallende Licht vollständig über den gesamten Bereich des sichtbaren Spektrums zu absorbieren. Bei Verwendung von Nitrofarbstoffen ist dies nur unvollständig mög¬ lich, da die gebräuchlichen "blauen" Nitrofarbstoffe immer einen kleinen Teil des roten Lichts reflektieren und somit zu wärmeren Farbnuancen führen. Bestimmte Anthrachinonfarbstoffe absorbieren den roten Bereich des sichtbaren Lichtes völlig, führen - alleine ausge¬ färbt - zu reinen, blauen Farbtönen und sind damit eine wichtige Komponente für die Nuancierung schwarzer Farb¬ töne, insbesondere in direktziehenden, nicht oxidativen Haarfarben.To achieve very dark, especially black, shades in the coloring of hair, it is necessary to use a number of different dyes in order to completely absorb the incident light over the entire range of the visible spectrum. When using nitro dyes, this is only incompletely possible, since the customary "blue" nitro dyes always reflect a small part of the red light and thus lead to warmer color shades. Certain anthraquinone dyes completely absorb the red area of visible light, lead - when colored alone - to pure, blue shades and are therefore an important component for the nuance of black shades, especially in direct, non-oxidative hair colors.
An Farbstoffe, die zur Färbung menschlicher Haare Ver¬ wendung finden, sind besondere Anforderungen gestellt. So müssen sie in toxikologischer und dermatologischer Hinsicht unbedenklich sein und Färbungen in der ge¬ wünschten Intensität ermöglichen. Ferner wird für die erzielten Haarfärbungen eine gute Licht-, Dauerwell-, Säure- und Reibechtheit gefordert. Auf jeden Fall aber müssen solche Haarfärbungen ohne Einwirkung von Licht, Reibung und chemischen Mitteln über einen Zeitraum von mindestens 4 bis 6 Wochen stabil bleiben.There are special requirements for dyes which are used for coloring human hair. For example, they have to be harmless from a toxicological and dermatological point of view and enable coloring in the desired intensity. Furthermore, good light, permanent wave, Acid and rub fastness required. In any case, such hair coloring must remain stable over a period of at least 4 to 6 weeks without exposure to light, rubbing and chemical agents.
Die bisher bekannten blaufärbenden Anthrachinonfarb- stoffe vermögen diese Anforderungen nur unzureichend zu erfüllen.The previously known blue-coloring anthraquinone dyes are unable to meet these requirements sufficiently.
Bei dem aus der GB-PS 137 9991 bekannten 1,4-Bis- (methylamino)-anthrachinon (Disperse Blue 14) sowie bei dem in der JP-OS 1-180 816 beschriebenen 1,4-Bis- (ethylamino)-anthrachinon (Sudan Blue) handelt es sich um sehr schwer lösliche Farbstoffe, die nur ein geringes Aufziehvermögen auf menschliches Haar besitzen und somit nur zu Anfärbungen geringer Intensität führen.In the 1,4-bis (methylamino) anthraquinone (Disperse Blue 14) known from GB-PS 137 9991 and in the 1,4-bis (ethylamino) anthraquinone described in JP-OS 1-180 816 (Sudan Blue) are very poorly soluble dyes, which have only a low absorption capacity on human hair and therefore only lead to stains of low intensity.
Eine etwas größere Löslichkeit besitzen das in der DE-PS 35 34 885 beschriebene l-Methylamino-4-(2'-hy- droxyethyl)amino-anthrachinon (Disperse Blue 3) sowie das in der DE-OS 16 19 616 beschriebene 1-Methylamino- 4-(3'-aminopropyl)amino-anthrachinon; aber auch mit diesen Farbstoffen werden nur Ausfärbungen geringer Intensität erreicht.The l-methylamino-4- (2'-hydroxyethyl) aminoanthraquinone (Disperse Blue 3) described in DE-PS 35 34 885 and the 1- 1- 19 described in DE-OS 16 19 616 have a somewhat greater solubility. Methylamino-4- (3'-aminopropyl) amino-anthraquinone; but even with these dyes, only low-intensity colorations are achieved.
Zur Erhöhung der Farbintensität von Faser-Anfärbungen werden in der technischen Anwendung oft Gemische aus unterschiedlichen Farbstoffen des gleichen Typs einge¬ setzt. So beschreibt zum Beispiel K. Venkataraman in The Chemistry of Synthetic Dyes, Academic Press, New York, Vol. II, S. 809 (1952), daß das Handelsprodukt Celliton Fast Blue FFR® der BASF AG, Ludwigshaften aus den Einzelkomponenten Disperse Blue 3, Disperse Blue 14 und Disperse 23 besteht und deutlich farbintensivere Färbungen erzeugt als sie bei Verwendung der reinen Farbstoffe erreicht werden können. Gut wasserlösliche Farbstoffe lassen sich durch Einfüh¬ rung geladener Gruppen erhalten, wie sie zum Beispiel die quaternisierten, in der DE-OS 17 94 384 beziehungs¬ weise DE-OS 17 94 385 beschriebenen 1,4-Diaminoanthra- chinon-Derivate darstellen. Diese kationischen Farb¬ stoffe führen allerdings zu ungleichmäßigen Anfärbung- en, da sich diese Farbstoffe bevorzugt an geschädigte Stellen des Haares anlagern.To increase the color intensity of fiber dyeings, mixtures of different dyes of the same type are often used in industrial applications. For example, K. Venkataraman in The Chemistry of Synthetic Dyes, Academic Press, New York, Vol. II, p. 809 (1952) describes that the commercial product Celliton Fast Blue FFR® from BASF AG, Ludwigshaft, consists of the individual components Disperse Blue 3 , Disperse Blue 14 and Disperse 23 exists and produces significantly more color intensive stains than can be achieved using the pure dyes. Highly water-soluble dyes can be obtained by introducing charged groups, such as the quaternized 1,4-diaminoanthraquinone derivatives described in DE-OS 17 94 384 and DE-OS 17 94 385, for example. However, these cationic dyes lead to uneven coloring, since these dyes preferentially attach to damaged areas of the hair.
Das bekannte 1,4-Bis- (2'-hydroxyethyl)aminoj -anthra- chinon (Disperse Blue 23) besitzt zwar eine ausreichen¬ de Wasserlöslichkeit, kann jedoch in bezug auf die to¬ xikologischen Eigenschaften nicht befriedigen. So zeigt dieser Farbstoff zum Beispiel im Amestest eine mutagene Wirkung.The known 1,4-bis (2'-hydroxyethyl) amino-anthraquinone (Disperse Blue 23) has sufficient water solubility, but cannot be satisfactory in terms of the toxicological properties. For example, this dye shows a mutagenic effect in the Amestest.
Es bestand daher die Aufgabe, Haarfärbemittel mit einem Gehalt an blaufärbenden Anthrachinonderivaten zur Verfü¬ gung zu stellen, wobei die blaufärbenden Anthrachinon- derivate, neben einer guten physiologischen Verträg¬ lichkeit, eine gute Wasserlöslichkeit aufweisen sollen. Zudem sollen die neuen blaufärbenden Anthrachinonderi¬ vaten farbintensivere blaue Färbungen ermöglichen als die bisher bekannten blaufärbenden Anthrachinone oder deren handelsübliche Gemische wie Celliton Fast Blue FFR®.The object was therefore to provide hair colorants containing blue-coloring anthraquinone derivatives, the blue-coloring anthraquinone derivatives being said to have good water solubility in addition to good physiological compatibility. In addition, the new blue-coloring anthraquinone derivatives should enable more intense blue colorations than the previously known blue-coloring anthraquinones or their commercially available mixtures such as Celliton Fast Blue FFR®.
Es wurde nun gefunden, daß durch ein Mittel zur Färbung von Haaren mit einem Gehalt an für Haarfärbemittel üblichen Zusätzen, welches mindestens ein 1,4-Bis- |(dihydroxyalkyl)amino j-anthrachinon der allgemeinen Formel (I) O HN'It has now been found that an agent for dyeing hair containing additives customary for hair dyes which contains at least one 1,4-bis- (dihydroxyalkyl) amino j-anthraquinone of the general formula (I) O HN '
Figure imgf000006_0001
Figure imgf000006_0001
wobei Rl und R2 gleich oder verschieden sein können und unabhängig voneinander einen geradkettigen oder ver¬ zweigten C3- bis C4-Dihydroxyalkylrest bedeuten, die gestellte Aufgabe in hervorragender Weise gelöst wird.where R1 and R2 can be the same or different and independently of one another represent a straight-chain or branched C3- to C4-dihydroxyalkyl radical, the object is achieved in an outstanding manner.
Die Verbindungen der allgemeinen Formel (I) zeichnen sich durch eine gute physiologische Verträglichkeit und ein sehr gutes Aufziehvermögen auf das Haar aus. Mit den Verbindungen der allgemeinen Formel (I) ausge¬ führte Haarfärbungen zeichnen sich durch einen farbrei¬ nen Blauton aus und weisen eine deutlich größere Farb¬ intensität auf als Haarfärbungen, die mit Disperse Blue 3, Disperse Blue 14 oder Disperse Blue 23 oder deren üblicherweise verwendeten Gemisch, zum Beispiel in Form des Handelsproduktes Celliton Fast Blue FFR® (BASF AG, Ludwigshafen) , ausgeführt wurden.The compounds of the general formula (I) are notable for good physiological tolerance and very good absorbency on the hair. Hair dyeings carried out with the compounds of the general formula (I) are distinguished by a color-free shade of blue and have a significantly greater color intensity than hair dyeings which are customary with Disperse Blue 3, Disperse Blue 14 or Disperse Blue 23 or their used mixture, for example in the form of the commercial product Celliton Fast Blue FFR® (BASF AG, Ludwigshafen).
Die Nuancierung von Haarfarben durch Verwendung eines einzelnen definierten Farbstoffes der allgemeinen Formel (I) ist einfacher durchzuführen und daher wesentlich vorteilhafter als die Verwendung von Gemischen wie Celliton Fast Blue FFR® oder die Verwendunσ mehrerer Farbstoffe des gleichen Farbtons. Von den erfindungsgemäßen Mitteln ist jenes bevorzugt, welches das 1,4-Bis- j(2' ,3'-dihydroxypropyl)amino - anthrachinon enthält. Die Farbstoffe der allgemeinen Formel (I) sollen in dem erfindungsgemäßen Mittel in einer Konzentration von 0,01 bis 1,0 Gewichtsprozent, vorzugsweise in einer Konzentration von 0,01 bis 0,4 Gewichtsprozent, enthalten sein.The shading of hair colors by using a single defined dye of the general formula (I) is easier to carry out and therefore much more advantageous than the use of mixtures such as Celliton Fast Blue FFR® or the use of several dyes of the same color. Of the agents according to the invention, the one which contains the 1,4-bis-j (2 ', 3'-dihydroxypropyl) amino-anthraquinone is preferred. The dyes of the general formula (I) should be present in the agent according to the invention in a concentration of 0.01 to 1.0 percent by weight, preferably in a concentration of 0.01 to 0.4 percent by weight.
Das erfindungsgemäße Mittel zur Färbung von Haaren betrifft sowohl eine Ausführungsform, bei der es ohne Zugabe eines Oxidationsmittels angewendet wird, als auch eine weitere Ausführungsform, bei der die Zugabe eines Oxidationsmittels erforderlich ist.The hair coloring agent according to the invention relates both to an embodiment in which it is used without the addition of an oxidizing agent and to a further embodiment in which the addition of an oxidizing agent is required.
Bei dem ersteren Haarfärbemittel ohne Oxidationsmittel- zugabe handelt es sich um ein Mittel, das mindestens einen Farbstoff der allgemeinen Formel (I) enthält, oder um ein Mittel, das zusätzlich zu mindestens einem Farbstoff der allgemeinen Formel (I) noch einen oder mehrere weitere direkt auf das Haar aufziehende Farb¬ stoffe enthält. Von diesen direkt auf das Haar aufziehenden Farbstoffen seien beispielsweise die folgenden erwähnt: aromatische Nitrofarbstoffe, wie zum Beispiel 2-Amino-4-nitrophenol, 2-Nitro-l,4-diami- nobenzol, 2-Amino-5-nitrophenol, Pikraminsäure, 2-Amino-5-(2'-hydroxyethyl)amino-nitrobenzol, 4-(2'- Hydroxyethyl)amino-3-nitrophenol, 1-(2'-Hydroxy¬ ethyl)amino-2-amino-4-nitrobenzol, 4-(2'-Ureidoethyl)- amino-nitrobenzol, 4-(2' ,3'-Dihydroxypropyl)amino-3- nitro-trifluormethylbenzol, 1,4-Bis- j(2'-hydroxyethyl)- aminol-4-N-ethyl-2-nitrobenzol, 4-(2'-Hydroxyethyl)- amino-3-nitro-toluol, 2,5-Bis- j(2'-hydroxyethyl)amino j- nitrobenzol, 2-(2'-Hydroxyethyl)amino-4,6-dinitrophe- nol, l-Amino-4-(2' ,3'-dihydroxypropyl)amino-2-nitro- 5-chlorbenzol, 4- JBis-(2'-hydroxyethyl)amino]-l-(2'-hy¬ droxyethyl)amino-2-nitrobenzol, l-Amino-2-nitro-4-[bis- (2'-hydroxyethyl)aminoj-benzol; Triphenylmethanfarb¬ stoffe, wie zum Beispiel Basic Violet 1 (C.I. 42 535), Basic Violet 14 (C.I. 42 510), Basic Violet 2 (C.I. 42 520); Azofarbstoffe, wie beispielweise Acid Brown 4 (C.I. 14 805); Anthrachinonfarbstoffe, wie zum Beispiel Disperse Violet 4 (C.I. 61 105), 1,4,5,8-Tetraamino- anthrachinon (C.I. 64 500) und 1,4-Diaminoanthrachinon, wobei die Farbstoffe dieser Klassen je nach Art ihrer Substituenten sauren, nicht-ionogenen oder basischen Charakter haben können. Weitere geeignete, direkt auf das Haar aufziehende Farbstoffe sind beispielsweise in dem Buch von J. C. Johnson, "Hair Dyes", Noyes Data Corp., Park-Ridge (USA) (1973), Seiten 3-91 und 113-139 (ISBN: 0-8155-0477-2) beschrieben.The former hair dye without addition of oxidizing agent is an agent which contains at least one dye of the general formula (I), or an agent which, in addition to at least one dye of the general formula (I), also contains one or more others directly contains dyes on the hair. Of these dyes which are directly absorbed onto the hair, the following may be mentioned, for example: aromatic nitro dyes, such as, for example, 2-amino-4-nitrophenol, 2-nitro-l, 4-diaminobenzene, 2-amino-5-nitrophenol, picraminic acid, 2-amino-5- (2'-hydroxyethyl) amino-nitrobenzene, 4- (2'-hydroxyethyl) amino-3-nitrophenol, 1- (2'-hydroxyethyl) amino-2-amino-4-nitrobenzene, 4- (2'-ureidoethyl) amino-nitrobenzene, 4- (2 ', 3'-dihydroxypropyl) amino-3-nitro-trifluoromethylbenzene, 1,4-bis-j (2'-hydroxyethyl) aminol-4- N-ethyl-2-nitrobenzene, 4- (2'-hydroxyethyl) amino-3-nitro-toluene, 2,5-bis-j (2'-hydroxyethyl) amino j-nitrobenzene, 2- (2'-hydroxyethyl ) amino-4,6-dinitrophenol, l-amino-4- (2 ', 3'-dihydroxypropyl) amino-2-nitro-5-chlorobenzene, 4-JBis- (2'-hydroxyethyl) amino] -l - (2'-hydroxyethyl) amino-2-nitrobenzene, l-amino-2-nitro-4- [bis- (2'-hydroxyethyl) aminoj-benzene; Triphenylmethane dyes, such as, for example, Basic Violet 1 (CI 42 535), Basic Violet 14 (CI 42 510), Basic Violet 2 (CI 42 520); Azo dyes such as Acid Brown 4 (CI 14 805); Anthraquinone dyes, such as, for example, Disperse Violet 4 (CI 61 105), 1,4,5,8-tetraaminoanthraquinone (CI 64 500) and 1,4-diaminoanthraquinone, the dyes of these classes not being acidic, depending on the nature of their substituents can have an ionic or basic character. Further suitable hair-absorbing dyes are described, for example, in the book by JC Johnson, "Hair Dyes", Noyes Data Corp., Park-Ridge (USA) (1973), pages 3-91 and 113-139 (ISBN: 0 -8155-0477-2).
Die Farbstoffe der allgemeinen Formel (I) sollen in diesem Haarfärbemittel ohne Oxidationsmittelzugäbe in einer Konzentration von etwa 0,01 bis 1,0 Gewichtspro¬ zent, vorzugsweise in einer Konzentration von 0,01 bis 0,4 Gewichtsprozent, enthalten sein. Der Gesamtgehalt an den direkt auf das Haar aufziehenden Farbstoffen liegt in den Grenzen von etwa 0,01 bis 3,0 Gewichtspro¬ zent.The dyes of the general formula (I) should be present in this hair dye without addition of oxidizing agents in a concentration of about 0.01 to 1.0 percent by weight, preferably in a concentration of 0.01 to 0.4 percent by weight. The total content of the dyes which are applied directly to the hair is in the range of about 0.01 to 3.0 percent by weight.
Die Zubereitungsform des hier beschriebenen Haarfärbe¬ mittels ohne Oxidationsmittelzugäbe kann beispielsweise die einer Lösung, insbesondere einer wäßrigen oder wäßrig-alkoholischen Lösung, sein. Bevorzugte Zuberei¬ tungsformen sind weiterhin die einer Creme, eines Gels, einer Emulsion oder die eines Schaumes, wobei sie auch im Gemisch mit einem Treibgas oder mittels einer Pumpe versprüht werden können. Die Farbstoffe der allgemeinen Formel (I) sollen in diesem Haarfärbemittel ohne Oxidationsmittelzugabe in einer Konzentration von etwa 0,01 bis 1,0 Gewichtspro¬ zent, vorzugsweise in einer Konzentration von 0,01 bis 0,4 Gewichtsprozent, enthalten sein. Der Gesamtgehalt an den direkt auf das Haar aufziehenden Farbstoffen liegt in den Grenzen von etwa 0,01 bis 3,0 Gewichtspro¬ zent.The preparation of the hair dye described here without the addition of oxidizing agents can be, for example, that of a solution, in particular an aqueous or aqueous-alcoholic solution. Preferred forms of preparation are furthermore those of a cream, a gel, an emulsion or that of a foam, it also being possible to spray them in a mixture with a propellant gas or by means of a pump. The dyes of the general formula (I) should be present in this hair dye without adding any oxidizing agent in a concentration of about 0.01 to 1.0 percent by weight, preferably in a concentration of 0.01 to 0.4 percent by weight. The total content of the dyes which are applied directly to the hair is in the range of about 0.01 to 3.0 percent by weight.
Der pH-Wert dieses Färbemittels liegt im Bereich von 3 bis 10,5, insbesondere bei pH 7,5 bis 9,5, wobei die Einstellung des gewünschten alkalischen pH-Wertes hauptsächlich mit Ammoniak erfolgt, jedoch auch mit organischen Aminen wie beispielsweise Monoethanolamin oder Triethanolamin vorgenommen werden kann.The pH of this colorant is in the range from 3 to 10.5, in particular at pH 7.5 to 9.5, the desired alkaline pH being set primarily with ammonia, but also with organic amines such as, for example, monoethanolamine or Triethanolamine can be made.
Die Verwendung des hier beschriebenen Haarfärbemittels ohne Oxidationsmittelzugabe erfolgt üblicherweise durch Aufbringen einer für die Haarfärbung ausreichenden Menge des Mittels auf die Haare, mit denen es etwa 5 bis 30 Minuten lang, in Berührung bleibt. Anschließend wird mit Wasser, gegebenenfalls noch mit wäßriger Lösung einer schwachen organischen Säure, gespült und getrock¬ net. Als schwache organische Säure können beispiels¬ weise Essigsäure, Zitronensäure, Weinsäure und ähnliche Verwendung finden.The use of the hair dye described here without the addition of an oxidizing agent is usually carried out by applying to the hair an amount sufficient for hair dyeing with which it remains in contact for about 5 to 30 minutes. It is then rinsed with water, if appropriate also with an aqueous solution of a weak organic acid, and dried. For example, acetic acid, citric acid, tartaric acid and the like can be used as the weak organic acid.
Das vorstehend beschriebene Haarfärbemittel ohne Oxi¬ dationsmittelzugabe kann in Form eines Haarfärbemittels mit zusätzlicher Haarfestigung vorliegen, das minde¬ stens ein in der Kosmetik üblicherweise verwendetes Polymerisat oder natürliches Polymer enthält. Solche Mittel werden im allgemeinen als Tönungsfestiger oder Farbfestiger bezeichnet. Von den für diesen Zweck in der Kosmetik bekannten Polymerisaten seien beispielsweise Polyvinylpyrrolidon, Polyvinylacetat, Polyvinylalkohol oder Polyacrylverbin- dungen wie Polyacrylsäure beziehungsweise Polymeth- acrylsäure, basische Polymerisate der Ester der Polyacrylsäure oder Polymethracylsäure mit Aminoalko- holen beziehungsweise deren Salze oder Quater- nisierungsprodukte, Polyacrylnitril, Polyvinyllactame sowie Copolymerisate aus diesen Verbindungen wie zum Beispiel Polyvinylpyrrolidon-Vinylacetat und der¬ gleichen erwähnt.The hair dye described above without the addition of an oxidizing agent can be in the form of a hair dye with additional hair fixation, which contains at least one polymer or natural polymer that is commonly used in cosmetics. Such agents are generally referred to as tinting or color strengthening agents. Of the polymers known for this purpose in cosmetics are, for example, polyvinyl pyrrolidone, polyvinyl acetate, polyvinyl alcohol or polyacrylic compounds such as polyacrylic acid or polymethacrylic acid, basic polymers of the esters of polyacrylic acid or polymethracrylic acid with amino alcohols or their salts or quaternization products, polyacrylonitrile, Polyvinyl lactams and copolymers of these compounds, such as polyvinylpyrrolidone-vinyl acetate and the like, are mentioned.
Auch natürliche Polymere, wie Chitosan (entacetyliertes Chitin) oder Chitosanderivate, können für den genannten Zweck eingesetzt werden.Natural polymers, such as chitosan (deacetylated chitin) or chitosan derivatives, can also be used for the purpose mentioned.
Die Polymerisate und natürlichen Polymere sind in dem zuvor beschriebenen Haarfärbemittel ohne Oxidations- mittelangabe in der für solche Mittel üblichen Menge von etwa 1 bis 5 Gewichtsprozent enthalten. Der pH-Wert des Mittels liegt im Bereich von etwa 6,0 bis 9,0. Die Anwendung dieses Haarfärbemittels mit zusätzlicher Festigung erfolgt in bekannter und üblicher Weise durch Befeuchten des Haares mit dem Festiger, Festlegen (Ein¬ legen) des Haares zur Frisur und anschließende Trock¬ nung.The polymers and natural polymers are contained in the hair colorant described above without any oxidizing agent in the amount of about 1 to 5 percent by weight customary for such agents. The pH of the agent is in the range of about 6.0 to 9.0. This hair dye with additional setting is used in a known and customary manner by moistening the hair with the setting agent, setting (inserting) the hair for the hairstyle and subsequent drying.
Selbstverständlich kann das vorstehend beschriebene Haarfärbemittel ohne Oxidationsmittelzugabe gegebenen¬ falls weitere, für Haarfärbemittel übliche Zusätze, wie zum Beispiel Pflegestoffe, Netzmittel, Verdicker, Weichmacher, Konservierungsstoffe und Parfümöle sowie auch andere, nachstehend für Haarfärbemittel mit Oxi¬ dationsmittelzugabe (Oxidationshaarfärbemittel) aufge¬ führte übliche Zusätze enthalten. Zum Gegenstand der vorliegenden Erfindung gehört auch, wie eingangs erwähnt, ein Haarfärbemittel, bei dem die Zugabe eines Oxidationsmittels erforderlich ist (Oxida- tionshaarfärbemittel) . Es enthält außer den Farbstoffen gemäß der angegebenen Formel (I) zusätzlich noch min¬ destens eine Entwicklersubstanz-Kupplersubstanz- Kombination, die einer oxidativen Entwicklung bedarf.Of course, the hair colorant described above can, if required, without the addition of an oxidizing agent, further additives which are customary for hair coloring agents, such as, for example, care substances, wetting agents, thickeners, plasticizers, preservatives and perfume oils, and also other customary additives listed below for hair coloring agents with addition of an oxidizing agent (oxidizing hair dye) Additives included. As mentioned at the beginning, the subject matter of the present invention also includes a hair colorant in which the addition of an oxidizing agent is necessary (oxidation hair colorant). In addition to the dyes according to the formula (I) indicated, it additionally contains at least one developer substance-coupler substance combination which requires oxidative development.
Das erfindungsgemäße Oxidationshaarfärbemittel kann mindestens einen direkt auf das Haar aufziehenden Farbstoff enthalten, der ausgewählt sein soll aus: 2-Amino-4-nitrophenol, 2-Nitro-l,4-diamino-benzol, 2-Amino-5-nitrophenol, 2-Amino-4,6-dinitrophenol, 2-Amino-5-(2'-hydroxyethyl)amino-3-nitrobenzol, 4-(2'-Hydroxyethyl)amino-3-nitrotoluol, 4-(2'-Ureido- ethyl)amino-nitrobenzol, Basic Violet 14 (C.I. 42 510), Basic Violet 2 (C.I. 42 520), Acid Brown 4 (C.I. 14 805), 1,4-Diaminoanthrachinon und 1,4,5,8-Tetra- aminoanthrachinon.The oxidation hair dye according to the invention can contain at least one dye which is applied directly to the hair and which should be selected from: 2-amino-4-nitrophenol, 2-nitro-l, 4-diamino-benzene, 2-amino-5-nitrophenol, 2- Amino-4,6-dinitrophenol, 2-amino-5- (2'-hydroxyethyl) amino-3-nitrobenzene, 4- (2'-hydroxyethyl) amino-3-nitrotoluene, 4- (2'-ureido-ethyl) amino-nitrobenzene, Basic Violet 14 (CI 42 510), Basic Violet 2 (CI 42 520), Acid Brown 4 (CI 14 805), 1,4-diaminoanthraquinone and 1,4,5,8-tetra-aminoanthraquinone.
Das erfindungsgemäße Oxidationshaarfärbemittel kann weiterhin auch mit sich selbst kuppelnde Farbvorstufen, wie zum Beispiel 2-Amino-5-methylphenol und 6-Amino-2- methylphenol, enthalten.The oxidation hair dye according to the invention can also contain self-coupling dye precursors, such as 2-amino-5-methylphenol and 6-amino-2-methylphenol.
Von den bekannten Entwicklersubstanzen kommen als Be¬ standteil des erfindungsgemäßen Mittels hauptsächlich aromatische p-Diamine und p-Aminophenole wie 1,4-Di- aminobenzol, 2,5-Diaminotoluol, 2,5-Diaminobenzylalko- hol, 2-(2'-Hydroxyethyl)-1,4-diaminobenzol, 4-Amino- phenol, 4-Amino-3-methylphenol, 4-Amino-2-methoxy- methylphenol, 4-Amino-2-ethoxymethylphenol sowie Tetraaminopyrimidin oder ähnliche Verbindungen in Betracht. Von den bekannten Kupplersubstanzen kann das erfindungsgemäße Mittel insbesondere Resorcin, 4-Chlor- resorcin, 4,6-Dichlorresorcin, 2-Methylresorcin, 2-Amino-4-(2'-hydroxyethylamino)-anisol, 2,4-Diamino- benzylalkohol, m-Phenylendiamin, 5-Amino-2-methylphe- nol, 2,4-Diamino-phenoxyethanol, 1-Naphthol, m-Amino- phenol, 3-Amino-4-chlor-6-methylphenol, 3-Amino-2-me- thylphenol, 4-Amino-2-hydroxyphenoxyethanol, 4-Hydro- xy-1,2-methylendioxybenzol, 4-(2'-Hydroxyethyl)amino- 1,2-methylendioxybenzol, 2,4-Diamino-5-ethoxytoluol, 4-Hydroxyindol, 3-Amino-5-hydroxy-2,6-dimethoxypyridin und 3,5-Diamino-2,6-dimethoxypyridin enthalten.Of the known developer substances, mainly aromatic p-diamines and p-aminophenols such as 1,4-diamino benzene, 2,5-diaminotoluene, 2,5-diaminobenzyl alcohol, 2- (2'- Hydroxyethyl) -1,4-diaminobenzene, 4-aminophenol, 4-amino-3-methylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-ethoxymethylphenol and tetraaminopyrimidine or similar compounds. Of the known coupler substances that can Agents according to the invention in particular resorcinol, 4-chlororesorcinol, 4,6-dichlororesorcinol, 2-methylresorcinol, 2-amino-4- (2'-hydroxyethylamino) anisole, 2,4-diamino-benzyl alcohol, m-phenylenediamine, 5- Amino-2-methylphenol, 2,4-diaminophenoxyethanol, 1-naphthol, m-aminophenol, 3-amino-4-chloro-6-methylphenol, 3-amino-2-methylphenol, 4- Amino-2-hydroxyphenoxyethanol, 4-hydroxy-1,2-methylenedioxybenzene, 4- (2'-hydroxyethyl) amino-1,2-methylenedioxybenzene, 2,4-diamino-5-ethoxytoluene, 4-hydroxyindole, 3- Amino-5-hydroxy-2,6-dimethoxypyridine and 3,5-diamino-2,6-dimethoxypyridine included.
Derartige zur Haarfärbung bekannte und übliche Entwick¬ ler- und Kupplersubstanzen sind unter anderem in dem Buch E. Sagarin, "Cosmetics", Science and Technology (1957), Interscience Publishers Inc., New York, Seiten 503 ff sowie in dem Buch von H. Janistyn, "Handbuch der Kosmetika und Riechstoffe" (1973), Seiten 338 ff, beschrieben.Such known and customary developer and coupler substances for hair coloring are found, inter alia, in the book E. Sagarin, "Cosmetics", Science and Technology (1957), Interscience Publishers Inc., New York, pages 503 ff and in the book by H Janistyn, "Handbook of Cosmetics and Fragrances" (1973), pages 338 ff.
Das erfindungsgemäße Oxidationshaarfärbemittel soll die Entwickler- und Kupplersubstanzen in einer Menge von jeweils 0,01 bis 5 Gewichtsprozent, bevorzugt in einer Menge von jeweils 0,1 bis 3 Gewichtsprozent enthalten. Die genannten Kuppler- und Entwicklersubstanzen können in den erfindungsgemäßen Haarfärbemittel jeweils ein¬ zeln oder im Gemisch miteinander enthalten sein.The oxidation hair dye according to the invention should contain the developer and coupler substances in an amount of 0.01 to 5 percent by weight, preferably in an amount of 0.1 to 3 percent by weight. The coupler and developer substances mentioned can in each case be present individually or in a mixture with one another in the hair colorants according to the invention.
Die Entwicklersubstanzen werden im allgemeinen in etwa äquimolaren Mengen, bezogen auf die Kupplersubstanzen, eingesetzt. Es ist jedoch nicht nachteilig, wenn die Entwicklersubstanz diesbezüglich in einem gewissen Überschuß oder Unterschuß vorhanden ist.The developer substances are generally used in approximately equimolar amounts, based on the coupler substances. However, it is not a disadvantage if the developer substance is present in a certain excess or deficit in this regard.
Selbstverständlich können die Kuppler- und Entwickler¬ substanzen sowie die anderen Farbkomponenten, sofern es Basen sind, auch in Form der physiologisch verträg¬ lichen Säureadditionssalze, wie beispielsweise als Hydrochlorid beziehungsweise Sulfat oder - sofern sie aromatische Hydroxygruppen besitzen - in Form der Salze mit Basen, zum Beispiel als Alkaliphenolate, eingesetzt werden.Of course, the coupler and developer substances as well as the other color components, if it Bases can also be used in the form of the physiologically compatible acid addition salts, such as, for example, as hydrochloride or sulfate or - if they have aromatic hydroxyl groups - in the form of the salts with bases, for example as alkali phenolates.
Die Gesamtmenge der in dem hier beschriebenen Oxida¬ tionshaarfärbemittel enthaltenen Entwicklersubstanz- Kupplersubstanz-Kombination soll etwa 0,1 bis 5,0 Gewichtsprozent, vorzugsweise 0,5 bis 4,0 Gewichtspro¬ zent, betragen.The total amount of the developer substance-coupler substance combination contained in the oxidation hair colorant described here should be about 0.1 to 5.0 percent by weight, preferably 0.5 to 4.0 percent by weight.
Die Farbstoffe der allgemeinen Formel (I) sollen in dem zuvor beschriebenen Oxidationshaarfärbemittel in einer Konzentration von 0,01 bis 1,0 Gewichtsprozent, vor¬ zugsweise in einer Konzentration von 0,01 bis 0,4 Gewichtsprozent, enthalten sein.The dyes of the general formula (I) should be present in the oxidation hair dye described above in a concentration of 0.01 to 1.0 percent by weight, preferably in a concentration of 0.01 to 0.4 percent by weight.
Darüber hinaus können in dem Oxidationshaarfärbemittel noch weitere kosmetische Zusätze, beispielsweise Anti- oxidantien wie Ascorbinsäure, Thioglykolsäure oder Natriumsulfit, Parfümöle, Komplexbildner, Netzmittel, Emulgatoren, Verdicker, Pflegestoffe und andere vorhan¬ den sein.In addition, the cosmetic hair dye can also contain other cosmetic additives, for example antioxidants such as ascorbic acid, thioglycolic acid or sodium sulfite, perfume oils, complexing agents, wetting agents, emulsifiers, thickeners, care agents and others.
Je nach Zusammensetzung können die erfindungsgemäßen Oxidationshaarfärbemittel schwach sauer, neutral oder alkalisch reagieren. Insbesondere weisen sie einen pH-Wert im alkalischen Bereich zwischen 8,0 und 11,5 auf, wobei die Einstellung vorzugsweise mit Ammoniak erfolgt. Es können aber auch organische A ine, zum Beispiel Monoethanolamin und Triethanolamin, oder auch anorganische Basen wie Natriumhydroxid und Kaliumhy¬ droxid, Verwendung finden. Als Oxidationsmittel zur Entwicklung der Haarfärbungen kommen hauptsächlich Wasserstoffperoxid und dessen Additionsverbindungen an Harnstoff, Melanin oder Na¬ triumborat in Form der 3 bis 12%igen, vorzugsweise der 6%igen wäßrigen Lösungen in Betracht. Wird eine 6%ige Wasserstoffperoxidlösung als Oxidationsmittel verwen¬ det, so beträgt das Gewichtsverhältnis zwischen dem Haarfärbemittel und dem Oxidationsmittel 5:1 bis 1:2, vorzugsweise jedoch 1:1. Größere Mengen an Oxidations¬ mittel werden vor allem bei höheren Farbstoffkonzentra¬ tionen im Haarfärbemittel oder wenn gleichzeitig eine stärkere Bleichung des Haares beabsichtigt ist, ver¬ wendet.Depending on the composition, the oxidation hair colorants according to the invention can react weakly acidic, neutral or alkaline. In particular, they have a pH in the alkaline range between 8.0 and 11.5, the setting preferably being made with ammonia. However, organic amines, for example monoethanolamine and triethanolamine, or else inorganic bases such as sodium hydroxide and potassium hydroxide can also be used. The main oxidizing agents used to develop hair color are hydrogen peroxide and its addition compounds to urea, melanin or sodium borate in the form of 3 to 12%, preferably 6%, aqueous solutions. If a 6% hydrogen peroxide solution is used as the oxidizing agent, the weight ratio between the hair dye and the oxidizing agent is 5: 1 to 1: 2, but preferably 1: 1. Larger amounts of oxidizing agent are used above all in the case of higher dye concentrations in the hair dye or when more bleaching of the hair is intended at the same time.
Die Zubereitungsform des Oxidationshaarfärbemittels kann die gleiche wie bei dem zuvor beschriebenen Haar¬ färbemittel ohne Oxidationsmittelzugabe, zum Beispiel die einer wäßrigen oder wäßrig-alkoholischen Lösung, sein. Vorzugsweise ist die Zubereitungsform jedoch die einer Creme, eines Gels oder die einer Emulsion.The form of preparation of the oxidizing hair dye can be the same as that of the previously described hair dye without the addition of an oxidizing agent, for example that of an aqueous or aqueous-alcoholic solution. However, the preparation form is preferably that of a cream, a gel or that of an emulsion.
Übliche Zusätze in Lösungen, Cremes, Emulsionen oder Gelen sind zum Beispiel Lösungsmittel wie Wasser, niedere aliphatische Alkohole, beispielsweise Ethanol, Propanol und Isopropanol oder Glykole wie Glycerin und 1,2-Propylenglykol, weiterhin Netzmittel oder Emulga- toren aus den Klassen der anionischen, kationischen, amphoteren oder nichtionogenen oberflächenaktiven Substanzen wie Fettalkoholsulfate, oxethylierte Fett¬ alkoholsulfate, Alkylsulfonate, Alkylbenzolsulfonate, Alkyltrimethylammoniumsalze, Alkylbetaine, oxethylierte Fettalkohole, oxethylierte Nonylphenole, Fettsäure- alkanolamide, oxethylierte Fettsäureester, ferner Ver¬ dicker wie höhere Fettalkohole, Stärke oder Cellulose- derivate, weiterhin Vaseline, Paraffinöl und Fettsäuren sowie außerdem Pflegestoffe wie kationische Harze, Lanolinderivate, Cholesterin, Pantothensäure und Betain. Die erwähnten Bestandteile werden in den für solche Zwecke üblichen Mengen verwendet, zum Beispiel die Netzmittel und Emulgatoren in Konzentrationen von etwa 0,5 bis 30 Gewichtsprozent, die Verdicker in einer Menge von etwa 0,1 bis 25 Gewichtsprozent und die Pflegestoffe in einer Konzentration von etwa 0,1 bis 5,0 Gewichtsprozent.Usual additives in solutions, creams, emulsions or gels are, for example, solvents such as water, lower aliphatic alcohols, for example ethanol, propanol and isopropanol or glycols such as glycerol and 1,2-propylene glycol, furthermore wetting agents or emulsifiers from the classes of the anionic, cationic, amphoteric or nonionic surfactants such as fatty alcohol sulfates, ethoxylated fatty alcohol sulfates, alkylsulfonates, alkylbenzenesulfonates, alkyltrimethylammonium salts, alkylbetaines, oxyethylated fatty alcohols, oxyethylated nonylphenols, fatty acid alkanolamides, ethoxylated fatty acid ester, further Ver¬ thicker such as higher fatty alcohols, starch or cellulose derivatives, petroleum jelly, paraffin oil and fatty acids as well as care products such as cationic resins, lanolin derivatives, cholesterol, pantothenic acid and betaine. The components mentioned are used in the amounts customary for such purposes, for example the wetting agents and emulsifiers in concentrations of about 0.5 to 30 percent by weight, the thickeners in an amount of about 0.1 to 25 percent by weight and the care substances in a concentration of about 0.1 to 5.0 weight percent.
Für die Anwendung zur oxidativen Färbung von Haaren vermischt man das vorstehend beschriebene Oxidations¬ haarfärbemittel unmittelbar vor dem Gebrauch mit einem Oxidationsmittel und trägt eine für die Haarfärbebe¬ handlung ausreichende Menge, je nach Haarfülle, im all¬ gemeinen etwa 60 bis 200 g, dieses Gemisches auf das Haar auf.For use in the oxidative dyeing of hair, the oxidizing hair dye described above is mixed with an oxidizing agent immediately before use and an amount sufficient for the hair dyeing treatment, depending on the fullness of the hair, is generally about 60 to 200 g of this mixture on the hair.
Man läßt das Gemisch bei 15 bis 50°C etwa 10 bis 45 Minuten lang, vorzugsweise 30 Minuten lang, auf das Haar einwirken, spült sodann das Haar mit Wasser aus und trocknet es. Gegebenenfalls wird im Anschluß an diese Spülung mit einem Shampoo gewaschen und eventuell mit einer schwachen organischen Säure, wie zum Beispiel Zitronensäure oder Weinsäure, nachgespült. Anschließend wird das Haar getrocknet.The mixture is allowed to act on the hair at 15 to 50 ° C for about 10 to 45 minutes, preferably 30 minutes, then the hair is rinsed with water and dried. If necessary, this rinse is washed with a shampoo and possibly rinsed with a weak organic acid, such as citric acid or tartaric acid. The hair is then dried.
Die erfindungsgemäßen Oxidationshaarfärbemittel mit einem Gehalt an mindestens einem 1,4-Bis- |(dihydroxy¬ alkyl)amino]-anthrachinon der allgemeinen Formel (I) führen zu Haarfärbungen mit ausgezeichneten Echtheits¬ eigenschaften und hoher Farbintensität, nie in den hier beschriebenen Haarfärbemitteln mit und ohne Oxidations¬ mittelzugabe enthaltenen Verbindungen der Formel (I) sind toxikologisch und dermatologisch unbedenklich, gut wasserlöslich und färben allein in einem klaren Blau¬ ton. In Kombination mit anderen Farbstoffen sind die Verbindungen der allgemeinen Formel (I) insbesondere zur Nuancierung intensiver schwarzer Farbtöne hervor¬ ragend geeignet.The oxidation hair colorants according to the invention containing at least one 1,4-bis- (dihydroxyalkyl) amino] anthraquinone of the general formula (I) lead to hair colorations with excellent fastness properties and high color intensity, never in the hair colorants described here and compounds of the formula (I) which do not contain any oxidizing agent are toxicologically and dermatologically harmless, readily water-soluble and stain alone in a clear shade of blue. In combination with other dyes, the compounds of the general formula (I) are particularly suitable for shading intense black shades.
Gegenstand dieser Anmeldung ist zudem das 1,4-Bis j(dihydroxyalkyl)amino]-anthrachinon der allgemeinen Formel (II)This application also relates to the 1,4-bis j (dihydroxyalkyl) amino] anthraquinone of the general formula (II)
Figure imgf000016_0001
wobei Rl und R2 gleich oder verschieden sein können und unabhängig voneinander einen geradkettigen oder ver¬ zweigten C3- bis C4-Dihydroxyalkylrest bedeuten.
Figure imgf000016_0001
where R1 and R2 can be the same or different and independently of one another represent a straight-chain or branched C3- to C4-dihydroxyalkyl radical.
Als Beispiel für die neuen 1,4-Bis- |(dihydroxyalkyl)- aminoj -anthrachinone der allgemeinen Formel (II) sei das 1,4-Bis- (2',3'-dihydroxypropyl)amino J-anthrachinon genannt.An example of the new 1,4-bis- (dihydroxyalkyl) aminoj -anthraquinones of the general formula (II) is 1,4-bis- (2 ', 3'-dihydroxypropyl) amino J-anthraquinone.
Die neuen 1,4-Bis- ((dihydroxyalkyl)aminoj-anthrachinone lassen sich nach einem, zum Beispiel in dem Lehrbuch N.N. Woroshzow, Grundlagen der Synthese von Zwischen¬ produkten und Farbstoffen, Akademie Verlag, Berlin (1966), Seite 481 - 482, beschriebenen Verfahren her¬ stellen, bei dem das technisch verfügbare 1,4-Dihydro- xyanthrachinon zunächst mit einem üblichen Reduktions¬ mittel, beispielsweise Natriumdithionit, in einer alka¬ lischen wäßrigen Lösung zum 1,4,5,8-Tetrahydroanthra- chinon reduziert wird. Das 1,4,5,8-Tetrahydroanthra- chinon wird anschließend unter einer Schutzgas¬ atmosphäre, zum Beispiel unter Stickstoff, mit einer wäßrigen Lösung des entsprechenden Amino-alkyldiols in der Wärme umgesetzt. Zur Reoxidation des Chinon Systems wird sodann Sauerstoff in das Reaktionsgemisch eingeleitet, wodurch das 1,4-Bis- |(dihydroxyalkyl)- aminoj-anthrachinon ausgefällt wird.The new 1,4-bis- ((dihydroxyalkyl) aminoj-anthraquinones can be described according to, for example, in the textbook NN Woroshzow, Basics of the Synthesis of Intermediates and Dyes, Akademie Verlag, Berlin (1966), pages 481-482 to produce the described process, in which the industrially available 1,4-dihydroxyanthraquinone is first reduced to 1,4,5,8-tetrahydroanthraquinone in a alkaline aqueous solution using a conventional reducing agent, for example sodium dithionite The 1,4,5,8-tetrahydroanthraquinone is then treated under a protective gas atmosphere, for example under nitrogen, with a implemented aqueous solution of the corresponding amino-alkyldiol in the heat. Oxygen is then passed into the reaction mixture to reoxidize the quinone system, causing the 1,4-bis- (dihydroxyalkyl) aminoj-anthraquinone to precipitate.
Die Verbindungen der allgemeinen Formel (II) stellen intensiv blaufärbende Anthrachinonfarbstoffe dar, die sich neben einer guten Wasserlöslichkeit auch durch ihre gute physiologische Verträglichkeit auszeichnen. Die Verbindungen der Formel (II) sind aufgrund ihrer Eigenschaften wertvolle blaufärbende Haarfarbstoffe.The compounds of the general formula (II) are intensely blue-coloring anthraquinone dyes which, in addition to good water solubility, are also notable for their good physiological tolerance. Because of their properties, the compounds of the formula (II) are valuable blue-coloring hair dyes.
Die nachfolgenden Beispiele sollen den Gegenstand der vorliegenden Anmeldung erläutern, ohne ihn darauf zu beschränken.The following examples are intended to explain the subject matter of the present application without restricting it thereto.
B e i s p i e l eB e i s p i e l e
Beispiel 1: Herstellung von 1,4-Bis-f(2',3'-dihydroxy propyl)amino1-anthrachinonExample 1: Preparation of 1,4-bis-f (2 ', 3'-dihydroxy propyl) amino1-anthraquinone
Figure imgf000017_0001
Figure imgf000017_0001
50 g 1,4-Dihydroxyanthrachinon werden in 1.000 ml 5prc- zentiger Natronlauge gelöst und mit 500 ml 20prozenti- ger Natriumdithionitlösung reduziert. Nach langsamer Zugabe von 75,8 g 3-Amino-propan-l,2-diol in 30 ml Was¬ ser wird 8 Stunden unter Stickstoff auf 100° Celsius erwärmt. Anschließend wird 3 Stunden lang Sauerstoff eingeleitet. Das 1,4-Bis- ((2',3'-dihydroxypropyl)- aminoj-anthrachinon wird sodann abfiltriert und mit Aceton gewaschen. Es werden 38 g tiefblaue Kristalle, entsprechend einer Ausbeute von 47 % der Theorie, mit einem Zersetzungsschmelzpunkt von 220° Celsius erhalten.50 g of 1,4-dihydroxyanthraquinone are dissolved in 1,000 ml of 5 percent sodium hydroxide solution and reduced with 500 ml of 20 percent sodium dithionite solution. After slower 75.8 g of 3-aminopropane-1,2-diol in 30 ml of water are added and the mixture is heated to 100 ° C. under nitrogen for 8 hours. Then oxygen is introduced for 3 hours. The 1,4-bis ((2 ', 3'-dihydroxypropyl) aminoj-anthraquinone is then filtered off and washed with acetone. 38 g of deep blue crystals, corresponding to a yield of 47% of theory, with a decomposition melting point of 220 ° C obtained.
iH-NMR (DMSO-Dδ): = 3.40-3.78 (m, 10 H, -C≤2 undiH-NMR (DMSO-Dδ): = 3.40-3.78 (m, 10 H, -C≤2 and
-C.H-), 4.9 (breit, 4 H, OH; tauscht mit-C.H-), 4.9 (broad, 4 H, OH; exchanges with
D2O aus) , 7.48 (s, 2 H, 2-H, 3-H) , 7.76 (dd, 2 H, J = 5.8 und 3.3 Hz,D2O off), 7.48 (s, 2 H, 2-H, 3-H), 7.76 (dd, 2 H, J = 5.8 and 3.3 Hz,
6-H, 7-H), 8.25 (dd, 2 H, J = 5.8 und 3.3 Hz,6-H, 7-H), 8.25 (dd, 2 H, J = 5.8 and 3.3 Hz,
5-H, 8-H), 11.00 ppm (t, 2 H, J = 5.9 Hz,5-H, 8-H), 11.00 ppm (t, 2 H, J = 5.9 Hz,
-NH-; tauscht mit D2O aus).-NH-; exchanges with D2O).
MS (70 ev) : 386 (M+)MS (70 ev): 386 (M +)
B e i s p i e l eB e i s p i e l e
Beispiel A: Flüssiges HaarfärbemittelExample A: Liquid hair dye
0,05 g 4-Amino-4'-Ibis-(2'-hydroxyethyl)amino - .1 phenylazobenzol0.05 g of 4-amino-4'-ibis- (2'-hydroxyethyl) amino - .1 phenylazobenzene
0,05 g 1,4-Bis- 1(2' ,3'-dihydroxypropyl)aminoI- anthrachinon0.05 g 1,4-bis-1 (2 ', 3'-dihydroxypropyl) aminoI-anthraquinone
0,10 g 2-(2'Hydroxyethyl)amino-5-ibis-(2'-hydroxy¬ ethyl)aminoj-nitrσbenzol0.10 g of 2- (2'-hydroxyethyl) amino-5-ibis (2'-hydroxyethyl) aminoj-nitrσbenzene
0,50 g Hydroxyethylcellulose0.50 g hydroxyethyl cellulose
5,00 g Laurylalkohol-diglykolethersulfat-Natriu - salz, 28prozentige wäßrige Lösung 10,00 g Isopropanol5.00 g of lauryl alcohol diglycol ether sulfate sodium salt, 28 percent aqueous solution 10.00 g isopropanol
10,00 g Ammoniak, 25prozentige wäßrige Lösung10.00 g ammonia, 25 percent aqueous solution
74,30 g Wasser 100 g74.30 g water 100 g
Gebleichtes Naturhaar wird 20 Minuten lang bei Raumtem¬ peratur mit dem vorstehenden flüssigen Haarfärbemittel behandelt. Nach der Spülung des Haares mit Wasser und der anschließenden Trocknung ist das Haar in einem blond-aschfarbenen Ton eingefärbt.Bleached natural hair is treated with the above liquid hair dye at room temperature for 20 minutes. After rinsing the hair with water and then drying it, the hair is colored in a blonde-ash color.
Beispiel B: Haarfärbemittel in CremeformExample B: Hair dye in cream form
4-(2'Hydroxyethyl)amino-3-nitrobenzol 1 ,4-Bis- |(2'-hydroxyethyl)amino]-4-N-ethyl- 2-nitrobenzol l-Amino-2-nitro-4-[bis-(2'-hydroxyethyl)ami¬ no]-benzol4- (2'-hydroxyethyl) amino-3-nitrobenzene 1,4-bis- | (2'-hydroxyethyl) amino] -4-N-ethyl-2-nitrobenzene l-amino-2-nitro-4- [bis- (2'-hydroxyethyl) amino] benzene
1,4-Bis- (2' ,3'-dihydroxypropyl)aminoj- anthrachinon Cetylalkohol1,4-bis (2 ', 3'-dihydroxypropyl) aminoj-anthraquinone cetyl alcohol
Laurylalkohol-diglykolethersulfat-Natrium- salz, 28prozentige wäßrige Lösung p-Hydroxybenzoesäuremethylester Ammoniak, 25prozentige wäßrige Lösung Wasser
Figure imgf000019_0001
Lauryl alcohol diglycol ether sulfate sodium salt, 28 percent aqueous solution of methyl p-hydroxybenzoate ammonia, 25 percent aqueous solution of water
Figure imgf000019_0001
50 g des vorstehenden Haarfärbemittels werden auf weiße menschliche Haare aufgetragen und nach einer Einwirk¬ zeit von 20 Minuten im Wasser ausgespült. Das Haar wird anschließend getrocknet. Es ist in einem natürlichen, Beispiel C: Farbfestiger50 g of the above hair dye are applied to white human hair and rinsed in water after an exposure time of 20 minutes. The hair is then dried. It’s in a natural, Example C: Color fastener
0,01 g 1,4-Bis- |(2' ,3'-dihydroxypropyl)aminoj- anthrachinon0.01 g 1,4-bis- | (2 ', 3'-dihydroxypropyl) aminoj-anthraquinone
0,02 g 1,4-Diamino-anthrachinon0.02 g of 1,4-diamino-anthraquinone
2,00 g Polyvinylpyrrolidon2.00 g polyvinyl pyrrolidone
0,10 g Glycerin -0.10 g glycerin -
40,00 g Isopropanol40.00 g isopropanol
57,87 g Wasser 100,00 g57.87 g water 100.00 g
Weiße menschliche Haare werden mit der Farbfestiger- Lösung eingelegt und getrocknet. Das Haar ist in einem modischen Silberton gefärbt und gefestigt.White human hair is inserted with the color fixer solution and dried. The hair is colored and set in a fashionable silver tone.
Beispiel D: Haarfärbemittel in CremeformExample D: Hair dye in cream form
1,100 g 1,4-Bis- jj2'-hydroxyethyl)aminoj-4-N-ethyl-1,100 g of 1,4-bis-2'-hydroxyethyl) aminoj-4-N-ethyl
2-nitrobenzol 0,100 g 4-Amino-4'-Ibis-(2'-hydroxyethyl)amino]- phenylazobenzol 0,047 g 1,4-Bis- f~(2',3'-dihydroxypropyl)amino - anthrachinon 0,040 g 1,4-Diaminoanthrachinon 0,170 g 4-(2'-Hydroxyethyl)amino-3-nitrotoluol 7,500 g Cetylalkohol 1,750 g Laurylalkohol-diglykolethersulfat-Natrium- salz, 28 prozentige wäßrige Lösung 0,100 g p-Hydroxybenzoesäuremethylester 0,200 g Ammoniak, 25 prozentige wäßrige Lösung 88,993 g Wasser 100,000 g 50 g des vorstehenden Haarfärbemittels in Cremeform werden auf weiße menschliche Haare aufgetragen. Nach einer Einwirkungszeit von 20 Minuten wird das Haar mit Wasser ausgespült und getrocknet. Das Haar ist in einem intensiven schwarzen Farbton gefärbt.2-nitrobenzene 0.100 g 4-amino-4'-ibis- (2'-hydroxyethyl) amino] - phenylazobenzene 0.047 g 1,4-bis-f ~ (2 ', 3'-dihydroxypropyl) amino - anthraquinone 0.040 g 1, 4-diaminoanthraquinone 0.170 g 4- (2'-hydroxyethyl) amino-3-nitrotoluene 7.500 g cetyl alcohol 1.750 g lauryl alcohol diglycol ether sulfate sodium salt, 28% aqueous solution 0.100 g methyl p-hydroxybenzoate 0.200 g ammonia, 25% aqueous solution 88.993 g Water 100,000 g 50 g of the above hair dye in cream form is applied to white human hair. After an exposure time of 20 minutes, the hair is rinsed with water and dried. The hair is colored in an intense black shade.
Beispiel E: Oxidationshaarfärbemittel in GelformExample E: Oxidation hair dye in gel form
2,5-Diaminotoluol-sulfat2,5-diaminotoluene sulfate
ResorcinResorcinol
3-Aminophenol3-aminophenol
1,4-Bis- I(2' ,3'-dihydroxypropyl)amino]■ anthrachinon1,4-bis-I (2 ', 3'-dihydroxypropyl) amino] ■ anthraquinone
AscorbinsäureAscorbic acid
ÖlsäureOleic acid
IsopropanolIsopropanol
Ammoniak, 25 %ige wäßrige LösungAmmonia, 25% aqueous solution
Wasser
Figure imgf000021_0001
water
Figure imgf000021_0001
Kurz vor dem Gebrauch werden 50 g des vorstehenden Oxi- dationshaarfärbemittels in Gelform mit 50 g einer 6 %igen Wasserstoffperoxidlösung vermischt und auf weiße, menschliche Haare aufgetragen. Nach einer Einwirkungszeit von 30 Minuten bei 40 Grad Celsius wird das Haar mit Wasser gespült, gegebenenfalls shampoo- niert und getrocknet. Das Haar ist in einem natürlichen mittelblonden Farbton mit leichtem Ascheffekt gefärbt.Shortly before use, 50 g of the above oxidation hair dye in gel form are mixed with 50 g of a 6% hydrogen peroxide solution and applied to white human hair. After an exposure time of 30 minutes at 40 degrees Celsius, the hair is rinsed with water, if necessary shampooed and dried. The hair is dyed in a natural medium blonde shade with a slight ash effect.
Alle in der vorliegenden Anmeldung angegebenen Prozent¬ zahlen stellen, sofern nicht anders vermerkt, Gewichts¬ prozent dar. Unless otherwise noted, all the 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 mit einem Gehalt an für Haarfärbemittel üblichen Zusätzen, dadurch gekennzeichnet, daß es mindestens ein 1,4-Bis- I (dihydroxyalkyl)aminoj-anthrachinon der allge¬ meinen Formel (I)1. Means for coloring hair with a content of additives customary for hair colorants, characterized in that it contains at least one 1,4-bis- I (dihydroxyalkyl) aminoj-anthraquinone of the general formula (I)
Figure imgf000022_0001
Figure imgf000022_0001
wobei R und R2 gleich oder verschieden sein kön¬ nen und unabhängig voneinander einen geradkettigen oder verzweigten C3-bis C4-Dihydroxyalkylrest be¬ deuten, enthält.where R and R 2 may be the same or different and independently of one another denote a straight-chain or branched C3 to C4 dihydroxyalkyl radical.
Mittel nach Anspruch 1, dadurch gekennzeichnet, daß es 1,4-Bis- (2' ,Agent according to claim 1, characterized in that it is 1,4-bis- (2 ',
3'-dihydroxypropyl)amino -an¬ thrachinon enthält.Contains 3'-dihydroxypropyl) amino-anthraquinone.
Mittel nach Anspruch 1 oder 2, dadurch gekenn¬ zeichnet, daß es 0,01 bis 1,0 Gewichtsprozent des 1,4-Bis- j(dihydroxyalkyl)amino]-anthrachinons der allgemeinen Formel (I) enthält. Agent according to claim 1 or 2, characterized gekenn¬ characterized in that it contains 0.01 to 1.0 percent by weight of 1,4-bis-j (dihydroxyalkyl) amino] anthraquinone of the general formula (I).
4. Mittel nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß es zusätzlich zu mindestens einem Farbstoff der allgemeinen Formel (I), noch einen oder mehrere weitere direkt auf das Haar aufziehende Farbstoffe enthält.4. Composition according to one of claims 1 to 3, characterized in that it contains, in addition to at least one dye of the general formula (I), one or more further dyes which are absorbed directly onto the hair.
5. Mittel nach Anspruch 4, dadurch gekennzeichnet, daß der zusätzlich enthaltene direkt auf das Haar aufziehende Farbstoff ausgewählt ist aus 2-Amino- 4-nitrophenol, 2-Nitro-l,4-diaminobenzol, 2-Amino- 5-nitrophenol, Pikraminsäure, 2-Amino-5-(2'-hydro¬ xyethyl)amino-nitrobenzol, 4-(2'-Hydroxyethyl)- amino-3-nitrophenol, 1-(2'-Hydroxyethyl)amino- 2-amino-4-nitrobenzol, 4-(2'-Ureidoethyl)amino- nitrobenzol, 4-(2' ,3'-Dihydroxypropyl)amino-3- nitro-trifluormethylbenzol, 1,4-Bis- l~(2 '-hydroxy¬ ethyl)aminoJ-4-N-ethyl-2-nitrobenzol, 4-(2'-Hy¬ droxyethyl)amino-3-nitrotoluol, 2,5-Bis-j~(2'hy¬ droxyethyl)aminoj-nitrobenzol, 2-(2'-Hydroxy¬ ethyl)amino-4,5. Composition according to claim 4, characterized in that the additionally contained dye directly absorbed on the hair is selected from 2-amino-4-nitrophenol, 2-nitro-l, 4-diaminobenzene, 2-amino-5-nitrophenol, picramic acid , 2-amino-5- (2'-hydroxyethyl) amino-nitrobenzene, 4- (2'-hydroxyethyl) amino-3-nitrophenol, 1- (2'-hydroxyethyl) amino-2-amino-4- nitrobenzene, 4- (2'-ureidoethyl) amino-nitrobenzene, 4- (2 ', 3'-dihydroxypropyl) amino-3-nitro-trifluoromethylbenzene, 1,4-bis-1 ~ (2'-hydroxyethyl) aminoJ -4-N-ethyl-2-nitrobenzene, 4- (2'-hydroxyethyl) amino-3-nitrotoluene, 2,5-bis-j ~ (2'-hydroxyethyl) aminoj-nitrobenzene, 2- (2nd '-Hydroxy¬ ethyl) amino-4,
6-dinitrophenol, l-Amino-4-(2' ,3'- dihydroxypropyl)amino-2-nitro-5-chlorbenzol, 4- j~Bis-(2'-hydroxyethyl)aminoj-1-(2'-hydroxyethyl)- amino-2-nitrobenzol, l-Amino-2-nitro-4- bis-(2'-6-dinitrophenol, l-amino-4- (2 ', 3'-dihydroxypropyl) amino-2-nitro-5-chlorobenzene, 4- j ~ bis- (2'-hydroxyethyl) aminoj-1- (2'-hydroxyethyl ) - amino-2-nitrobenzene, l-amino-2-nitro-4- bis- (2'-
1 hydroxyethyl)aminoj-benzol, Basic Violet 1 (C.I. 42 535), Basic Violet 14 (C.I. 42 510), Basic Vio¬ let 2 (C.I. 42 520), Acid Brown 4 (C.I. 14 805), Disperse Violet 4 (C.I. 61 105), 1,4,5,8-Tetra- aminoanthrachinon (C.I. 64 500) und 1,4-Diamino- anthrachinon.1 hydroxyethyl) aminoj-benzene, Basic Violet 1 (CI 42 535), Basic Violet 14 (CI 42 510), Basic Violet 2 (CI 42 520), Acid Brown 4 (CI 14 805), Disperse Violet 4 (CI 61 105), 1,4,5,8-tetraaminoanthraquinone (CI 64 500) and 1,4-diaminoanthraquinone.
Mittel nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß es in Form eines Haarfärbe¬ mittels mit zusätzlicher Haarfestigung vorliegt und mindestens ein in der Kosmetik üblicherweise verwendetes Polymerisat oder natürliches Polymer enthält.Agent according to one of claims 1 to 5, characterized in that it is in the form of a Haarfärbe¬ means with additional hair fixation and contains at least one polymer or natural polymer commonly used in cosmetics.
7. Mittel nach Anspruch 6, dadurch gekennzeichnet, daß das Polymerisat oder das natürliche Polymer ausgewählt ist aus Polyvinylpyrrolidon, Poly- vinylacetat, Polyvinylalkohol, Polyacrylsäure, Polymethacrylsäure sowie basischen Polymerisaten der Ester der Polyacrylsäure oder Polymethacryl¬ säure mit Aminoalkoholen, deren Salze oder Quater- nisierungsprodukten, Polyacrylnitril, Polyvinyl- lactamen oder Copolymerisaten aus diesen Verbin¬ dungen, Chitosan und Chitosanderivaten.7. Composition according to claim 6, characterized in that the polymer or the natural polymer is selected from polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, polyacrylic acid, polymethacrylic acid and basic polymers of the esters of polyacrylic acid or Polymethacryl¬ acid with amino alcohols, their salts or quaternary products, polyacrylonitrile, polyvinyl lactams or copolymers of these compounds, chitosan and chitosan derivatives.
8. Mittel nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß es mindestens eine Entwickler¬ substanz-Kupplersubstanz-Kombination enthält.8. Composition according to one of claims 1 to 3, characterized in that it contains at least one developer-substance-coupler substance combination.
9. Mittel nach Anspruch 8, dadurch gekennzeichnet, daß die Gesamtmenge der Entwicklersubstanz-Kupp¬ lersubstanz-Kombination etwa 0,1 bis 5,0 Gewichtsprozent beträgt.9. Composition according to claim 8, characterized in that the total amount of developer substance-coupler substance combination is about 0.1 to 5.0 percent by weight.
10. Mittel nach Anspruch 8 oder 9, dadurch gekenn¬ zeichnet, daß die Entwicklersubstanz ausgewählt ist aus 1,4-Diaminobenzol, 2,5-Diaminotoluol, 2,5- Diaminobenzylalkohol, 2-(2'-Hydroxyethyl)-1,4- diaminobenzol, 4-Aminophenol, 4-Amino-3-methyl- phenol, 4-Amino-2-methoxymethylphenol, 4-Amino-2- ethoxymethylphenol und Tetraaminopyrimidin.10. Composition according to claim 8 or 9, characterized gekenn¬ characterized in that the developer substance is selected from 1,4-diaminobenzene, 2,5-diaminotoluene, 2,5-diaminobenzyl alcohol, 2- (2'-hydroxyethyl) -1.4 - diaminobenzene, 4-aminophenol, 4-amino-3-methylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-ethoxymethylphenol and tetraaminopyrimidine.
11. Mittel nach einem der Ansprüche 8 bis 10, dadurch gekennzeichnet, daß die Kupplersubstanz ausgewählt ist aus Resorcin, 4-Chlorresorcin, 4,6-Dichlor- resorcin, 2-Methylresorcin, 2-Amino-4-(2'-hydroxy- ethylamino)-anisol, 2,4-Diaminobenzylalkohol, m-Phenylendiamin, 5-Amino-2-methylphenol, 2,4-Di- a inophenoxyethanol, 1-Naphthol, m-Aminophenol, 3-Amino-4-chlor-6-methylphenol, 3-Amino-2-methyl- phenol, 4-Amino-2-hydroxyphenoxyethanol, 4-Hydro- xy-1,2-methylendioxybenzol, 4-(2'-Hydroxyethyl)- amino-1,2-methylendioxybenzol, 2,4-Diamino-5- ethoxytoluol, 4-Hydroxyindol, 3-Amino-5-hydroxy- 2,6-dimethoxypyridin und 3,5-Diamino-2,6-di- methoxypyridin.11. A composition according to any of Ans p rüche 8 to 10, characterized in that the coupler substance is selected from resorcinol, 4-chlororesorcinol, 4,6-dichloro- resorcinol, 2-methylresorcinol, 2-amino-4- (2'-hydroxyethylamino) anisole, 2,4-diaminobenzyl alcohol, m-phenylenediamine, 5-amino-2-methylphenol, 2,4-di-a-inophenoxyethanol, 1-naphthol, m-aminophenol, 3-amino-4-chloro-6-methylphenol, 3-amino-2-methylphenol, 4-amino-2-hydroxyphenoxyethanol, 4-hydroxy-1,2-methylenedioxybenzene, 4- (2'-hydroxyethyl) - amino-1,2-methylenedioxybenzene, 2,4-diamino-5-ethoxytoluene, 4-hydroxyindole, 3-amino-5-hydroxy-2,6-dimethoxypyridine and 3,5-diamino -2,6-di-methoxypyridine.
12. Mittel nach einem der Ansprüche 8 bis 11, dadurch gekennzeichnet, daß es mindestens einen direkt auf das Haar aufziehenden Farbstoff enthält, der aus¬ gewählt ist aus: 2-Amino-4-nitrophenol, 2-Nitro-12. Composition according to one of claims 8 to 11, characterized in that it contains at least one dye which is applied directly to the hair and which is selected from: 2-amino-4-nitrophenol, 2-nitro-
1,4-diaminobenzol, 2-Amino-5-nitrophenol, 2-Amino-4,6-dinitrophenol, 2-Amino-5-(2'-hydroxy¬ ethyl)amino-3-nitrobenzol, 4-(2'-Hydroxyethyl)- amino-3-nitrotoluol, 4-(2'-Ureidoethyl)amino- nitrobenzol, Basic Violet 14 (C.I. 42 510), Basic Violet 2 (C.I. 42 520), Acid Brown 4 (C.I. 14 805), 1,4-Diaminoanthrachinon und 1,4,5,8-Tetra- aminoanthrachinon.1,4-diaminobenzene, 2-amino-5-nitrophenol, 2-amino-4,6-dinitrophenol, 2-amino-5- (2'-hydroxyethyl) amino-3-nitrobenzene, 4- (2'- Hydroxyethyl) - amino-3-nitrotoluene, 4- (2'-ureidoethyl) amino-nitrobenzene, Basic Violet 14 (CI 42 510), Basic Violet 2 (CI 42 520), Acid Brown 4 (CI 14 805), 1, 4-diaminoanthraquinone and 1,4,5,8-tetraaminoanthraquinone.
13. 1,4-Bis- [(dihydroxyalkyl)aminoj-anthrachinon der allgemeinen Formel (II)13. 1,4-bis- [(dihydroxyalkyl) aminoj-anthraquinone of the general formula (II)
(II)
Figure imgf000025_0001
wobei Rl und R2 gleich oder verschieden sein kön¬ nen und unabhängig voneinander einen geradkettigen oder verzweigten Cß-bis C4-Dihydroxyalkylrest be¬ deuten.(II)
Figure imgf000025_0001
where R 1 and R 2 can be the same or different and independently of one another denote a straight-chain or branched C 1 -C 4 -dihydroxyalkyl radical.
14. 1,4-Bis- [(2',3'-dihydroxypropyl)aminoJ-anthra¬ chinon 14. 1,4-bis- [(2 ', 3'-dihydroxypropyl) aminoJ-anthraquinone
PCT/EP1991/001836 1990-10-15 1991-09-26 Hair colorant containing 1,4-bis-[(dihydroxyalkyl)amino]-anthrachinone and novel 1,4-bis-[(dihydroxyalkyl)amino)]-anthrachinones WO1992006670A1 (en)

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DE19904032607 DE4032607A1 (en) 1990-10-15 1990-10-15 AGENT FOR DYING HAIR CONTAINING 1,4-BIS ((DIHYDROXYALKYL) AMINO) ANTHRACHINONE AND NEW 1,4-BIS - ((DIHYDROXYALKYL) AMINO) ANTHRACHINONE

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993019037A1 (en) * 1992-03-18 1993-09-30 Imperial Cancer Research Technology Limited Compounds
US5733880A (en) * 1993-09-30 1998-03-31 Napier University Ventures Limited Anthracene derivatives for use as anticancer agents
WO1999002124A2 (en) * 1997-07-10 1999-01-21 Bristol-Myers Squibb Company Direct hair dye compositions and methods containing novel anthraquinone mixtures

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10222819A1 (en) * 2002-05-21 2003-12-04 Bayer Ag Process for the preparation of N, N'-disubstituted 1,4-diaminoanthraquinones
DE10347600A1 (en) * 2003-10-14 2005-05-25 Görlach, Bernd, Dr. Diesel engine leak detection procedure uses spectroscopically detectable anthraquinone dye introduced into one of two separate fluids

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE191221C1 (en) * 1964-01-01
DE1617709A1 (en) * 1966-02-15 1971-10-14 Oreal Process for coloring and simultaneous lightening of human hair and means for carrying out this process
GB1379991A (en) * 1971-04-05 1975-01-08 Bristol Myers Co Stable oil-in-water emulsion hair dye composition
DE3534885A1 (en) * 1984-10-01 1986-04-10 L'oreal, Paris A COLOR CONTAINING AZO DYE FOR KERATINE FIBERS AND METHOD FOR PRODUCING THIS DYE

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE191221C1 (en) * 1964-01-01
DE1617709A1 (en) * 1966-02-15 1971-10-14 Oreal Process for coloring and simultaneous lightening of human hair and means for carrying out this process
GB1379991A (en) * 1971-04-05 1975-01-08 Bristol Myers Co Stable oil-in-water emulsion hair dye composition
DE3534885A1 (en) * 1984-10-01 1986-04-10 L'oreal, Paris A COLOR CONTAINING AZO DYE FOR KERATINE FIBERS AND METHOD FOR PRODUCING THIS DYE

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Chemical Abstracts Service Registry Handbook Number Section 1986 Supplement, Columbus, Ohio, US, Seite 114RO, RN=99788-75-7. *
Chemical Abstracts, Band 104, Nr. 12, 24 März 1986, Columbus, Ohio, US, Seite 735, Zusammenfassung 99595y, & JP,A,60 172 591 (Mitsubishi Chemical Industries Co., Ltd) 06 September 1985. *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993019037A1 (en) * 1992-03-18 1993-09-30 Imperial Cancer Research Technology Limited Compounds
US5733880A (en) * 1993-09-30 1998-03-31 Napier University Ventures Limited Anthracene derivatives for use as anticancer agents
WO1999002124A2 (en) * 1997-07-10 1999-01-21 Bristol-Myers Squibb Company Direct hair dye compositions and methods containing novel anthraquinone mixtures
US5961664A (en) * 1997-07-10 1999-10-05 Bristol-Myers Squibb Company Direct hair dye compositions and methods containing novel anthraquinone mixtures
WO1999002124A3 (en) * 1997-07-10 2005-03-24 Bristol Myers Squibb Co Direct hair dye compositions and methods containing novel anthraquinone mixtures

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