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WO2001047485A1 - Agent for colouring fibres containing keratin - Google Patents

Agent for colouring fibres containing keratin Download PDF

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Publication number
WO2001047485A1
WO2001047485A1 PCT/EP2000/012821 EP0012821W WO0147485A1 WO 2001047485 A1 WO2001047485 A1 WO 2001047485A1 EP 0012821 W EP0012821 W EP 0012821W WO 0147485 A1 WO0147485 A1 WO 0147485A1
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WO
WIPO (PCT)
Prior art keywords
amino
acid
amιno
group
hydroxy
Prior art date
Application number
PCT/EP2000/012821
Other languages
German (de)
French (fr)
Inventor
Hinrich Möller
Doris Oberkobusch
Horst Höffkes
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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 Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to AU20114/01A priority Critical patent/AU2011401A/en
Publication of WO2001047485A1 publication Critical patent/WO2001047485A1/en

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Classifications

    • 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
    • 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

Definitions

  • the invention relates to an agent for dyeing keratin-containing fibers, in particular human hair, which contains benzofurazanes or their N-oxides, and to a method for dyeing keratin-containing fibers, in particular human hair
  • keratin fibers for example hair, wool or furs
  • either direct dyes or oxidation dyes which result from the oxidative coupling of one or more developer components with one another or with one or more coupler components, are generally used as coupler and developer components also referred to as oxidation dye precursors
  • Special representatives are, for example, p-phenylenediamine, p-toluenediamine, 2,4,5,6-tetraaminopy ⁇ midin, p-aminophenol, N, N-B ⁇ s- (2-hydroxyethyl) -p-phenylened ⁇ am ⁇ n, 2- (2.5 - D ⁇ am ⁇ nophenyl) -ethanoi, 2- (2,5-D ⁇ am ⁇ nophenoxy) -ethanol, 1-phenyl-3-carboxyam ⁇ do-4-amino-pyrazolon-5, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-Hydroxy-methyl-4-aminophenol, 2-hydroxy-4,5,6-tr ⁇ am ⁇ nopy ⁇ m ⁇ d ⁇ n, 2,4-d ⁇ hydroxy-5,6-d ⁇ am ⁇ nopy- nmidine and 2,5,6-tr ⁇ am ⁇ no-4-hydroxypy ⁇ m ⁇ d ⁇ n
  • M-Phenylenediamined ⁇ vate, naphthols, resorcinol and resorcindenvate, pyrazolones, m-aminophenols and substituted py ⁇ dinedevices are generally used as coupler components.
  • Oxidation dyes With oxidation dyes it is possible to achieve intensive dyeings with good fastness properties, but the development of the color usually takes place under the influence of oxidizing agents such as BH 2 0 2 , which in some cases can damage the fiber. Furthermore, some oxidation dye precursors or certain mixtures of Oxidation dye precursors sometimes have a sensitizing effect on people with sensitive skin. Direct dyes are applied under gentler conditions, but their disadvantage is that the dyeings often have insufficient fastness properties
  • the colorants may have no or only a very low sensitization potential
  • the invention relates to an agent for coloring keratin-containing fibers, in particular human hair, containing at least one benzofurazane with the formula I or its N-oxide,
  • R ' is a hydrogen atom or halogen atom
  • R 2 is a hydrogen atom, a nitro, sulfo, sulfonate or sulfonamide group, in which the nitrogen can be substituted by C alkyl or hydroxyalkyl groups, which together with the nitrogen atom can also form a heterocyclic ring,
  • R 3 and R 4 are hydrogen, halogen, C, 4 alkyl, C,. 4 -alkoxy or hydroxy-C, 4 -alkyl group, a hydroxy, nitro, amino group, which may be substituted by C, ⁇ - alkyl groups, or C, 4 -acyl group, both of which together can form a fused aromatic ring with the proviso that at least one of the radicals R 1 to R 4 is a halogen atom
  • Keratin-containing fibers are to be understood as meaning wool, furs, feathers and in particular human hair.
  • the colorants according to the invention can also be used to dye other natural fibers such as cotton, jute, sisal, linen or silk, modified natural fibers such as regenerated cellulose nitro-, Alkyl or hydroxyalkyl or acetyl cellulose and synthetic fibers such as polyamide, polyacrylonitrile, polyurethane and polyester fibers can be used
  • the compounds with the formula I are largely known from the literature, are commercially available or can be prepared by known synthetic processes.
  • the N-oxides of the benzofurazanes with the formula I are also referred to as benzofuroxanes
  • the compounds of the formula I are preferably selected from 7-chloro-4-nitrobenzofurazane, 7-fluoro-4-nitrobenzofurazane, 7-chloro-benzofurazane-4-sulfonic acid, ammonium salt, 7-fluoro-benzofurazane-4-sulfonic acid, Ammonium salt, 7-chloro-benzofurazan-4-sulfonamide, 7-chloro-4-morpholosnosulfonyl-, 7-chloro-4-dimethylaminosulfonyl-, 7-fluoro-4-dimethylamosulfonylbenzofurazane, 5-fluorobenzofuroxane, 5-chloro-benzofuroxane 7-chloro-benzofuroxane, 4,6-dichlorobenzofuroxane, 5-chlorobenzofurazane and any mixtures thereof
  • benzofurazanes or their N-oxides with the formula I are preferably used in the agents according to the invention in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the total colorant. They can be used as direct agents Colorants or in the presence of customary oxidation dye precursors are used
  • Colorants which contain benzofurazanes with the formula I or their N-oxides alone as the coloring component are preferably used for lighter colorations.
  • Colorings with an even higher brilliance and improved fastness properties (light fastness, fastness to washing, rubbing fastness) over a wide range of shades from brown-yellow to brown-orange, brown-red , light brown, medium brown, dark brown, dark purple to blue-black and black are achieved if the compounds of the formula I used according to the invention together with at least one further component (hereinafter referred to as component B), selected from compounds having a primary or secondary amino group or hydroxyl group, selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds, amino acids, oligopeptides and / or CH-active compounds composed of 2 to 9 amino acids.
  • component B further component selected from compounds having a primary or secondary amino group or hydroxyl group, selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds, amino acids,
  • reaction products which are reaction products of benzofurazanes of the formula I or their N-oxides with the compounds of component B mentioned as direct colorants.
  • reaction products can, for example, be stoichiometrically by briefly heating the two components Amounts in an aqueous neutral to weakly alkaline medium are obtained, they either precipitate out of the solution as a solid or are isolated therefrom by evaporation of the solution.
  • the reaction products can also be used in combination with other dyes or dye precursors
  • Suitable compounds with a primary or secondary amino group as component B are, for example, primary aromatic amines such as N, N-dimethyl-, N, N-dimethyl-, N- (2-hydroxyethyl) -N-ethyl-, N, N- B ⁇ s- (2-hydroxyethyl) -, N- (2-methoxyethyl-), 2,3-, 2,4-, 2,5-d ⁇ chloro-p-phenylenediamine, 2-chloro-p-phenylenediamine, 2,5- D ⁇ hydroxy-4-morphoi ⁇ noan ⁇ i ⁇ n-d ⁇ hydro- bromide, 2-, 3-, 4-aminophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, o-, p-phenylenediamine, o-toluenediamine, 2.5 -D ⁇ am ⁇ notoluol, -phenoi, - phenethol, 4-amino-3
  • R 6 , R 7 , R ⁇ , R 9 and R 10 represent hydrogen, a hydroxyl or an amino group, which are formed by
  • C 1 _ 4 alkyl, C 1 . 4- hydroxyalkyl, or C 1 _ 4 alkoxy-C 1 . 4 alkyl groups can be substituted, and
  • P for a direct bond a saturated or unsaturated carbon chain with 1 to 4 carbon atoms, optionally substituted by hydroxyl groups, a carbonyl, sulfonyl or imino group, an oxygen or sulfur atom, or a group with the formula
  • Y is a direct bond, a CH 2 or CHOH group
  • Suitable nitrogen-containing heterocyclic compounds are e.g. B. 2-, 3-, 4-amino, 2- amino-3-hydroxy, 2,6-dimo, 2,5-dimo, 2,3-dimo, 2-dimethylamo-5-amoo -, 2-Methylam ⁇ no-3-amino-6-methoxy-, 2,3-dimo-6-methoxy-, 2,6-dimethoxy-3,5-dia-mino-, 2,4,5-tri-amino-, 2,6-dihydroxy-3,4-dimethylpyr ⁇ d ⁇ n, 2,4-dihydroxy-5,6-dimethyl-, 4,5,6-triamino-, 4-hydroxy-2,5,6-tri-amino, 2-hydroxy -4,5,6-tr ⁇ am ⁇ no-, 2,4,5,6-tetraam ⁇ - ⁇ o-, 2-methylam ⁇ no-4,5,6-tr ⁇ am ⁇ no-, 2,4-, 4,5-d ⁇ am ⁇ no
  • heterocyclic compounds which can be found in DE-U1-299 08 573 disclosed hydroxypyrimidines can be used.
  • the abovementioned compounds can be used both in free form and in the form of their physiologically acceptable salts, for example as salts of inorganic acids, such as hydrochloric or sulfuric acid
  • Suitable aromatic hydroxy compounds are, for example, 2-, 4-, 5-methylresorcin, 2,5-dim-methylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, pyrogallol, phioroglucin, hydroxyhydroquinone, 2-, 3-, 4-methoxy , 3-dimethylamino, 2- (2-hydroxyethyl) -, 3,4-methylenedoxoxyphenol, 2,4-, 3,4-dihydroxybenzoic acid, phenylacetic acid, gallic acid, 2,4,6-tetrahydroxybenzoic acid, acetophenone, 2-, 4-chlororesorc ⁇ n, 1-naphthol, 1, 5-, 2,3-, 2,7-dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid, 3,6-dihydroxy-2 , 7-naphthal ⁇ nsulfonsaure
  • Preferred amino acids are all naturally occurring and synthetic ⁇ -amino acids, for example the amino acids accessible by hydrolysis from vegetable or animal proteins, for example collagen, keratin casein, elastin, soy protein, wheat gluten or almond protein. Both acidic and alkaline reactions can occur Amino acids are used. Preferred amino acids are arginine, histidine, tyrosine, phenylalanine. DOPA (dihydroxyphenylalanine), ornithine, lysine and tryptophan. But also other amino acids, such as 6-aminocaproic acid, can be used
  • the oligopeptides can be naturally occurring or synthetic oligopeptides, but also the oligopeptides contained in polypeptide or protein hydrolyzates, provided they have sufficient water solubility for use in the colorants according to the invention.
  • examples include glutathione or those in the hydrolysates of collagen, Keratin, casem, elastin, soy protein, wheat gluten or almond protein containing oligopeptides are preferred.
  • Use together with compounds having a primary or secondary amino group or with aromatic hydroxy compounds is preferred
  • CH-active compounds which may be mentioned are 1, 2,3,3-tetramethyl-3H-indolumium, 1, 2,3,3-tetramethyl-3H-indolum-p-toluenesulfonate, 1, 2,3,3-tetramethyl - 3H- ⁇ dol ⁇ um methanesulfonate, Fischer's base (1, 3,3-tr ⁇ methyl-2-methylen ⁇ ndol ⁇ n), 2,3-dimethyl-benzothiazolium iodide, 2,3-dimethyl-benzoth ⁇ azol ⁇ um-p-toluenesulfonate, 1, 2-dimethyl-thyl -naphtho [1, 2-d] th ⁇ azol ⁇ um-p-toluenesulfonate, 1-ethyl-2-methyl-naphtho [1, 2-d] th ⁇ azol ⁇ um-p-toluenesulfonate, rhodanine, rho
  • the compounds of component B are particularly preferably selected from the group consisting of N- (2-hydroxyethyl) -N-ethyl-, 2-chloro-p-phenylenediamine, N, N-B ⁇ s- (2-hydroxyethyl) -p-phenylenediamine , 4-aminophenol, p-phenylenediamine, 2- (2,5-diminophenyl) ethanol, 2,5-diminotoluene, 3,4-methylenedoxyanol, 2-amino-4- (2-hydroxyethylamino) ananol , 2- (2,4-diminophenoxy) ethanol, 3-amino-2,4-dichloro, 2-methyl-5-amino, 3-methyl-4-amino, 2-methyl-5- (2nd -hydroxyethylam ⁇ no) -, 2-methyl-5-amino-4-chloro, 6-methyl-3-amino-2-chloro, 2-amino-methyl-4-a
  • the above-mentioned compounds of component B can be used in an amount of 0.03 to 65, in particular 1 to 40 mmol, in each case based on 100 g of the total colorant. Furthermore, it can be particularly preferred according to the invention to use the compound of the formula I and to use the compound of component B in a molar ratio of 2 1 to 1 2, in particular approximately equimolar, when using compounds of component B which contain one or more amino groups, the compounds of formula I on the one hand and the compounds of component B on the other hand are preferred in such Quantities used that the sum of the number of carbonyl groups of the compounds of formula I and the sum of the number of amino groups of the compounds of component B in a ratio of 2 1 to 1 2
  • the agents according to the invention can additionally contain color enhancers.
  • the color enhancers are preferably selected from the group consisting of Pipe ⁇ din P ⁇ per ⁇ d ⁇ n-2-carboxylic acid, Pipe ⁇ din- 3-carboxylic acid, P ⁇ per ⁇ d ⁇ n-4-carboxylic acid, Pyndin, 2-hydroxypyridium, 3- Hydroxypy ⁇ d ⁇ n, 4-hydroxypy ⁇ din, imidazole, 1-methyl ⁇ m ⁇ dazol, histidine, pyrrolidine, proline, pyrrolidone, pyrrolidone-5-carboxylic acid, pyrazole, 1, 2,4-tr ⁇ azole, piperazidine, their derivatives and their physiologically acceptable salts
  • the above-mentioned color enhancers can be used in an amount of 0.03 to 65, in particular 1 to 40 mmol, based in each case on 100 g of the total colorant
  • oxidizing agents for example BH 2 0 2
  • it may be desirable to add hydrogen peroxide or other oxidizing agents to the agents according to the invention to achieve the shades that are lighter than the keratin-containing fibers to be colored are generally used in an amount of 0.01 to 6% by weight, based on the application solution.
  • the colorants according to the invention contain, in addition to the compounds contained according to the invention, customary direct dyes, for example from the group of the nitrophenylenediamines, nitroaminophenols, anthraquinones or indophenols, such as those with the international names or trade names HC Yeilow, for further modification of the color shades 2, HC Yeilow 4, HC Yeilow 6, Basic Yeilow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16 and Basic Brown 17 known compounds as well as picramic acid 2-amino-6-chloro-4-non-trophenol, 4-amino-2-non -ododiphenylamine-2'-carboxylic acid, 6-non-1, 2,3,4-tetrahydr
  • preparations according to the invention can also contain naturally occurring dyes such as, for example, henna red, henna neutral, henna black, chamomile blood, sandalwood, black tea, faulbaum ⁇ de, sage, blue wood, madder root, catechu, sedre and alkanna root
  • naturally occurring dyes such as, for example, henna red, henna neutral, henna black, chamomile blood, sandalwood, black tea, faulbaum ⁇ de, sage, blue wood, madder root, catechu, sedre and alkanna root
  • oxidation dye precursors or the optional direct dyes each represent uniform compounds. Rather, in the colorants according to the invention, due to the manufacturing processes for the individual dyes, further components may be present in minor amounts, provided that these do not adversely affect the color result or for other reasons, e.g. toxicological, must be excluded
  • the colorants according to the invention already give intense colorations at physiologically acceptable temperatures of below 45 ° C. They are therefore particularly suitable for coloring human hair.
  • the colorants can usually be incorporated into a water-containing cosmetic carrier.
  • Suitable water-containing cosmetic carriers are e.g. B creams, Emulsione ⁇ , gels or surfactant-containing foaming solutions such.
  • B Shampoos or other preparations that are suitable for use on the keratin fibers If necessary, it is also possible to incorporate the colorants into anhydrous carriers
  • the colorants according to the invention can contain all of the active ingredients, additives and auxiliaries known in such preparations.
  • the colorants contain at least one surfactant, and in principle both anionic and zwitter ⁇ onic, ampholytic, nonionic and cationic surfactants are suitable.
  • Suitable anionic surfactants in preparations according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as, for example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group about 10 to 22 carbon atoms
  • the molecule may contain glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups.
  • suitable anionic surfactants are in the form of the sodium, potassium and ammonium and the mono- , Di- and T ⁇ alkanolammoniumsalze with 2 or 3 carbon atoms in the alkanol group,
  • Ether carboxylic acids of the formula R-0- (CH 2 -CH 2 0) x -CH 2 -COOH, in which R is a linear alkyl group with 10 to 22 C atoms and x 0 or 1 to 16, acyl sarcosides with 10 to 18 Carbon atoms in the acyl group, acyltaundes with 10 to 18 carbon atoms in the acyl group, acyl isethionates with 10 to 18 carbon atoms in the acyl group,
  • Sulfosuccinic acid mono- and dialkyl esters with 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl esters with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkane sulfonates with 12 to 18 carbon atoms, linear alpha-olefin sulfonates with 12 to 18 carbon atoms, alpha-sulfofatty acid methyl ester of fatty acids with 12 to 18 carbon atoms, Alkyl sulfates and alkyl polyglycol ether sulfates of the formula R-0 (CH 2 -CH 2 0) x -S0 3 H, in which R is a preferably linear alkyl group with 10 to 18 C atoms and x 0 or 1
  • Esters of tartaric acid and citric acid with alcohols which are adducts of about 2 to 15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols with 8 to 22 carbon atoms
  • Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and in particular salts of saturated and in particular unsaturated C 8 -C 22 carboxylic acids, such as oleic acid, stearic acid , Isostearic acid and palmitic acid
  • Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one -COO ( ⁇ - or -S0 3 (" 'group in the molecule.
  • Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycate, for example the cocoalkyl-dimethylammomumglycinate, N-acyl-aminopropyl-N, N-dimethylamomomumglycinate, for example the cocoacylaminopropyl-dimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl-ole 18 carbon atoms in the alkyl or acyl group and cocoacylaminoethylhydroxyethylcarboxymethyl glycate
  • a preferred zwitterionic surfactant is the fatty acid amide de ⁇ vat known
  • Ampholytic surfactants are understood to mean those surface-active compounds which, in addition to a C 8 18 -alkyl or -acyl group, contain at least one free amino group and at least one -COOH or -S0 3 H group in the molecule and are capable of forming internal salts.
  • ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkyaminobutyric acids, N-alkylimidodipropionic acidic, N-hydroxyethyl-N-alkylamidopropylgly ⁇ e, N-alkyltaunne, N-alkylsarcosines, 2-alkylammopropionic acids and alkylaminoacetic acids, each with about 8 to 18 carbon atoms in the alkyl group.
  • Particularly preferred ampholytic surfactants are N-cocosalkylaminopropionate, cocoacylaminoethylaminopropionate the C 12 18 acyl sarcos ⁇ n
  • Nonionic surfactants contain, for example, a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups as the hydrophilic group. Examples of such compounds are
  • KAT ionic surfactants are in particular quaternary ammonium compounds are preferred as Ammo ⁇ iumhalogenide chlo ⁇ de Alkyltrimethylammoniumchlo ⁇ de, dialkyldimethylammonium and T ⁇ alkylmethylammoniumchlo ⁇ de, z B Cetylt ⁇ methylammoniumchlond, Stearyltnmethylammoniumchiorid, Distearyldimethylammoniumchlo ⁇ d, lauryl dimethyl ammoniumchlo ⁇ d, lauryldimethylbenzylammonium chloride and T ⁇ cetylnnethylammonium- chlo ⁇ d More inventively useful cationic surfactants are the quaternized protein hydrolyzates
  • cationic silicone fluids such as, for example, the commercially available products Q2-7224 (manufacturer Dow Corning, a stabilized T ⁇ -methylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone) , SM-2059 (manufacturer General Electric), SLM-55067 (manufacturer Wacker) and Ab ⁇ l ® -Quat 3270 and 3272 (manufacturer Th Goldschmidt, diquaternary polydimethylsiloxanes, Quatem ⁇ um-80)
  • Alkylamidoamines especially fatty acid amidoamines such as the stearylamidopropyldimethylamine available under the name Tego Am ⁇ d ® S 18, are characterized not only by a good conditioning effect, but also by their good biodegradability
  • esters such as the methylhydroxy- marketed under the trade Stepantex® ® are alkyldialkoyloxyalkylammoniummethosulfate
  • quaternary sugar derivative that can be used as a cationic surfactant is the commercial product Glucquat ® 100, according to the CTFA nomenclature a "lauryl methyl gluceth-10 hydroxypropyl dimonium chloride"
  • the compounds with alkyl groups used as surfactants can in each case be uniform substances. However, it is generally preferred to use native vegetable or animal raw materials in the production of these substances, so that substance mixtures with different alkyl chain lengths depending on the respective raw material are obtained
  • both products with a "normal” homolog distribution and those with a narrow homolog distribution can be used.
  • "Normal" homolog distribution is understood to mean mixtures of homologs Which are obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts.
  • narrow homolog distributions are obtained if, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxide hydroxides or -alcoholates are used as products with catalysts narrow homolog distribution may be preferred
  • non-ionic polymers such as, for example, vinyl pyrrolidone / vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone / vinyl acetate copolymers and polysiloxanes
  • cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyldiallylammonium chloride methyldimethylethyldimethylethyldimethylolidylethyldimethylethyldiamidyldimethyloloxymethyllaminophenylethylpolyamidyldiamethyldiamidylethyldiamidylethylpolyamidylethyldimethylamidylethylpolyamidylethyldimethylamidylethylpolyamidyldimethyllaminophenylethylpolymer methacrylate-
  • Thickeners such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, for example methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such as bentonite or fully synthetic hydrocolloids such as polyvinyl alcohol,
  • Structurants such as glucose and maleic acid, hair-conditioning compounds such as phosphohpides, for example soy lecithin, egg lecithin and cephaiins, and silicone oils,
  • Protein hydrolyzates in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolyzates, perfumes, dimethyl isosorbide and cyclodextins,
  • Solubilizers such as ethanol, isopropanol, ethylene glycol, propylene glycol, Glycenn and diethylene glycol,
  • Anti-dandruff agents such as piroctone olamine and zinc omadine, other substances for adjusting the pH value,
  • Active substances such as panthenol, pantothenic acid, allantoin, pyrrolidone carboxylic acids and their salts, plant extracts and vitamins, Choleste ⁇ n, light stabilizers,
  • Consistency enhancers such as sugar esters, polyol esters or polyol alkyl ethers, fats and waxes such as walrus, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters, fatty acid alkanolamides,
  • Swelling and penetration substances such as glycene, propylene glycol monoethyl ether, carbonates, hydrogecarbonates, guanidines, ureas and primary, secondary and tertiary phosphates, imidazoles, tinines, pyrrole, opacifiers such as latex,
  • Pearlescent agents such as ethylene glycol mono- and distearate
  • Blowing agents such as propane-butane mixtures, N 2 0, dimethyl ether, C0 2 and air and antioxidants
  • constituents of the water-containing carrier are used to produce the colorants according to the invention in amounts customary for this purpose, for example emulsifiers are used in concentrations of 0.5 to 30% by weight and thickeners are used in concentrations of 0.1 to 25% by weight of the total colorant used
  • Suitable metal salts are, for example, formates, carbonates, halides, sulfates, butyrates, valenates, capronates, acetates, lactates, glycolates, tartrates, citrates, gluconates, propionates, phosphates and Phosphonates of alkali metals, such as potassium, sodium or lithium, alkaline earth metals, such as magnesium, calcium, strontium or barium, or of aluminum, manganese, iron, cobalt, copper or zinc, where Natnumace- tat, lithium bromide, calcium bromide, Cal ⁇ umgiuconat, Zinkchlo ⁇ d, zinc sulfate , Magnesium chloride, magnesium sulfate, ammonium carbonate chloride and acetate are preferred. These salts are preferably present in an amount of 0.03 to 65, in particular 1 to 40, mmol, based
  • the pH of the ready-to-use color preparations is usually between 2 and 11, preferably between 5 and 10
  • Another object of the present invention relates to the use of benzofurazanes with the formula I or their N-oxides,
  • R 2 is a hydrogen atom, a nitro, sulfo, sulfonate or sulfonamide group in which the nitrogen can be substituted by C 1-4 alkyl or hydroxyalkyl groups, which together with the nitrogen atom can also form a heterocyclic ring,
  • R 3 and R 4 represent a hydrogen, halogen atom, a C 1-4 alkyl, C 1 . 4 -alkoxy or hydroxy-C ⁇ alkyl group, a hydroxy, nitro, amino group, which can be substituted by C ⁇ - alkyl groups, or C ⁇ -acyl group, both of which together can form a fused aromatic ring, mean with with the proviso that at least one of the radicals R 1 to R 4 is a halogen atom, as a coloring component in oxidation hair colorants
  • Yet another object of the present invention relates to a process for coloring keratin-containing fibers, in particular human hair, in which a colorant comprising A) at least one benzofurazane with the formula I or its N-oxide,
  • R 1 is a hydrogen atom or halogen atom
  • R 2 is a hydrogen atom, a nitro, sulfo, sulfonate or sulfonamide group in which the nitrogen can be substituted by C 1-4 alkyl or hydroxyalkyl groups, which together with the nitrogen atom can also form a heterocyclic ring
  • R 3 and R 4 are a hydrogen, halogen atom, a C 1-4 alkyl, C 1 4 -alkoxy or hydroxy-C, 4- alkyl group, a hydroxy, nitro, amino group, which is substituted by C, _ 4 - alkyl groups can be substituted, or C, 4- acyl group, both of which can also together form a fused-on aromatic ring, with the proviso that at least one of the radicals R 1 to R 4 is a halogen atom, and
  • the benzofurazanes of the formula I or their N-oxides and the compounds of component B can either be applied to the hair simultaneously or else in succession, it being irrelevant which of the two components is applied first.
  • the optionally contained ammonium or metal salts can may be added to the first or the second component Between the application of the first and the second component there may be a time interval of up to 30 minutes. A pretreatment of the fibers with the salt solution is also possible
  • the benzofurazanes of the formula I or their N-oxides and the compounds of component B can either be stored separately or together, either in a liquid to pasty preparation (water or water-free) or as a dry powder If the components are stored together in a liquid preparation, this should be largely water-free to reduce a reaction of the components.
  • the reactive components are only intimately mixed with one another immediately before use Usually a defined amount of warm (30 to 80 ° C) water is added to the application and a homogeneous mixture is produced.
  • a slurry of 5 mmol of a benzofurazane of the formula I, optionally 5 mmol of an oxidanone dye precursor of component B and 5 mmol of sodium acetate and a drop of a 20% strength fatty alkyl ether sulfate solution in 50 ml of water at 50 ° C. were prepared.
  • the slurries were mixed together after cooling to 30 ° C. and adjusted to a pH of 9 with dilute NaOH or hydrochloric acid
  • a strand of 90% gray, untreated human hair was introduced into this color mixture at 30 ° C. for 30 minutes.
  • the strand was then rinsed with lukewarm water for 30 seconds, dried with warm air and then combed out
  • the color depth was rated on the following scale

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Abstract

The invention relates to an agent for colouring fibres containing keratin, especially human hair. The agents contain at least one benzofurazane of formula (I) or its N-oxide, R1 being a hydrogen atom or a halogen atom, R2 being a hydrogen atom, a nitro, sulfo-, sulfonate or sulfonamide group in which the nitrogen can be substituted by C¿1-4?-alkyl- or hydroxyalkyl groups which can also form a heterocyclic ring with the nitrogen atom; R?3 and R4¿ being a hydrogen atom or a halogen atom, a C¿1-4?-alkyl-, C1-4alkoxy- or hydroxy-C1-4-alkyl group, a hydroxy-, nitro- or amino group which can be substituted by C1-4-alkyl groups, or a C1-4-acyl group, the two groups also being able to form a fused aromatic ring together, on the condition that at least one of the radicals R?1 to R4¿ is a halogen atom.

Description

"Mittel zum Farben von keratinhaltigen Fasern" "Means for dyeing keratin fibers"
Die Erfindung betrifft ein Mittel zum Farben von keratinhaltigen Fasern, insbesondere menschlichen Haaren, das Benzofurazane oder deren N-Oxide enthalt, sowie ein Verfahren zum Farben von keratinhaltigen Fasern, insbesondere menschlichen HaarenThe invention relates to an agent for dyeing keratin-containing fibers, in particular human hair, which contains benzofurazanes or their N-oxides, and to a method for dyeing keratin-containing fibers, in particular human hair
Für das Farben von keratinhaltigen Fasern, z B Haaren, Wolle oder Pelzen, kommen im allgemeinen entweder direktziehende Farbstoffe oder Oxidationsfarbstoffe, die durch oxidative Kupplung einer oder mehrerer Entwicklerkompoπenten untereinander oder mit einer oder mehreren Kupplerkomponenten entstehen, zur Anwendung Kuppler- und Ent- wicklerkomponenten werden auch als Oxidationsfarbstoffvorprodukte bezeichnetFor the dyeing of keratin fibers, for example hair, wool or furs, either direct dyes or oxidation dyes, which result from the oxidative coupling of one or more developer components with one another or with one or more coupler components, are generally used as coupler and developer components also referred to as oxidation dye precursors
Als Entwicklerkomponenten werden üblicherweise primäre aromatische Amme mit einer weiteren, in para- oder ortho-Position befindlichen freien oder substituierten Hydroxy- oder Aminogruppe, Diaminopyπdindeπvate, heterocyclische Hydrazone, 4-Amιnopyra- zolondeπvate sowie 2,4,5,6-Tetraamιnopyπmιdιn und dessen Derivate eingesetztPrimary aromatic ames with a further free or substituted hydroxy or amino group in the para or ortho position, diaminopyπdindeπvate, heterocyclic hydrazones, 4-aminopyrazolondeπvate and 2,4,5,6-tetraamnopyπmιdιn and their derivatives are usually used as developer components used
Spezielle Vertreter sind beispielsweise p-Phenylendiamin, p-Toluylendiamin, 2,4,5,6-Te- traaminopyπmidin, p-Aminophenol, N,N-Bιs-(2-hydroxyethyl)-p-phenylendιamιn, 2-(2,5- Dιamιnophenyl)-ethanoi, 2-(2,5-Dιamιnophenoxy)-ethanol, 1-Phenyl-3-carboxyamιdo-4- amιno-pyrazolon-5, 4-Amιno-3-methylphenol, 2-Amιnomethyl-4-amιnophenol, 2-Hydroxy- methyl-4-amιnophenol, 2-Hydroxy-4,5,6-trιamιnopyπmιdιn, 2,4-Dιhydroxy-5,6-dιamιnopy- nmidin und 2,5,6-Trιamιno-4-hydroxypyπmιdιnSpecial representatives are, for example, p-phenylenediamine, p-toluenediamine, 2,4,5,6-tetraaminopyπmidin, p-aminophenol, N, N-Bιs- (2-hydroxyethyl) -p-phenylenedιamιn, 2- (2.5 - Dιamιnophenyl) -ethanoi, 2- (2,5-Dιamιnophenoxy) -ethanol, 1-phenyl-3-carboxyamιdo-4-amino-pyrazolon-5, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-Hydroxy-methyl-4-aminophenol, 2-hydroxy-4,5,6-trιamιnopyπmιdιn, 2,4-dιhydroxy-5,6-dιamιnopy- nmidine and 2,5,6-trιamιno-4-hydroxypyπmιdιn
Als Kupplerkomponenten werden in der Regel m-Phenylendiamindeπvate, Naphthole, Resorcin und Resorcindenvate, Pyrazolone, m-Aminophenole und substituierte Pyπdin- deπvate verwendet Als Kuppiersubstanzen eignen sich insbesondere α-Naphthol, 1 ,5-, 2,7- und 1 ,7-Dιhydroxynaphthalιn, 5-Amιno-2-methylphenol, m-Aminophenol, Resorcin, Resorcinmonomethylether, p-Phenylendiamin, 2,4-Dιamιnophenoxyethanol, 2-Amιno-4- (2-hydroxyethylamιπo)-anιsol (Lehmanns Blau), 1-Phenyl-3-methyl-pyrazolon-5, 2,4-Dι- chlor-3-amιnophenol, 1 ,3-Bιs-(2,4-dιamιnophenoxy)-propan, 2-Chlorresorcιn, 4-Chlorre- sorcin, 2-Chlor-6-methyl-3-amιnophenol, 2-Methylresorcιn, 5-Methylresorcιn, 3-Amιno-6- methoxy-2-methylamιno-pyπdιn und 3,5-Dιamιno-2,6-dιmethoxypyπdιnM-Phenylenediaminedπvate, naphthols, resorcinol and resorcindenvate, pyrazolones, m-aminophenols and substituted pyπdinedevices are generally used as coupler components. Α-Naphthol, 1, 5-, 2,7- and 1, 7- 7- Dιhydroxynaphthalιn, 5-Amιno-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, p-phenylenediamine, 2,4-Dιamιnophenoxyethanol, 2-Amιno-4- (2-hydroxyethylamιπo) -anιsol (Lehmanns Blau), 1-phenyl- 3-methyl-pyrazolone-5, 2,4-di-chloro-3-aminophenol, 1, 3-bis (2,4-diminophenoxy) -propane, 2-chloro-resorcinol, 4-chloro- sorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcin, 5-methylresorcin, 3-amino-6-methoxy-2-methylaminno-pyπdin and 3,5-dimin-2,6-dimethoxypyπdin
Bezüglich weiterer üblicher Farbstoffkomponenten wird ausdrücklich auf die Reihe "Der- matology", herausgeben von Ch Culnan, H Maibach, Verlag Marcel Dekker Ine , New York, Basel, 1986, Bd 7, Ch Zviak, The Science of Hair Care, Kap 7, Seiten 248 - 250 (Direktziehende Farbstoffe), und Kap 8, Seiten 264 - 267 (Oxidationsfarbstoffe), sowie das "Europaische Inventar der Kosmetikrohstoffe", 1996, herausgegeben von der Europaischen Kommission, erhältlich in Diskettenform vom Bundesverband der deutschen Industrie- und Handelsunternehmen für Arzneimittel, Reformwaren und Korperpflegemittel e V , Mannheim, Bezug genommenWith regard to other conventional dye components, reference is expressly made to the "Dermatology" series, edited by Ch Culnan, H Maibach, Verlag Marcel Dekker Ine, New York, Basel, 1986, Vol. 7, Ch Zviak, The Science of Hair Care, Chap. 7, Pages 248 - 250 (direct dyes), and Chap. 8, pages 264 - 267 (oxidation dyes), as well as the "European Inventory of Cosmetic Raw Materials", 1996, published by the European Commission, available in disk form from the Federal Association of German Industry and Commerce for Pharmaceuticals, health products and body care products e V, Mannheim, reference
Mit Oxidatioπsfarbstoffen lassen sich zwar intensive Färbungen mit guten Echtheitseigenschaften erzielen, die Entwicklung der Farbe geschieht jedoch i a unter dem Einfluss von Oxidationsmitteln wie z B H202, was in einigen Fallen Schädigungen der Faser zur Folge haben kann Desweiteren können einige Oxidationsfarbstoffvorprodukte bzw bestimmte Mischungen von Oxidationsfarbstoffvorprodukten bisweilen bei Personen mit empfindlicher Haut sensibilisierend wirken Direktziehende Farbstoffe werden unter schonenderen Bedingungen appliziert, ihr Nachteil liegt jedoch dann, dass die Färbungen häufig nur über unzureichende Echtheitseigenschaften verfugenWith oxidation dyes it is possible to achieve intensive dyeings with good fastness properties, but the development of the color usually takes place under the influence of oxidizing agents such as BH 2 0 2 , which in some cases can damage the fiber. Furthermore, some oxidation dye precursors or certain mixtures of Oxidation dye precursors sometimes have a sensitizing effect on people with sensitive skin. Direct dyes are applied under gentler conditions, but their disadvantage is that the dyeings often have insufficient fastness properties
Die Verwendung der unten naher beschriebenen Benzofurazane zum Farben von keratinhaltigen Fasern ist bislang nicht bekanntThe use of the benzofurazans described below for dyeing keratin-containing fibers is not yet known
Aufgabe der vorliegenden Erfindung ist es, Farbemittel für Keratinfasern, insbesondere menschliche Haare, bereitzustellen, die hinsichtlich der Farbtiefe, der Grauabdeckung und den Echtheitseigenschaften qualitativ den üblichen Oxidationshaarfarbemitteln mindestens gleichwertig sind, ohne jedoch unbedingt auf Oxidationsmittel wie z B H202 angewiesen zu sein Darüber hinaus dürfen die Farbemittel kein oder lediglich ein sehr geringes Sensibihsierungspoteπtial aufweisenIt is an object of the present invention to provide colorants for keratin fibers, in particular human hair, which are at least equivalent in quality to the usual oxidation hair colorants in terms of color depth, gray coverage and fastness properties, but without necessarily being dependent on oxidizing agents such as BH 2 0 2 In addition, the colorants may have no or only a very low sensitization potential
Überraschenderweise wurde nun gefunden, dass die ir der Formel I dargestellten Benzofurazane sich auch in Abwesenheit von oxidierendeπ Agentien hervorragend zum Farben von keratinhaltigen Fasern eignen Sie ergebe . Ausfarbungen mit hervor- ragender Brillanz und Farbtiefe und fuhren zu vielfaltigen Farbnuancen Der Einsatz von oxidierenden Agentien soll dabei jedoch nicht prinzipiell ausgeschlossen werdenSurprisingly, it has now been found that the benzofurazanes represented by formula I are outstandingly suitable for dyeing keratin-containing fibers even in the absence of oxidizing agents. Colorings with excellent outstanding brilliance and depth of color and lead to diverse color nuances The use of oxidizing agents should not, however, be excluded in principle
Gegenstand der Erfindung ist ein Mittel zum Farben von keratinhaltigen Fasern, insbesondere menschlichen Haaren, enthaltend mindestens ein Benzofurazan mit der Formel I oder dessen N-Oxid,The invention relates to an agent for coloring keratin-containing fibers, in particular human hair, containing at least one benzofurazane with the formula I or its N-oxide,
Figure imgf000004_0001
Figure imgf000004_0001
in der R' ein Wasserstoffatom oder Halogenatom ist,in which R 'is a hydrogen atom or halogen atom,
R2 ein Wasserstoffatom, eine Nitro, Sulfo-, Sufonat- oder Sulfonamidgruppe, in der der Stickstoff durch C -Alkyl- oder Hydroxyalkylgruppen, die auch zusammen mit dem Stickstoffatom einen heterocyc schen Ring bilden können, substituiert sein kann, ist,R 2 is a hydrogen atom, a nitro, sulfo, sulfonate or sulfonamide group, in which the nitrogen can be substituted by C alkyl or hydroxyalkyl groups, which together with the nitrogen atom can also form a heterocyclic ring,
R3 und R4 ein Wasserstoff-, Halogenatom, eine C, 4-Alkyl-, C,.4-Alkoxy- oder Hydroxy-C, 4-alkylgruppe, eine Hydroxy-, Nitro-, Aminogruppe, die durch C,^- Alkylgruppen substituiert sein kann, oder C, 4-Acylgruppe, wobei auch beide gemeinsam einen ankondensierten aromatischen Ring bilden können, bedeuten mit der Maßgabe, dass mindestens einer der Reste R1 bis R4 ein Halogenatom istR 3 and R 4 are hydrogen, halogen, C, 4 alkyl, C,. 4 -alkoxy or hydroxy-C, 4 -alkyl group, a hydroxy, nitro, amino group, which may be substituted by C, ^ - alkyl groups, or C, 4 -acyl group, both of which together can form a fused aromatic ring with the proviso that at least one of the radicals R 1 to R 4 is a halogen atom
Unter keratinhaltigen Fasern sind Wolle, Pelze, Federn und insbesondere menschliche Haare zu verstehen Die erfindungsgemaßen Farbemittel können prinzipiell aber auch zum Farben anderer Naturfasern, wie z B Baumwolle, Jute, Sisal, Leinen oder Seide, modifizierter Naturfasern, wie z B Regeneratcellulose Nitro-, Alkyl- oder Hydroxyalkyl- oder Acetylcellulose und synthetischer Fasern, wie z B Polyamid-, Polyacrylnitnl-, Polyurethan- und Polyesterfasern verwendet werden Die Verbindungen mit der Formel I sind zum großen Teil literaturbekannt, im Handel erhältlich oder nach bekannten Syntheseverfahren herstellbar Die N-Oxide der Benzofurazane mit der Formel I werden auch als Benzofuroxane bezeichnetKeratin-containing fibers are to be understood as meaning wool, furs, feathers and in particular human hair. In principle, however, the colorants according to the invention can also be used to dye other natural fibers such as cotton, jute, sisal, linen or silk, modified natural fibers such as regenerated cellulose nitro-, Alkyl or hydroxyalkyl or acetyl cellulose and synthetic fibers such as polyamide, polyacrylonitrile, polyurethane and polyester fibers can be used The compounds with the formula I are largely known from the literature, are commercially available or can be prepared by known synthetic processes. The N-oxides of the benzofurazanes with the formula I are also referred to as benzofuroxanes
Vorzugsweise sind die Verbindungen mit der Formel I ausgewählt aus 7-Chlor-4-nιtro- benzofurazan, 7-Fluor-4-nιtrobenzofurazan, 7-Chlor-benzofurazan-4-sulfonsaure, Ammoniumsalz, 7-Fluor-benzofurazan-4-sulfonsaure, Ammoniumsalz, 7-Chlor- benzofurazan-4-sulfonamιd, 7-Chlor-4-morpholιnosulfonyl-, 7-Chlor-4- dimethylaminosulfonyl-, 7-Fluor-4-dιmethylamιnosulfonylbeπzofurazan, 5-Fluor- benzofuroxan, 5-Chlor-benzofuroxan, 7-Chlor-benzofuroxan, 4,6-Dιchlorbenzofuroxan, 5- Chlorbenzofurazan sowie deren beliebigen GemischeThe compounds of the formula I are preferably selected from 7-chloro-4-nitrobenzofurazane, 7-fluoro-4-nitrobenzofurazane, 7-chloro-benzofurazane-4-sulfonic acid, ammonium salt, 7-fluoro-benzofurazane-4-sulfonic acid, Ammonium salt, 7-chloro-benzofurazan-4-sulfonamide, 7-chloro-4-morpholosnosulfonyl-, 7-chloro-4-dimethylaminosulfonyl-, 7-fluoro-4-dimethylamosulfonylbenzofurazane, 5-fluorobenzofuroxane, 5-chloro-benzofuroxane 7-chloro-benzofuroxane, 4,6-dichlorobenzofuroxane, 5-chlorobenzofurazane and any mixtures thereof
Die voranstehend genannten Benzofurazane oder deren N-Oxide mit der Formel I werden vorzugsweise in den erfindungsgemaßen Mitteln in einer Menge von 0,03 bis 65 mmol, insbesondere von 1 bis 40 mmol, bezogen auf 100 g des gesamten Farbemittels, verwendet Sie können als direktziehende Farbemittel oder in Gegenwart von üblichen Oxidationsfarbstoffvorprodukten eingesetzt werdenThe above-mentioned benzofurazanes or their N-oxides with the formula I are preferably used in the agents according to the invention in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the total colorant. They can be used as direct agents Colorants or in the presence of customary oxidation dye precursors are used
Farbemittel, die als färbende Komponente Benzofurazane mit der Formel I oder deren N- Oxide allein enthalten, werden bevorzugt für hellere Färbungen eingesetzt Färbungen mit noch erhöhter Brillanz und verbesserten Echtheitseigenschaften (Lichtechtheit, Waschechtheit, Reibechtheit) über einen weiten Nuancenbereich von braungelb über braunorange, braunrot, hellbraun mittelbraun, dunkelbraun, dunkelviolett bis hin zu blauschwarz und schwarz werden erzielt, wenn die erfindungsgemaß eingesetzten Verbindungen mit der Formel I gemeinsam mit mindestens einer weiteren Komponente (im folgenden Komponente B genannt), ausgewählt aus Verbindungen mit primärer oder sekundärer Aminogruppe oder Hydroxygruppe, ausgewählt aus primären oder sekundären aromatischen Ammen, stickstoffhaltigen heterocyclischen Verbindungen und aromatischen Hydroxyverbindungen, Aminosäuren, aus 2 bis 9 Aminosäuren aufgebauten Oligopeptiden und/oder CH-aktiven Verbindungen, verwendet werden Dies sind einerseits Verbindungen, die für sich alleine keratinhaltige Fasern nur schwach färben und erst gemeinsam mit den Verbindungen der Formel I brillante Färbungen ergeben Andererseits sind darunter aber auch Verbindungen, die bereits als Oxidationsfarbstoffvorprodukte eingesetzt werden In allen Farbemitteln können auch mehrere verschiedene Carbazolaldehyde und/oder - ketone der Formel I gemeinsam zum Einsatz kommen, ebenso können auch mehrere verschiedene Verbindungen der Komponente B gemeinsam verwendet werdenColorants which contain benzofurazanes with the formula I or their N-oxides alone as the coloring component are preferably used for lighter colorations. Colorings with an even higher brilliance and improved fastness properties (light fastness, fastness to washing, rubbing fastness) over a wide range of shades from brown-yellow to brown-orange, brown-red , light brown, medium brown, dark brown, dark purple to blue-black and black are achieved if the compounds of the formula I used according to the invention together with at least one further component (hereinafter referred to as component B), selected from compounds having a primary or secondary amino group or hydroxyl group, selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds, amino acids, oligopeptides and / or CH-active compounds composed of 2 to 9 amino acids. These are on the one hand Compounds which only weakly dye fibers containing keratin on their own and which only produce brilliant colorations together with the compounds of the formula I On the other hand, however, include compounds which are already used as oxidation dye precursors Several different carbazolaldehydes and / or ketones of the formula I can also be used together in all colorants, and several different compounds of component B can also be used together
Unter die voranstehend beschriebene Ausfuhrungsform fallt auch die Verwendung von solchen Substanzen, die Reaktionsprodukte von Benzofurazanen der Formel I oder deren N-Oxide mit den genannten Verbindungen der Komponente B darstellen, als direktziehende Farbemittel Derartige Reaktionsprodukte können z B durch kurzes Erwarmen der beiden Komponenten in stochiometπschen Mengen in wassrigem neutralen bis schwach alkalischen Milieu erhalten werden, wobei sie entweder als Feststoff aus der Losung ausfallen oder durch Eindampfen der Losung daraus isoliert werden Die Reaktionsprodukte können auch in Kombination mit anderen Farbstoffen oder Farbstoffvorprodukten eingesetzt werdenThe embodiment described above also includes the use of such substances which are reaction products of benzofurazanes of the formula I or their N-oxides with the compounds of component B mentioned as direct colorants. Such reaction products can, for example, be stoichiometrically by briefly heating the two components Amounts in an aqueous neutral to weakly alkaline medium are obtained, they either precipitate out of the solution as a solid or are isolated therefrom by evaporation of the solution. The reaction products can also be used in combination with other dyes or dye precursors
Geeignete Verbindungen mit primärer oder sekundärer Aminogruppe als Komponente B sind z B primäre aromatische Amme wie N,N-Dιmethyl-, N,N-Dιethyl-, N-(2-Hydroxy- ethyl)-N-ethyl-, N,N-Bιs-(2-hydroxyethyl)-, N-(2-Methoxyethyl-), 2,3-, 2,4-, 2,5-Dιchlor-p- phenylendiamin, 2-Chlor-p-phenylendιamιn, 2,5-Dιhydroxy-4-morphoiιnoanιiιn-dιhydro- bromid, 2-, 3-, 4-Amιnophenol, 2-Amιnomethyl-4-amιnophenol, 2-Hydroxymethyl-4- aminophenol, o-, p-Phenylendiamin, o-Toluylendiamin, 2,5-Dιamιnotoluol, -phenoi, - phenethol, 4-Amιno-3-methylphenol, 2-(2,5-Dιamιnophenyl)-ethanol, 2,4-Dιamιnophen- oxyethaπol, 2-(2,5-Dιamιnophenoxy)-ethanol, 4-Methylamιno-, 3-Amιno-4-(2'-hydroxy- ethyloxy)-, 3,4-Methylendιamιno-, 3,4-Methylendιoxyanιlιn, 3-Amιno-2,4-dιchlor-, 4-Me- thylamino-, 2-Methyl-5-amιno-, 3-Methyl-4-amιno-, 2-Methyl-5-(2-hydroxyethylamιno)-, 6- Methyl-3-amιno-2-chlor-, 2-Methyl-5-amιno-4-chlor-, 3,4-Methylendιoxy-, 5-(2-Hydroxy- ethylamιno)-4-methoxy-2-methyl-, 4-Amιno-2-hydroxymethylphenol, 1 ,3-Dιamιno-2,4-dι- methoxybenzol, 2-, 3-, 4-Amιnobenzoesaure, -phenylessigsaure, 2,3-, 2,4-, 2,5-, 3,4-, 3,5-Dιamιnobenzoesaure, 4-, 5-Amιnosalιcylsaure, 3-Amιno-4-hydroxy-, 4-Amιno-3-hy- droxy-benzoesaure, 2-, 3-, 4-Amιnobenzolsuifonsaure, 3-Amιno-4-hydroxybenzolsulfon- saure, 4-Amιno-3-hydroxynaphthalιn-1 -sulfonsaure, 6-Amιno-7-hydroxynaphthalιn-2-sul- fonsaure, 7-Amιno-4-hydroxynaphthalιn-2-sulfonsaure, 4-Amιno-5-hydroxynaphthaIιn- 2,7-dιsulfonsaure, 3-Amιno-2-naphthoesaure, 3-Amιπophthalsaure, 5-Amιnoιsophthal- saure, 1 ,3,5-, 1 ,2,4-Tπamιπobenzol, 1 ,2,4,5-Tetraamιnobeπzol, 2,4,5-Tπamιπophenol, Pentaaminobenzol, HexaaminoDenzol, 2,4,6-Trιamιnoresorcιn, 4,5-Dιamιnobrenzcate- chin, 4,6-Dιamιnopyrogallol, 3,5-Dιamιno-4-hydroxybrenzcatechιn, aromatische Nitnle, Nitrogruppen-haltige Aminoverbindungen, wie 3-Amιno-6-methylamιno-2-nιtro-pyrιdιn, Pikraminsaure, 1 -(2(3)-Nιtro-4-amιno)-phenylazo-2-hydroxy-7- trimethylammoniumπaphthalin-chlorid, 1 -Hydroxy-2-amιno-4,6-dιnιtro-benzol, 1 -Amιno-2- nιtro-4-bιs-(2-hydroxyethyl)-amιno-benzol, 1-Amιno-2-(2-hydroxyethyl)-amιno-5-nιtro- benzol (HC Yeilow Nr 5), 1-Amιno-2-nιtro-4-(2-hydroxyethyl)-amιnobenzol (HC Red Nr 7), 2-Chloro-5-nιtro-N-hydroxyethyl-1 ,4-phenylendιamιn, 1-(2-Hydroxyethyl)-amιno-2- nιtro-4-amιno-benzol (HC Red Nr 3), 4-Amιno-3-nιtrophenol, 4-Amιno-2-nιtrophenol, 6- Nιtro-o-toluιdιn, 1-Amιno-3-methyl-4-(2-hydroxyethyl)-amιno-6-nιtrobenzol (HC Violet Nr 1), 1-Amιno-2-nιtro-4-(2,3-dιhydroxypropyl)-amιno-5-chlorobenzol an (HC Red Nr 10), 4-Amιno-2-nιtrodιphenyl-amιno-2'-carbonsaure (2-(4-Amιno-2-nιtroanιlιno)-ben- zoesaure), 6-Nιtro-2,5-dιamιnopyπdιn, 2-Amιno-6-chloro-4-nιtrophenol, 2-Amιno-6- chloro-4-nιtrophenol, 1-Amιno-2-(3-nιtrophenylazo)-7-phenylazo-8-naphthol-3,6- disulfonsaure, Dinatπumsalz (Acid blue Nr 29), 1-Amιno-2-(2-hydroxy-4-nιtrophenylazo)- 8-naphthol-3,6-dιsulfonsaure, Dinatπumsalz (Palatinchrome green), 1-Amιno-2-(3-chlor- 2-hydroxy-5-nιtrophenylazo)-8-naphthol-3,6-dιsulfonsaure, Dinatπumsalz (Galhon), 4- Amιno-4'-nιtrostιlben-2,2'-dιsulfonsaure, Dinatπumsalz, 2,4-Dιamιno-3',5'-dιnιtro-2'- hydroxy-5-methyl-azobenzol (Mordant brown 4), 4'-Amιno-4-nιtrodιphenylamιn-2- sulfonsaure, 4'-Amιno-3'-nιtrobenzophenon-2-carbonsaure, 1 -Amιno-4-nιtro-2-(2- nιtrobenzylιdenamιno)-benzol, 2-[2-(Dιethylamιno)-ethylamιno]-5-nιtroanιlιn, 3-Amιno-4- hydroxy-5-nιtrobenzolsulfonsaure, (Hydrat), 3-Amιno-3'-nιtrobιphenyl, 3-Amιno-4-nιtro- acenaphthen 2-Amιno-1-nιtronaphthalιn, 5-Amιno-6-nιtrobenzo-1 ,3-dιoxol, Aniline, insbesondere Nitrogruppen-haltige Aniline, wie 4-Nιtroanιlιn, 2-Nιtroanιiιn, 1 ,4-Dιamιno-2- nitrobenzol, 1 ,2-Dιamιno-4-nιtrobenzol, 1-Amιno-2-methyl-6-nιtrobenzol, 4-Nιtro-1 ,3- phenylendiamin, 2-Nιtro-4-amιno-1-(2-hydroxyethylamιno)-benzol, 2-Nιtro-1-amιno-4- [bιs-(2-hydroxyethyl)-amιno]-beπzol, 4-Amιno-2-nιtrodιphenylamιn-2'-carbonsaure, 2- Amιno-6-chlor-4-nιtrophenol, 1-Amιno-5-chlor-4-(2-hydroyethylamιno)-2-nιtrobenzol, aromatische Aniline bzw Phenole mit einem weiteren aromatischen Rest, wie sie in der Formel II dargestellt sind
Figure imgf000008_0001
Suitable compounds with a primary or secondary amino group as component B are, for example, primary aromatic amines such as N, N-dimethyl-, N, N-dimethyl-, N- (2-hydroxyethyl) -N-ethyl-, N, N- Bιs- (2-hydroxyethyl) -, N- (2-methoxyethyl-), 2,3-, 2,4-, 2,5-dιchloro-p-phenylenediamine, 2-chloro-p-phenylenediamine, 2,5- Dιhydroxy-4-morphoiιnoanιiιn-dιhydro- bromide, 2-, 3-, 4-aminophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, o-, p-phenylenediamine, o-toluenediamine, 2.5 -Dιamιnotoluol, -phenoi, - phenethol, 4-amino-3-methylphenol, 2- (2,5-diminophenyl) ethanol, 2,4-diminophen oxyethanol, 2- (2,5-diminophenoxy) ethanol, 4th -Methylamιno-, 3-amino-4- (2'-hydroxyethyloxy) -, 3,4-methylenediamine-, 3,4-methylenedoxyaniline, 3-amino-2,4-dichloro, 4-methylamino , 2-methyl-5-amino, 3-methyl-4-amino, 2-methyl-5- (2-hydroxyethylamino) -, 6-methyl-3-amino-2-chloro, 2-methyl-5th -amιno-4-chloro, 3,4-methylenedιoxy-, 5- (2-hydroxy-ethylamιno) -4-methoxy-2-methyl -, 4-Amιno-2-hydroxymethylphenol, 1, 3-Dιamιno-2,4-dι- methoxybenzene, 2-, 3-, 4-Amιnobenzoesaure, -phenylacetic acid, 2,3-, 2,4-, 2,5 -, 3,4-, 3,5-Dιamιnobenzoesaure, 4-, 5-Amιnosalιcylsaure, 3-Amιno-4-hydroxy-, 4-Amιno-3-hydroxy-benzoic acid, 2-, 3-, 4-Amιnobenzolsuifonsaure , 3-amino-4-hydroxybenzenesulfonic acid, 4-amino-3-hydroxynaphthalene-1 sulfonic acid, 6-amino-7-hydroxynaphthalene-2-sulphonic acid, 7-amino-4-hydroxynaphthalene-2-sulfonic acid, 4 -Amιno-5-hydroxynaphthaIιn- 2,7-disulfonic acid, 3-Amιno-2-naphthoic acid, 3-Amιπophthalic acid, 5-Amιnoιsophthalic acid, 1, 3,5-, 1, 2,4-Tπamιπobenzol, 1, 2, 4,5-tetra-aminophenol, 2,4,5-t-aminophenol, Pentaaminobenzene, HexaaminoDenzol, 2,4,6-Trιamιnoresorcιn, 4,5-Dιamιnobrenzcate- chin, 4,6-Dιamιnopyrogallol, 3,5-Dιamιno-4-hydroxybrenzcatechιn, aromatic nitrous, nitro group-containing amino compounds, such as 3-amino compounds -methylamιno-2-nιtro-pyrιdιn, picraminic acid, 1 - (2 (3) -nιtro-4-amιno) -phenylazo-2-hydroxy-7-trimethylammoniumπaphthalene chloride, 1 -hydroxy-2-amιno-4,6- dιnιtro-benzene, 1 -Amιno-2-nιtro-4-bιs- (2-hydroxyethyl) -amιno-benzene, 1-Amιno-2- (2-hydroxyethyl) -amιno-5-nιtro-benzene (HC Yeilow No. 5 ), 1-amino-2-nitro-4- (2-hydroxyethyl) aminobenzene (HC Red No. 7), 2-chloro-5-nitro-N-hydroxyethyl-1, 4-phenylenediamine, 1- (2-hydroxyethyl ) -amιno-2- nιtro-4-amιno-benzene (HC Red Nr 3), 4-Amιno-3-nιtrophenol, 4-Amιno-2-nιtrophenol, 6- Nιtro-o-toluιdιn, 1-Amιno-3- methyl-4- (2-hydroxyethyl) amino-6-nitrobenzene (HC Violet No. 1), 1-amino-2-nitro-4- (2,3-dihydroxypropyl) amino-5-chlorobenzene on (HC Red No. 10), 4-Amιno-2-nιtrodιphenyl-amιno-2'-car bonsacid (2- (4-amino-2-non-ionic) -ben- zoic acid), 6-non-2,5-diminopyrin, 2-amino-6-chloro-4-non-trophenol, 2-amino-6-chloro-4 -nιtrophenol, 1-amino-2- (3-nιtrophenylazo) -7-phenylazo-8-naphthol-3,6-disulfonic acid, disodium salt (Acid Blue No. 29), 1-amino-2- (2-hydroxy-4- nιtrophenylazo) - 8-naphthol-3,6-disulfonic acid, Dinatπumsalz (Palatinchrome green), 1-Amιno-2- (3-chloro-2-hydroxy-5-nιtrophenylazo) -8-naphthol-3,6-disulfonic acid, Dinatπumsalz (Galhon), 4-amino-4'-nitro-benzene-2,2'-disulfonic acid, disodium salt, 2,4-dimino-3 ', 5'-diminro-2'-hydroxy-5-methyl-azobenzene (Mordant brown 4th ), 4'-Amιno-4-nιtrodιphenylamιn-2-sulfonic acid, 4'-Amιno-3'-nιtrobenzophenon-2-carboxylic acid, 1 -Amιno-4-nιtro-2- (2-nιtrobenzylιdenamιno) -benzene, 2- [ 2- (Dιethylamιno) -ethylamιno] -5-nιtroanιlιn, 3-Amιno-4-hydroxy-5-nιtrobenzenesulfonic acid, (hydrate), 3-Amιno-3'-nιtrobιphenyl, 3-Amιno-4-nιtro-acenaphthene 2-Amιno -1-nιtronaphthalιn, 5-Amιno-6-nιtrobenzo- 1, 3-dimoxol, anilines, in particular nitro group-containing anilines, such as 4-nitroaniline, 2-nitroaniline, 1,4-dimino-2-nitrobenzene, 1,2-dimino-4-nitrobenzene, 1-amino-2-methyl -6-nitrobenzene, 4-nitro-1,3-phenylenediamine, 2-nitro-4-amino-1- (2-hydroxyethylamino) benzene, 2-nitro-1-amino-4- [bιs- (2-hydroxyethyl ) -amιno] -benπzol, 4-amιno-2-nιtrodιphenylamιn-2'-carboxylic acid, 2-amιno-6-chloro-4-nιtrophenol, 1-amino-5-chloro-4- (2-hydroyethylamιno) -2- nitrobenzene, aromatic anilines or phenols with a further aromatic radical, as shown in formula II
Figure imgf000008_0001
in der R5 für eine Hydroxy- oder eine Aminogruppe, die durch C^-Alkyl-, C^-Hydroxyal- kyl-, C1.4-Alkoxy- oder C1.4-Alkoxy-C,.4-alkylgruppen substituiert sein kann, steht,in the R 5 for a hydroxy or an amino group, which by C ^ alkyl, C ^ hydroxyalkyl, C 1 . 4 -alkoxy- or C 1 . 4 -alkoxy-C ,. 4 -alkyl groups can be substituted,
R6, R7, Rβ, R9 und R10 für Wasserstoff, eine Hydroxy- oder eine Aminogruppe, die durchR 6 , R 7 , R β , R 9 and R 10 represent hydrogen, a hydroxyl or an amino group, which are formed by
C1_4-Alkyl-, C1.4-Hydroxyalkyl,
Figure imgf000008_0002
oder C1_4-Alkoxy-C1.4-alkyl- gruppen substituiert sein kann, stehen, undC 1 _ 4 alkyl, C 1 . 4- hydroxyalkyl,
Figure imgf000008_0002
or C 1 _ 4 alkoxy-C 1 . 4 alkyl groups can be substituted, and
P für eine direkte Bindung, eine gesattigte oder ungesättigte, ggf. durch Hydroxygruppen substituierte Kohlenstoffkette mit 1 bis 4 Kohlenstoffatomen, eine Carbonyl-, Sulfonyl- oder Iminogruppe, ein Sauerstoff- oder Schwefelatom, oder eine Gruppe mit der FormelP for a direct bond, a saturated or unsaturated carbon chain with 1 to 4 carbon atoms, optionally substituted by hydroxyl groups, a carbonyl, sulfonyl or imino group, an oxygen or sulfur atom, or a group with the formula
Z-(CH2-Y-CH2-Z')0 (III)Z- (CH 2 -Y-CH 2 -Z ') 0 (III)
in der Y eine direkte Bindung, eine CH2- oder CHOH-Gruppe bedeutet,in which Y is a direct bond, a CH 2 or CHOH group,
Z und Z' unabhängig voneinander für ein Sauerstoffatom, eine NR11-Gruppe, worin R11 Wasserstoff, eine C,_4-Alkyl- oder eine Hydroxy-C,_4-aikylgruppe bedeutet, die Gruppe 0-(CH2)p-NH oder NH-(CH2)p'-0, worin p und p' 2 oder 3 sind, stehen und o eine Zahl von 1 bis 4 bedeutet, wie beispielsweise 4,4'-Dιamιnostιlben und dessen Hydrochlond, 4,4'-Dιamιnostιlben- 2,2'-dιsulfonsaure-mono- oder -di-Na-Salz, 4-Amιno-4'-dιmethylamιnostιlben und dessen Hydrochlond, 4,4'-Diamιnodιphenylmethan, -sulfid, -sulfoxid, -amin, 4,4'-Diamιnodιphe- nylamιn-2-sulfonsaure, 4,4'-Diamιnobenzophenon, -diphenylether, 3,3',4,4'-Tetraamιno- diphenyl, 3,3',4,4'-Tetraamιno-beπzophenon, 1 ,3-Bis-(2,4-dιamιnophenoxy)-propan, 1 ,8- Bis-(2,5-dιamιnophenoxy)-3,6-dιoxaoctaπ, 1 ,3-Bis-(4-amιnophenylamιno)propan, -2-pro- panol, 1 ,3-Bis-[N-(4-amιnophenyl)-2-hydroxyethylamιno]-2-propanol, N,N-Bis-[2-(4- amιnophenoxy)-ethyl]-methylamιn, N-Phenyl-1 ,4-phenylendιamιn Die vorgenannten Verbindungen können sowohl in freier Form als auch in Form ihrer physiologisch vertraglichen Salze, insbesondere als Salze anorganischer Sauren, wie Salz- oder Schwefelsaure, eingesetzt werdenZ and Z 'independently of one another for an oxygen atom, an NR 11 group in which R 11 is hydrogen, a C, _ 4 -alkyl or a hydroxy-C, _ 4 -aikyl group, the group 0- (CH 2 ) p -NH or NH- (CH 2 ) p '-0, where p and p' are 2 or 3, and o is a number from 1 to 4, such as 4,4'-diminostilbene and its hydrochloride, 4,4 '-Dιamιnostιlben- 2,2'-dιsulfonsaure-mono- or -di-Na salt, 4-Amιno-4'-dιmethylamιnostιlben and its hydrochloride, 4,4'-diamιnodιphenylmethane, sulfide, sulfoxide, amine, 4th , 4'-diamino-nylamine-2-sulfonic acid, 4,4'-diamino-benzophenone, -diphenyl ether, 3,3 ', 4,4'-tetraamine-diphenyl, 3,3', 4,4'-tetraamine-beπzophenone, 1, 3-bis (2,4-diminophenoxy) propane, 1,8-bis (2,5-diminophenoxy) -3,6-dimoxaoctaπ, 1,3-bis (4-aminophenylamino) propane, - 2-propanol, 1,3-bis- [N- (4-aminophenyl) -2-hydroxyethylamino] -2-propanol, N, N-bis- [2- (4-aminophenoxy) ethyl] methylamino, N-phenyl-1,4-phenylenediamine The abovementioned compounds can be used both in free form and in the form of their physiologically acceptable salts, in particular as salts of inorganic acids, such as hydrochloric or sulfuric acid
Geeignete stickstoffhaltige heterocyciische Verbindungen sind z. B. 2-, 3-, 4-Amιno-, 2- Amιno-3-hydroxy-, 2,6-Dιamιno-, 2,5-Dιamιno-, 2,3-Dιamιno-, 2-Dιmethylamιno-5-amιno-, 2-Methylamιno-3-amιno-6-methoxy-, 2,3-Dιamιno-6-methoxy-, 2,6-Dimethoxy-3,5-dιa- mino-, 2,4,5-Trιamιno-, 2,6-Dιhydroxy-3,4-dιmethylpyrιdιn, 2,4-Dιhydroxy-5,6-dιamιno-, 4,5,6-Tπamιno-, 4-Hydroxy-2,5,6-trιamιno-, 2-Hydroxy-4,5,6-trιamιno-, 2,4,5,6-Tetraamι- πo-, 2-Methylamιno-4,5,6-trιamιno-, 2,4-, 4,5-Dιamιno-, 2-Amιno-4-methoxy-6-methyl-py- πmidin, 3,5-Dιamιnopyrazol, -1 ,2,4-tπazol, 3-Amιno-, 3-Amιno-5-hydroxypyrazol, 2-, 3-, 8- Aminochinohn, 4-Amιnochιna!dιn, 2-, 6-Amιnonιcotιnsaure, 5-Amιnoιsochιnolιn, 5-, 6- Aminoindazol, 5-, 7-Amιnobenzιmιdazol, -benzothiazol, 2,5-Dιhydroxy-4-morpholιnoanι n sowie Indol- und Indolindeπvaten, wie 4-, 5-, 6-, 7-Amιnoιndol, 5,6-Dιhydroxyιndol, 5,6- Dihydroxyindolin und 4-Hydroxyιndolιn Weiterhin als heterocyciische Verbindungen können erfindungsgemaß die in der DE-U1-299 08 573 offenbarten Hydroxypyrimidine eingesetzt werden Die vorgenannten Verbindungen können sowohl in freier Form als auch in Form ihrer physiologisch vertraglichen Salze, z B als Salze anorganischer Sauren, wie Salz- oder Schwefelsaure, eingesetzt werdenSuitable nitrogen-containing heterocyclic compounds are e.g. B. 2-, 3-, 4-amino, 2- amino-3-hydroxy, 2,6-dimo, 2,5-dimo, 2,3-dimo, 2-dimethylamo-5-amoo -, 2-Methylamιno-3-amino-6-methoxy-, 2,3-dimo-6-methoxy-, 2,6-dimethoxy-3,5-dia-mino-, 2,4,5-tri-amino-, 2,6-dihydroxy-3,4-dimethylpyrιdιn, 2,4-dihydroxy-5,6-dimethyl-, 4,5,6-triamino-, 4-hydroxy-2,5,6-tri-amino, 2-hydroxy -4,5,6-trιamιno-, 2,4,5,6-tetraamι- πo-, 2-methylamιno-4,5,6-trιamιno-, 2,4-, 4,5-dιamιno-, 2- Amιno-4-methoxy-6-methyl-py- πmidin, 3,5-Dιamιnopyrazol, -1, 2,4-tπazol, 3-Amιno-, 3-Amιno-5-hydroxypyrazole, 2-, 3-, 8- Aminoquinohn, 4-amino-diac, 2-, 6-amino-nicotinic acid, 5-amino-chloro-noline, 5-, 6- amino-indazole, 5-, 7-amino-idazole, benzothiazole, 2,5-di-hydroxy-4-morpholino-nano and Indoline derivatives such as 4-, 5-, 6-, 7-amino-indole, 5,6-dihydroxy-indole, 5,6-dihydroxyindoline and 4-hydroxy-indoline. According to the invention, further heterocyclic compounds which can be found in DE-U1-299 08 573 disclosed hydroxypyrimidines can be used. The abovementioned compounds can be used both in free form and in the form of their physiologically acceptable salts, for example as salts of inorganic acids, such as hydrochloric or sulfuric acid
Geeignete aromatische Hydroxyverbindungen sind z B 2-, 4-, 5-Methylresorcιn, 2,5-Dι- methylresorcin, Resorcin, 3-Methoxyphenol, Brenzkatechin, Hydrochinon, Pyrogallol, Phioroglucin, Hydroxyhydrochinon, 2-, 3-, 4-Methoxy-, 3-Dιmethylamιno-, 2-(2-Hydroxy- ethyl)-, 3,4-Methylendιoxyphenol, 2,4-, 3,4-Dιhydroxybenzoesaure, -phenylessigsaure, Gallussäure, 2,4,6-Tπhydroxybenzoesaure, -acetophenon, 2-, 4-Chlorresorcιn, 1-Naph- thol, 1 ,5-, 2,3-, 2,7-Dιhydroxynaphthalιn, 6-Dιmethylamιno-4-hydroxy-2-naphthalιnsulfon- saure, 3,6-Dιhydroxy-2,7-naphthalιnsulfonsaureSuitable aromatic hydroxy compounds are, for example, 2-, 4-, 5-methylresorcin, 2,5-dim-methylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, pyrogallol, phioroglucin, hydroxyhydroquinone, 2-, 3-, 4-methoxy , 3-dimethylamino, 2- (2-hydroxyethyl) -, 3,4-methylenedoxoxyphenol, 2,4-, 3,4-dihydroxybenzoic acid, phenylacetic acid, gallic acid, 2,4,6-tetrahydroxybenzoic acid, acetophenone, 2-, 4-chlororesorcιn, 1-naphthol, 1, 5-, 2,3-, 2,7-dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid, 3,6-dihydroxy-2 , 7-naphthalιnsulfonsaure
Als Aminosäuren kommen bevorzugt alle natürlich vorkommenden und synthetischen α- Aminosauren in Frage, z B die durch Hydrolyse aus pflanzlichen oder tierischen Proteinen, z B Kollagen, Keratin Casein, Elastin, Sojaprotein, Weizengluten oder Mandelprotein zugänglichen Aminosäuren Dabei können sowohl sauer als auch alkalisch reagierende Aminosäuren eingesetzt werden Bevorzugte Aminosäuren sind Arginin, Histidin, Tyrosin, Phenylalanin. DOPA (Dihydroxyphenylalanin), Ornithin, Lysin und Tryptophan Aber auch andere Aminosäuren, wie z B 6-Amιnocapronsaure, können eingesetzt werdenPreferred amino acids are all naturally occurring and synthetic α-amino acids, for example the amino acids accessible by hydrolysis from vegetable or animal proteins, for example collagen, keratin casein, elastin, soy protein, wheat gluten or almond protein. Both acidic and alkaline reactions can occur Amino acids are used. Preferred amino acids are arginine, histidine, tyrosine, phenylalanine. DOPA (dihydroxyphenylalanine), ornithine, lysine and tryptophan. But also other amino acids, such as 6-aminocaproic acid, can be used
Die Oligopeptide können dabei natürlich vorkommende oder synthetische Oligopeptide, aber auch die in Polypeptid- oder Proteinhydrolysaten enthaltenen Oligopeptide sein, sofern sie über eine für die Anwendung in den erfindungsgemaßen Farbemitteln ausreichende Wasserloslichkeit verfugen Als Beispiele sind z B Glutathion oder die in den Hydrolysaten von Kollagen, Keratin, Casem, Elastin, Sojaprotein, Weizengluten oder Mandelprotein enthaltenen Oligopeptide zu nennen Bevorzugt ist dabei die Verwendung gemeinsam mit Verbindungen mit primärer oder sekundärer Aminogruppe oder mit aromatischen HydroxyverbindungenThe oligopeptides can be naturally occurring or synthetic oligopeptides, but also the oligopeptides contained in polypeptide or protein hydrolyzates, provided they have sufficient water solubility for use in the colorants according to the invention. Examples include glutathione or those in the hydrolysates of collagen, Keratin, casem, elastin, soy protein, wheat gluten or almond protein containing oligopeptides are preferred. Use together with compounds having a primary or secondary amino group or with aromatic hydroxy compounds is preferred
Als CH-aktive Verbindungen können beispielhaft genannt werden 1 ,2,3,3-Tetramethyl- 3H-ιndolιumιodιd, 1 ,2,3,3-Tetramethyl-3H-ιndolιum-p-toluolsulfonat, 1 ,2,3,3-Tetramethyl- 3H-ιπdolιum-methansulfonat, Fischersche Base (1 ,3,3-Trιmethyl-2-methylenιndolιn), 2,3- Dimethyl-benzothiazoliumiodid, 2,3-Dιmethyl-benzothιazolιum-p-toluolsulfonat, 1 ,2-Dιme- thyl-naphtho[1 ,2-d]thιazolιum-p-toluolsulfonat, 1-Ethyl-2-methyl-naphtho[1 ,2-d]thιazolιum- p-toluolsulfonat, Rhodanin, Rhodanιn-3-essιgsaure, 1-Methyl-2-chιnaidιnιum-ιodιd, 1-E- thyl-2-chιnaldιnιum-ιodιd, 1 ,4-Dιmethylchιnolιnιum-ιodιd, Barbitursaure, Thiobar- bitursaure, 1 ,3-Dιmethylthιobarbιtursaure, 1 ,3-Dιethylthιobarbιtursaure, Diethylthiobarbi- tursaure, Oxindol, 3-lndoxylacetat, Cumaranon und 1-Methyl-3-phenyl-2-pyrazolιnonExamples of CH-active compounds which may be mentioned are 1, 2,3,3-tetramethyl-3H-indolumium, 1, 2,3,3-tetramethyl-3H-indolum-p-toluenesulfonate, 1, 2,3,3-tetramethyl - 3H-ιπdolιum methanesulfonate, Fischer's base (1, 3,3-trιmethyl-2-methylenιndolιn), 2,3-dimethyl-benzothiazolium iodide, 2,3-dimethyl-benzothιazolιum-p-toluenesulfonate, 1, 2-dimethyl-thyl -naphtho [1, 2-d] thιazolιum-p-toluenesulfonate, 1-ethyl-2-methyl-naphtho [1, 2-d] thιazolιum-p-toluenesulfonate, rhodanine, rhodanιn-3-essιgsaure, 1-methyl-2 -chιnaidιnιum-ιodιd, 1-E-thyl-2-chιnaldιnιum-ιodιd, 1, 4-Dιmethylchιnolιnιum-ιodιd, barbituric acid, Thiobar-bitursaure, 1, 3-Dιmethylthιobarbotarbarburate, 1 -Indoxylacetat, coumaranone and 1-methyl-3-phenyl-2-pyrazolιnon
Die Verbindungen der Komponente B werden besonders bevorzugt ausgewählt aus der Gruppe bestehend aus N-(2-Hydroxyethyl)-N-ethyl-, 2-Chlor-p-phenylendιamιn, N,N-Bιs- (2-hydroxyethyl)-p-phenylendιamιn, 4-Amιnophenol, p-Phenylendiamin, 2-(2,5-Dιamιno- phenyl)-ethanol, 2,5-Dιamιnotoluol, 3,4-Methylendιoxyanιlιn, 2-Amιno-4-(2-hydroxyethyl- amιno)-anιsol, 2-(2,4-Dιamιnophenoxy)-ethanol, 3-Amιno-2,4-dιchlor-, 2-Methyl-5-amιno-, 3-Methyl-4-amιno-, 2-Methyl-5-(2-hydroxyethylamιno)-, 2-Methyl-5-amιno-4-chlor-, 6-Me- thyl-3-amιno-2-chlor-, 2-Amιnomethyl-4-amιnophenol, 2-Dιethylamιnomethyl-4-amιno- phenol, 2-Dιmethylamιnomethyl-4-amιnophenol, 2,6-Dιchlor-4-amιnophenol, 2-Hydroxy- methyl-4-amιnophenol, 3 4-Methylendιoxyphenol, 3,4-Dιamιnobenzoesaure, 2,5-Dιamι- no-, 2-Dιmethylamιno-5-amιno-, 3-Amιno-2-methylamιno-6-methoxy-, 2,3-Dιamιno-6-me- thoxy- 3,5-Dιamιno-2,6-dιmethoxy-, 2,6-Dιhydroxy-3,4-dιmethyipyndιn, 2-Hydroxy-4,5,6- triamino- 4-Hydroxy-2,5,6-tπamιno-, 2,4,5,6-Tetraamιno-, 2-Methylamιno-4,5,6-tπamιno- pynmidin, 3,5-Dιamιnopyrazol, .3-Aπvno-5-hydroxypyrazol, 5,6-Dιhydroxyιndol und 5,6- Dihydroxyindolm, ß-Alanin, L-Pro n, L-Lysin, DL-Tyrosin sowie deren mit vorzugsweise anorganischen Sauren gebildeten physiologisch vertraglichen SalzeThe compounds of component B are particularly preferably selected from the group consisting of N- (2-hydroxyethyl) -N-ethyl-, 2-chloro-p-phenylenediamine, N, N-Bιs- (2-hydroxyethyl) -p-phenylenediamine , 4-aminophenol, p-phenylenediamine, 2- (2,5-diminophenyl) ethanol, 2,5-diminotoluene, 3,4-methylenedoxyanol, 2-amino-4- (2-hydroxyethylamino) ananol , 2- (2,4-diminophenoxy) ethanol, 3-amino-2,4-dichloro, 2-methyl-5-amino, 3-methyl-4-amino, 2-methyl-5- (2nd -hydroxyethylamιno) -, 2-methyl-5-amino-4-chloro, 6-methyl-3-amino-2-chloro, 2-amino-methyl-4-aminophenol, 2-dimethylamino-4-amino-phenol , 2-dimethylamino-4-aminophenol, 2,6-dichloro-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 3 4-methylenedoxoxyphenol, 3,4-diminobenzoic acid, 2,5-dimino-no-, 2 -Dιmethylamιno-5-amιno-, 3-Amιno-2-methylamιno-6-methoxy-, 2,3-Dιamιno-6-methoxy- 3,5-Dιamιno-2,6-dιmethoxy-, 2,6- Dιhydroxy-3,4-dιmethyipyndιn, 2-hydroxy-4,5,6-triamino- 4-hydro xy-2,5,6-tπamιno-, 2,4,5,6-tetraamιno-, 2-methylamιno-4,5,6-tπamιno- pynmidine, 3,5-diminopyrazole, .3-amino-5-hydroxypyrazole, 5,6-dihydroxy-indole and 5,6-dihydroxyindole, β-alanine, L-proline, L-lysine, DL-tyrosine and their preferably inorganic Acids formed physiologically acceptable salts
Die voranstehend genannten Verbindungen der Komponente B können in einer Menge von jeweils 0,03 bis 65, insbesondere 1 bis 40 mmol, jeweils bezogen auf 100 g des gesamten Farbemittels, eingesetzt werden Weiterhin kann es erfindungsgemaß besonders bevorzugt sein, die Verbindung der Formel I und die Verbindung der Komponente B im molaren Mengenverhältnis von 2 1 bis 1 2, insbesondere etwaaquimolar, einzusetzen Beim Einsatz von Verbindungen der Komponente B die eine oder mehrere Aminogruppen enthalten, werden die Verbindungen der Formel I einerseits und die Verbindungen der Komponente B andererseits bevorzugt in solchen Mengenverhältnissen eingesetzt, dass die Summe der Zahl der Carbonylgruppen der Verbindungen der Formel I und die Summe der Zahl der Aminogruppen der Verbindungen der Komponente B im Verhältnis 2 1 bis 1 2 stehenThe above-mentioned compounds of component B can be used in an amount of 0.03 to 65, in particular 1 to 40 mmol, in each case based on 100 g of the total colorant. Furthermore, it can be particularly preferred according to the invention to use the compound of the formula I and to use the compound of component B in a molar ratio of 2 1 to 1 2, in particular approximately equimolar, when using compounds of component B which contain one or more amino groups, the compounds of formula I on the one hand and the compounds of component B on the other hand are preferred in such Quantities used that the sum of the number of carbonyl groups of the compounds of formula I and the sum of the number of amino groups of the compounds of component B in a ratio of 2 1 to 1 2
Zur Erlangung weiterer und intensiverer Ausfarbungen können die erfindungsgemaßen Mittel zusätzlich Farbverstarker enthalten Die Farbverstarker sind vorzugsweise ausgewählt aus der Gruppe bestehend aus Pipeπdin Pιperιdιn-2-carbonsaure, Pipeπdin- 3-carbonsaure, Pιperιdιn-4-carbonsaure, Pyndin, 2-Hydroxypyrιdιn, 3-Hydroxypyπdιn, 4- Hydroxypyπdin, Imidazol, 1-Methylιmιdazol, Histidin, Pyrrolidin, Prolin, Pyrrolidon, Pyrroli- don-5-carbonsaure, Pyrazol, 1 ,2,4-Trιazol, Piperazidin, deren Derivate sowie deren physiologisch vertraglichen SalzenTo obtain further and more intense colorations, the agents according to the invention can additionally contain color enhancers. The color enhancers are preferably selected from the group consisting of Pipeπdin Pιperιdιn-2-carboxylic acid, Pipeπdin- 3-carboxylic acid, Pιperιdιn-4-carboxylic acid, Pyndin, 2-hydroxypyridium, 3- Hydroxypyπdιn, 4-hydroxypyπdin, imidazole, 1-methylιmιdazol, histidine, pyrrolidine, proline, pyrrolidone, pyrrolidone-5-carboxylic acid, pyrazole, 1, 2,4-trιazole, piperazidine, their derivatives and their physiologically acceptable salts
Die voranstehend genannten Farbverstarker können in einer Menge von jeweils 0,03 bis 65, insbesondere 1 bis 40 mmol, jeweils bezogen auf 100 g des gesamten Farbemittels, eingesetzt werdenThe above-mentioned color enhancers can be used in an amount of 0.03 to 65, in particular 1 to 40 mmol, based in each case on 100 g of the total colorant
Auf die Anwesenheit von Oxidationsmitteln, z B H202, kann dabei verzichtet werden Es kann jedoch u U wünschenswert sein, den erfindungsgemaßen Mitteln zur Erzielung der Nuancen, die heller als die zu färbende keratinhalti e Fε ser sind, Wasserstoffperoxid oder andere Oxidationsmittel zuzusetzen Oxidationsmittel werden in der Regel in einer Menge von 0,01 bis 6 Gew -%, bezogen auf die Anwendu πgslosung, eingesetzt. Ein für menschliches Haar bevorzugtes Oxidationsmittel ist H202 In einer bevorzugten Ausfuhrungsform enthalten die erfindungsgemaßen Farbemittel zur weiteren Modifizierung der Farbnuancen neben den erfindungsgemaß enthaltenen Verbindungen zusätzlich übliche direktziehende Farbstoffe, z B aus der Gruppe derNitro- phenylendiamine, Nitroaminophenole, Anthrachinone oder Indophenole, wie z B die unter den internationalen Bezeichnungen bzw Handelsnamen HC Yeilow 2, HC Yeilow 4, HC Yeilow 6, Basic Yeilow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, Disperse Blue 3, Basic Blue 99, HC Violet 1 , Disperse Violet 1 , Disperse Violet 4, Disperse Black 9, Basic Brown 16 und Basic Brown 17 bekannten Verbindungen sowie Pikramiπsaure 2-Amιno-6-chloro-4-nιtrophenol, 4-Amιno-2-nιtrodιphenylamιn-2'- carbonsaure, 6-Nιtro-1 ,2,3,4-tetrahydrochιnoxalιn, 4-N-Ethyl-1 ,4-bιs-(2'-hydroxyethyla- mιno)-2-nιtrobenzol-hydrochlorιd und 1 -Methyl-3-nιtro-4-(2'-hydroxyethyl)-amιnobenzol Die erfindungsgemaßen Mittel gemäß dieser Ausfuhrungsform enthalten die direktziehenden Farbstoffe bevorzugt in einer Menge von 0,01 bis 20 Gew -% bezogen auf das gesamte FarbemittelThe presence of oxidizing agents, for example BH 2 0 2 , can be dispensed with here. However, it may be desirable to add hydrogen peroxide or other oxidizing agents to the agents according to the invention to achieve the shades that are lighter than the keratin-containing fibers to be colored are generally used in an amount of 0.01 to 6% by weight, based on the application solution. A preferred oxidizing agent for human hair is H 2 0 2 In a preferred embodiment, the colorants according to the invention contain, in addition to the compounds contained according to the invention, customary direct dyes, for example from the group of the nitrophenylenediamines, nitroaminophenols, anthraquinones or indophenols, such as those with the international names or trade names HC Yeilow, for further modification of the color shades 2, HC Yeilow 4, HC Yeilow 6, Basic Yeilow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16 and Basic Brown 17 known compounds as well as picramic acid 2-amino-6-chloro-4-non-trophenol, 4-amino-2-non -ododiphenylamine-2'-carboxylic acid, 6-non-1, 2,3,4-tetrahydrochιnoxalιn, 4-N-ethyl-1, 4-bιs- (2'-hydroxyethyla- mιno) -2-nιtrobenzene-hydrochloride and 1-methyl-3-nιtro-4- (2'-hydroxyethyl ) -amιnobenzol The agents according to the present invention form, the substantive dyes preferably contain in an amount of 0.01 to 20% by weight, based on the total colorant
Weiterhin können die erfindungsgemaßen Zubereitungen auch in der Natur vorkommende Farbstoffe wie beispielsweise Henna rot, Henna neutral, Henna schwarz, Kamil- lenblute, Sandelholz, schwarzen Tee, Faulbaumππde, Salbei, Blauholz, Krappwurzel, Catechu, Sedre und Alkannawurzel enthaltenFurthermore, the preparations according to the invention can also contain naturally occurring dyes such as, for example, henna red, henna neutral, henna black, chamomile blood, sandalwood, black tea, faulbaumππde, sage, blue wood, madder root, catechu, sedre and alkanna root
Es ist nicht erforderlich, dass die Oxidationsfarbstoffvorprodukte oder die fakultativ enthaltenen direktziehenden Farbstoffe jeweils einheitliche Verbindungen darstellen Vielmehr können in den erfindungsgemaßen Farbemitteln, bedingt durch die Herstellungsverfahren für die einzelnen Farbstoffe, in untergeordneten Mengen noch weitere Komponenten enthalten sein, soweit diese nicht das Farbeergebnis nachteilig beeinflussen oder aus anderen Gründen, z B toxikologischen, ausgeschlossen werden müssenIt is not necessary that the oxidation dye precursors or the optional direct dyes each represent uniform compounds. Rather, in the colorants according to the invention, due to the manufacturing processes for the individual dyes, further components may be present in minor amounts, provided that these do not adversely affect the color result or for other reasons, e.g. toxicological, must be excluded
Die erfindungsgemaßen Farbemittel ergeben bereits bei physiologisch vertraglichen Temperaturen von unter 45°C intensive Färbungen Sie eignen sich deshalb besonders zum Farben von menschlichen Haaren Zur Anwendung auf dem menschlichen Haar können die Farbemittel üblicherweise in einen wasserhaltigen kosmetischen Trager eingearbeitet werden Geeignete wasserhaltige kosmetische Trager sind z. B Cremes, Emulsioneπ, Gele oder auch tensidhaltige schaumende Losungen wie z. B Shampoos oder andere Zubereitungen, die für die Anwendung auf den keratinhaltigen Fasern geeignet sind Falls erforderlich ist es auch möglich, die Farbemittel in wasserfreie Trager einzuarbeitenThe colorants according to the invention already give intense colorations at physiologically acceptable temperatures of below 45 ° C. They are therefore particularly suitable for coloring human hair. For use on human hair, the colorants can usually be incorporated into a water-containing cosmetic carrier. Suitable water-containing cosmetic carriers are e.g. B creams, Emulsioneπ, gels or surfactant-containing foaming solutions such. B Shampoos or other preparations that are suitable for use on the keratin fibers If necessary, it is also possible to incorporate the colorants into anhydrous carriers
Weiterhin können die erfindungsgemaßen Farbemittel alle in solchen Zubereitungen bekannten Wirk-, Zusatz- und Hilfsstoffe enthalten In vielen Fallen enthalten die Farbemittel mindestens ein Tensid, wobei prinzipiell sowohl anionische als auch zwitteπoni- sche, ampholytische, nichtionische und kationische Tenside geeignet sind In vielen Fallen hat es sich aber als vorteilhaft erwiesen, die Tenside aus anionischen, zwitteπoni- schen oder nichtionischen Tensiden auszuwählenFurthermore, the colorants according to the invention can contain all of the active ingredients, additives and auxiliaries known in such preparations. In many cases the colorants contain at least one surfactant, and in principle both anionic and zwitterπonic, ampholytic, nonionic and cationic surfactants are suitable. In many cases however, it has proven advantageous to select the surfactants from anionic, zwitterπonischen or nonionic surfactants
Als anionische Tenside eignen sich in erfindungsgemaßen Zubereitungen alle für die Verwendung am menschlichen Korper geeigneten anionischen oberflächenaktiven Stoffe Diese sind gekennzeichnet durch eine wasserlöslich machende, anionische Gruppe wie z B eine Carboxylat-, Sulfat-, Sulfonat- oder Phosphat-Gruppe und eine lipophile Alkylgruppe mit etwa 10 bis 22 C-Atomen Zusätzlich können im MolekulGlykol- oder Polygiykolether-Gruppen, Ester-, Ether- und Amidgruppen sowie Hydroxylgruppen enthalten sein Beispiele für geeignete anionische Tenside sind, jeweils in Form der Natrium- Kalium- und Ammonium- sowie der Mono-, Di- und Tπalkanolammoniumsalze mit 2 oder 3 C-Atomen in der Alkanolgruppe,Suitable anionic surfactants in preparations according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as, for example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group about 10 to 22 carbon atoms In addition, the molecule may contain glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups. Examples of suitable anionic surfactants are in the form of the sodium, potassium and ammonium and the mono- , Di- and Tπalkanolammoniumsalze with 2 or 3 carbon atoms in the alkanol group,
lineare Fettsauren mit 10 bis 22 C-Atomen (Seifen),linear fatty acids with 10 to 22 carbon atoms (soaps),
Ethercarbonsauren der Formel R-0-(CH2-CH20)x-CH2-COOH, in der R eine lineare Alkylgruppe mit 10 bis 22 C-Atomen und x = 0 oder 1 bis 16 ist, Acylsarcoside mit 10 bis 18 C-Atomen in der Acylgruppe, Acyltaunde mit 10 bis 18 C-Atomen in der Acylgruppe, Acylisethionate mit 10 bis 18 C-Atomen in der Acylgruppe,Ether carboxylic acids of the formula R-0- (CH 2 -CH 2 0) x -CH 2 -COOH, in which R is a linear alkyl group with 10 to 22 C atoms and x = 0 or 1 to 16, acyl sarcosides with 10 to 18 Carbon atoms in the acyl group, acyltaundes with 10 to 18 carbon atoms in the acyl group, acyl isethionates with 10 to 18 carbon atoms in the acyl group,
Sulfobernsteinsauremono- und -dialkylester mit 8 bis 18 C-Atomen in der Alkylgruppe und Sulfobernsteinsauremono-alkylpolyoxyethylester mit 8 bis 18 C-Atomen in der Alkylgruppe und 1 bis 6 Oxyethylgruppen, lineare Alkansulfonate mit 12 bis 18 C-Atomen, lineare Alpha-Olefinsulfonate mit 12 bis 18 C-Atomen, Alpha-Sulfofettsauremethylester von Fettsauren mit 12 bis 18 C-Atomen, Alkylsulfate und Alkylpolyglykolethersulfate der Formel R-0(CH2-CH20)x-S03H, in der R eine bevorzugt lineare Alkylgruppe mit 10 bis 18 C-Atomen und x = 0 oder 1Sulfosuccinic acid mono- and dialkyl esters with 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl esters with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkane sulfonates with 12 to 18 carbon atoms, linear alpha-olefin sulfonates with 12 to 18 carbon atoms, alpha-sulfofatty acid methyl ester of fatty acids with 12 to 18 carbon atoms, Alkyl sulfates and alkyl polyglycol ether sulfates of the formula R-0 (CH 2 -CH 2 0) x -S0 3 H, in which R is a preferably linear alkyl group with 10 to 18 C atoms and x = 0 or 1
Gemische oberflächenaktiver Hydroxysulfonate gemäß DE-A-37 25 030, sulfatierte Hydroxyalkylpolyethylen- und/oder Hydroxyalkylenpropylenglykolether gemäß DE-A-37 23 354,Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030, sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ethers according to DE-A-37 23 354,
Sulfonate ungesättigter Fettsauren mit 12 bis 24 C-Atomen und 1 bis 6 Doppelbindungen gemäß DE-A-39 26 344,Sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344,
Ester der Weinsaure und Zitronensaure mit Alkoholen, die Anlagerungsprodukte von etwa 2 bis 15 Molekülen Ethylenoxid und/oder Propylenoxid an Fettalkohole mit 8 bis 22 C-Atomen darstellenEsters of tartaric acid and citric acid with alcohols, which are adducts of about 2 to 15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols with 8 to 22 carbon atoms
Bevorzugte anionische Tenside sind Alkylsulfate, Alkylpolyglykolethersulfate und Ether- carbonsauren mit 10 bis 18 C-Atomen in der Alkylgruppe und bis zu 12 Glykolethergrup- pen im Molekül sowie insbesondere Salze von gesattigten und insbesondere ungesättigten C8-C22-Carbonsauren, wie Ölsaure, Stearinsaure, Isosteaπnsaure und Palmitin- saurePreferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and in particular salts of saturated and in particular unsaturated C 8 -C 22 carboxylic acids, such as oleic acid, stearic acid , Isostearic acid and palmitic acid
Als zwitterionische Tenside werden solche oberflächenaktiven Verbindungen bezeichnet, die im Molekül mindestens eine quartare Ammoniumgruppe und mindestens eine -COO( ■- oder -S03 ("'-Gruppe tragen Besonders geeignete zwitterionische Tenside sind die sogenannten Betaine wie die N-Alkyl-N,N-dιmethylammonιum-glycιnate, beispielsweise das Kokosalkyl-dimethylammomumglycinat, N-Acyl-amιnopropyl-N,N-dιmethylam- momumglycinate, beispielsweise das Kokosacylaminopropyl-dimethylammoniumglycinat, und 2-Alkyl-3-carboxymethyl-3-hydroxyethyl-ιmιdazolιne mit jeweils 8 bis 18 C-Atomen in der Alkyl- oder Acylgruppe sowie das Kokosacylaminoethylhydroxyethylcarboxymethyl- glycmat. Ein bevorzugtes zwitterionisches Tensid ist das unter der CTFA-Bezeichnung Cocamidopropyl Betaine bekannte Fettsaureamid-DeπvatZwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one -COO (■ - or -S0 3 (" 'group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycate, for example the cocoalkyl-dimethylammomumglycinate, N-acyl-aminopropyl-N, N-dimethylamomomumglycinate, for example the cocoacylaminopropyl-dimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl-ole 18 carbon atoms in the alkyl or acyl group and cocoacylaminoethylhydroxyethylcarboxymethyl glycate A preferred zwitterionic surfactant is the fatty acid amide deπvat known under the CTFA name Cocamidopropyl Betaine
Unter ampholytischen Tensiden werden solche oberflächenaktiven Verbindungen verstanden, die außer einer C8 18-Alkyl- oder -Acylgruppe im Molekül mindestens eine freie Aminogruppe und mindestens eine -COOH- oder -S03H-Gruppe enthalten und zur Ausbildung innerer Salze befähigt sind Beispiele für geeignete ampholytische Tenside sind N-Alkylglycine, N-Alkylpropionsauren, N-Alkyiaminobuttersauren, N-Alkylimiπodipropion- sauren, N-Hydroxyethyl-N-alkylamidopropylglyαπe, N-Alkyltaunne, N-Alkylsarcosine, 2- Alkylammopropionsauren und Alkylaminoessigsauren mit jeweils etwa 8 bis 18 C-Atomen in der Alkylgruppe Besonders bevorzugte ampholytische Tenside sind das N-Kokosal- kylaminopropionat, das Kokosacylaminoethylaminopropionat und das C12 18-AcylsarcosιnAmpholytic surfactants are understood to mean those surface-active compounds which, in addition to a C 8 18 -alkyl or -acyl group, contain at least one free amino group and at least one -COOH or -S0 3 H group in the molecule and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkyaminobutyric acids, N-alkylimidodipropionic acidic, N-hydroxyethyl-N-alkylamidopropylglyαπe, N-alkyltaunne, N-alkylsarcosines, 2-alkylammopropionic acids and alkylaminoacetic acids, each with about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocosalkylaminopropionate, cocoacylaminoethylaminopropionate the C 12 18 acyl sarcosιn
Nichtionische Tenside enthalten als hydrophile Gruppe z B eine Polyolgruppe, eine Polyalkylenglykolethergruppe oder eine Kombination aus Polyol- und Polyglykolether- gruppe Solche Verbindungen sind beispielsweiseNonionic surfactants contain, for example, a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups as the hydrophilic group. Examples of such compounds are
Anlagerungsprodukte von 2 bis 30 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylen- oxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsauren mit 12 bis 22 C-Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear fatty alcohols with 8 to 22 carbon atoms, with fatty acids with 12 to 22 carbon atoms
Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe,Atoms and on alkylphenols with 8 to 15 carbon atoms in the alkyl group,
C12 22-Fettsauremono- und -diester von Anlageruπgsprodukten von 1 bis 30 MolC 12 22 fatty acid monoesters and diesters of addition products from 1 to 30 mol
Ethylenoxid an Glyceπn,Ethylene oxide on Glyceπn,
C8 22-Alkylmono- und -oligoglycoside und deren ethoxylierte Analoga,C 8 22 alkyl mono- and oligoglycosides and their ethoxylated analogs,
Anlagerungsprodukte von 5 bis 60 Mol Ethylenoxid an Rizinusöl und gehärtetesAddition products of 5 to 60 moles of ethylene oxide with castor oil and hardened
Rizinusöl,Castor oil,
Anlagerungeprodukte von Ethylenoxid an SorbitanfettsaureesterAddition products of ethylene oxide onto sorbitan fatty acid esters
Anlagerungsprodukte von Ethylenoxid an FettsaurealkanolamideAddition products of ethylene oxide with fatty acid alkanolamides
Beispiele für die in den erfindungsgemaßen Haarbehandlungsmitteln verwendbaren kat- lonischen Tenside sind insbesondere quartare Ammoniumverbindungen Bevorzugt sind Ammoπiumhalogenide wie Alkyltrimethylammoniumchloπde, Dialkyldimethylammonium- chloπde und Tπalkylmethylammoniumchloπde, z B Cetyltπmethylammoniumchlond, Stearyltnmethylammoniumchiorid, Distearyldimethylammoniumchloπd, Lauryldimethyl- ammoniumchloπd, Lauryldimethylbenzylammoniumchlorid und Tπcetylnnethylammonium- chloπd Weitere erfindungsgemaß verwendbare kationische Tenside stellen die quaterni- sierten Proteinhydrolysate darExamples are for useful in the inventive hair treatment compositions KAT ionic surfactants are in particular quaternary ammonium compounds are preferred as Ammoπiumhalogenide chloπde Alkyltrimethylammoniumchloπde, dialkyldimethylammonium and Tπalkylmethylammoniumchloπde, z B Cetyltπmethylammoniumchlond, Stearyltnmethylammoniumchiorid, Distearyldimethylammoniumchloπd, lauryl dimethyl ammoniumchloπd, lauryldimethylbenzylammonium chloride and Tπcetylnnethylammonium- chloπd More inventively useful cationic surfactants are the quaternized protein hydrolyzates
Erfindungsgemaß ebenfalls geeignet sind kationische Sflikonole wie beispielsweise die im Handel erhältlichen Produkte Q2-7224 (Hersteller Dow Corning, ein stabilisiertes Tπ- methylsilylamodimethicon), Dow Corning 929 Emulsion (er thaltend ein hydroxyl-amino- modifiziertes Silicon, das auch als Amodimethicone bezeichnet wird), SM-2059 (Herstel- ler General Electric), SLM-55067 (Hersteller Wacker) sowie Abιl®-Quat 3270 und 3272 (Hersteller Th Goldschmidt, diquaternare Polydimethylsiloxane, Quatemιum-80)Also suitable according to the invention are cationic silicone fluids such as, for example, the commercially available products Q2-7224 (manufacturer Dow Corning, a stabilized Tπ-methylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone) , SM-2059 (manufacturer General Electric), SLM-55067 (manufacturer Wacker) and Abιl ® -Quat 3270 and 3272 (manufacturer Th Goldschmidt, diquaternary polydimethylsiloxanes, Quatemιum-80)
Alkylamidoamine, insbesondere Fettsaureamidoamine wie das unter der Bezeichnung Tego Amιd®S 18 erhältliche Stearylamidopropyldimethylamin, zeichnen sich neben einer guten konditionierenden Wirkung speziell durch ihre gute biologische Abbaubarkeit ausAlkylamidoamines, especially fatty acid amidoamines such as the stearylamidopropyldimethylamine available under the name Tego Amιd ® S 18, are characterized not only by a good conditioning effect, but also by their good biodegradability
Ebenfalls sehr gut biologisch abbaubar sind quaternare Esterverbindungen, sogenannte "Esterquats", wie die unter dem Warenzeichen Stepantex® vertriebenen Methylhydroxy- alkyldialkoyloxyalkylammoniummethosulfateAlso readily biodegradable quaternary Esterverbindungen, so-called "esterquats", such as the methylhydroxy- marketed under the trade Stepantex® ® are alkyldialkoyloxyalkylammoniummethosulfate
Ein Beispiel für ein als kationisches Tensid einsetzbares quaternares Zuckerderivat stellt das Handelsprodukt Glucquat®100 dar, gemäß CTFA-Nomenklatur ein "Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride"An example of a quaternary sugar derivative that can be used as a cationic surfactant is the commercial product Glucquat ® 100, according to the CTFA nomenclature a "lauryl methyl gluceth-10 hydroxypropyl dimonium chloride"
Bei den als Tenside eingesetzten Verbindungen mit Alkylgruppen kann es sich jeweils um einheitliche Substanzen handeln Es ist jedoch in der Regel bevorzugt, bei der Herstellung dieser Stoffe von nativen pflanzlichen oder tierischen Rohstoffen auszugehen, so dass man Substanzgemische mit unterschiedlichen, vom jeweiligen Rohstoff abhangigen Alkylketteπlangen erhaltThe compounds with alkyl groups used as surfactants can in each case be uniform substances. However, it is generally preferred to use native vegetable or animal raw materials in the production of these substances, so that substance mixtures with different alkyl chain lengths depending on the respective raw material are obtained
Bei den Tensiden, die Anlagerungsprodukte von Ethylen- und/oder Propylenoxid an Fettalkohole oder Derivate dieser Anlagerungsprodukte darstellen, können sowohl Produkte mit einer "normalen" Homologenverteilung als auch solche mit einer eingeengten Homologenverteilung verwendet werden Unter "normaler" Homologenverteilung werden dabei Mischungen von Homologen verstanden, die man bei der Umsetzung von Fettalkohol und Alkylenoxid unter Verwendung von Alkalimetallen, Alkalimetallhydroxiden oder Alkalimetallalkoholaten als Katalysatoren erhalt Eingeengte Homologenverteilungen werden dagegen erhalten, wenn beispielsweise Hydrotalcite, Erdalkalimetallsalze von Ethercarbonsauren, Erdalkalimetalloxide -hydroxide oder -alkoholate als Katalysatoren verwendet werden Die Verwendung von Produkten mit eingeengter Homologenverteilung kann bevorzugt seinWith the surfactants, which are addition products of ethylene and / or propylene oxide onto fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrow homolog distribution can be used. "Normal" homolog distribution is understood to mean mixtures of homologs Which are obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. On the other hand, narrow homolog distributions are obtained if, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxide hydroxides or -alcoholates are used as products with catalysts narrow homolog distribution may be preferred
Weitere Wirk-, Hilfs- und Zusatzstoffe sind beispielsweise nichtionische Polymere wie beispielsweise Vinylpyrrolidon/Vinylacrylat-Copolymere, Polyvinylpyrroiidon und Vinylpyrrolidon/Vinylacetat-Copolymere und Polysiloxane, kationische Polymere wie quaternisierte Celluloseether, Polysiloxane mit quaterna- ren Gruppen, Dimethyldiallylammoniumchlorid-Polymere, Acrylamid-Dimethyldiallyl- ammoniumchloπd-Copolymere, mit Diethylsulfat quaternierte Dimethylaminoethyl- methacrylat-Vinylpyrro don-Copolymere, Vinylpyrro don-Imidazoli- niummethochlond-Copolymere und quaternierter Polyvinylalkohol, zwitterionische und amphotere Polymere wie beispielsweise Acrylamidopropyl-tπ- methylammoniumchlorid/Acrylat-Copolymere und Octylacrylamid/Methylmethacry- lat/tert -Butylamιnoethylmethacrylat 2-Hydroxypropylmethacrylat-Copolymere, anionische Polymere wie beispielsweise Polyacryisauren, vernetzte Polyacrylsau- ren, Vinylacetat/Crotonsaure-Copolymere, Vinylpyrrolidon/Vinylacrylat-Copolymere, Vinylacetat/Butylmaleat/Isobornylacrylat-Copolymere, Methylvinylether/Maleinsaure- anhydπd-Copolymere und Acrylsaure/Ethylacrylat/N-tert -Butylacrylamid-Terpoly- mere,Other active ingredients, auxiliaries and additives are, for example non-ionic polymers such as, for example, vinyl pyrrolidone / vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone / vinyl acetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyldiallylammonium chloride methyldimethylethyldimethylethyldimethylolidylethyldimethylethyldiamidyldimethyloloxymethyllaminophenylethylpolyamidyldiamethyldiamidylethyldiamidylethylpolyamidylethyldimethylamidylethylpolyamidyldimethyllaminophenylethylpolymer methacrylate-vinylpyrrod copolymers, vinylpyrrodimidazolinium methochlone copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyl-tπ-methylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate-lat / tert-butyl methacrylate 2-methyl acrylate, butyl acrylate, 2-butyl acrylate, anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / Maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers,
Verdickungsmittel wie Agar-Agar, Guar-Gum, Alginate, Xanthan-Gum, Gummi ara- bicum, Karaya-Gummi, Johannisbrotkernmehl, Leinsamengummen, Dextrane, Cel- lulose-Deπvate, z B Methylcellulose, Hydroxyalkylcellulose und Carboxymethylcel- lulose, Starke-Fraktionen und Derivate wie Amylose, Amylopektin und Dextrine, Tone wie z B Bentonit oder vollsynthetische Hydrokolloide wie z B Polyvinylalkohol,Thickeners such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, for example methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such as bentonite or fully synthetic hydrocolloids such as polyvinyl alcohol,
Strukturanten wie Glucose und Maleinsäure, haarkonditionierende Verbindungen wie Phosphohpide, beispielsweise Sojalecithin, Ei-Lecitin und Kephaiine, sowie Silikonole,Structurants such as glucose and maleic acid, hair-conditioning compounds such as phosphohpides, for example soy lecithin, egg lecithin and cephaiins, and silicone oils,
Proteinhydrolysate, insbesondere Elastin-, Kollagen-, Keratin-, Milcheiweiß-, Soja- protein- und Weizenproteinhydrolysate, deren Kondensationsprodukte mit Fettsauren sowie quaternisierte Proteinhydrolysate, Parfumole, Dimethylisosorbid und Cyclodextπne,Protein hydrolyzates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolyzates, perfumes, dimethyl isosorbide and cyclodextins,
Losungsvermittler wie Ethanol, Isopropanol, Ethylenglykol, Propylenglykol, Glycenn und Diethylenglykol,Solubilizers such as ethanol, isopropanol, ethylene glycol, propylene glycol, Glycenn and diethylene glycol,
Antischuppenwirkstoffe wie Piroctone Olamine und Zink Omadine, weitere Substanzen zur Einstellung des pH-Wertes,Anti-dandruff agents such as piroctone olamine and zinc omadine, other substances for adjusting the pH value,
Wirkstoffe wie Panthenol, Pantothensaure, Allantoin, Pyrrolidoncarbonsauren und deren Salze, Pflanzenextrakte und Vitamine, Cholesteπn, Lichtschutzmittel,Active substances such as panthenol, pantothenic acid, allantoin, pyrrolidone carboxylic acids and their salts, plant extracts and vitamins, Cholesteπn, light stabilizers,
Konsistenzgeber wie Zuckerester, Polyolester oder Polyolalkylether, Fette und Wachse wie Walrat, Bienenwachs, Montanwachs, Paraffine, Fettalkohole und Fettsaureester, Fettsaurealkanolamide,Consistency enhancers such as sugar esters, polyol esters or polyol alkyl ethers, fats and waxes such as walrus, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters, fatty acid alkanolamides,
Komplexbildner wie EDTA, NTA und Phosphonsauren,Complexing agents such as EDTA, NTA and phosphonic acids,
Quell- und Penetrationsstoffe wie Glycenn, Propylenglykolmonoethylether, Carbo- nate, Hydrogeπcarbonate, Guanidine, Harnstoffe sowie primäre, sekundäre und tertiäre Phosphate, Imidazole, Taπnine, Pyrrol, Trubungsmittel wie Latex,Swelling and penetration substances such as glycene, propylene glycol monoethyl ether, carbonates, hydrogecarbonates, guanidines, ureas and primary, secondary and tertiary phosphates, imidazoles, tinines, pyrrole, opacifiers such as latex,
Perlglanzmittel wie Ethylenglykolmono- und -distearat,Pearlescent agents such as ethylene glycol mono- and distearate,
Treibmittel wie Propan-Butan-Gemische, N20, Dimethylether, C02 und Luft sowie AntioxidantienBlowing agents such as propane-butane mixtures, N 2 0, dimethyl ether, C0 2 and air and antioxidants
Die Bestandteile des wasserhaltigen Tragers werden zur Herstellung der erfindungsgemaßen Farbemittel in für diesen Zweck üblichen Mengen eingesetzt, z B werden Emulgiermittel in Konzentrationen von 0,5 bis 30 Gew -% und Verdickungsmittel in Konzentrationen von 0, 1 bis 25 Gew -% des gesamten Farbemittels eingesetztThe constituents of the water-containing carrier are used to produce the colorants according to the invention in amounts customary for this purpose, for example emulsifiers are used in concentrations of 0.5 to 30% by weight and thickeners are used in concentrations of 0.1 to 25% by weight of the total colorant used
Für das Farbeergebnis kann es vorteilhaft sein, den Farbemitteln Ammonium- oder Metallsalze zuzugeben Geeignete Metallsalze sind z B Formiate, Carbonate, Halogenide, Sulfate, Butyrate, Valenate, Capronate, Acetate, Lactate, Glykolate, Tartrate, Citrate, Gluconate, Propionate, Phosphate und Phosphonate von Alkalimetallen, wie Kalium, Natrium oder Lithium, Erdalkalimetallen, wie Magnesium, Calcium, Strontium oder Barium, oder von Aluminium, Mangan, Eisen, Kobalt, Kupfer oder Zink, wobei Natnumace- tat, Lithiumbromid, Calciumbromid, Calαumgiuconat, Zinkchloπd, Zinksulfat, Magnesium- chlond, Magnesiumsulfat, Ammoniumcarbonat -chloπd und -acetat bevorzugt sind Diese Salze sind vorzugsweise in einer Menge von 0,03 bis 65, insbesondere von 1 bis 40, mmol bezogen auf 100 g des gesamten Farbemittels, enthaltenFor the color result, it may be advantageous to add ammonium or metal salts to the colorants. Suitable metal salts are, for example, formates, carbonates, halides, sulfates, butyrates, valenates, capronates, acetates, lactates, glycolates, tartrates, citrates, gluconates, propionates, phosphates and Phosphonates of alkali metals, such as potassium, sodium or lithium, alkaline earth metals, such as magnesium, calcium, strontium or barium, or of aluminum, manganese, iron, cobalt, copper or zinc, where Natnumace- tat, lithium bromide, calcium bromide, Calαumgiuconat, Zinkchloπd, zinc sulfate , Magnesium chloride, magnesium sulfate, ammonium carbonate chloride and acetate are preferred. These salts are preferably present in an amount of 0.03 to 65, in particular 1 to 40, mmol, based on 100 g of the total colorant
Der pH-Wert der gebrauchsfertigen Farbezubereitungen liegt üblicherweise zwischen 2 und 1 1 , vorzugsweise zwischen 5 und 10 Ein weiterer Gegenstand der /orliegenden Erfindung betrifft die Verwendung von Benzofurazanen mit der Formel I oder deren N-Oxiden,The pH of the ready-to-use color preparations is usually between 2 and 11, preferably between 5 and 10 Another object of the present invention relates to the use of benzofurazanes with the formula I or their N-oxides,
Figure imgf000019_0001
Figure imgf000019_0001
(l) in der R1 ein Wasserstoffatom oder Halogenatom ist,(l) in which R 1 is a hydrogen atom or halogen atom,
R2 ein Wasserstoffatom, eine Nitro, Sulfo-, Sufonat- oder Sulfonamidgruppe, in der der Stickstoff durch C^-Alkyl- oder Hydroxyalkylgruppen, die auch zusammen mit dem Stickstoffatom einen heterocyc schen Ring bilden können, substituiert sein kann, ist,R 2 is a hydrogen atom, a nitro, sulfo, sulfonate or sulfonamide group in which the nitrogen can be substituted by C 1-4 alkyl or hydroxyalkyl groups, which together with the nitrogen atom can also form a heterocyclic ring,
R3 und R4 ein Wasserstoff-, Halogenatom, eine C^-Alkyl-, C1.4-Alkoxy- oder Hydroxy-C^-alkylgruppe, eine Hydroxy-, Nitro-, Aminogruppe, die durch C^- Alkylgruppen substituiert sein kann, oder C^-Acylgruppe, wobei auch beide gemeinsam einen ankondensierten aromatischen Ring bilden können, bedeuten mit der Maßgabe, dass mindestens einer der Reste R1 bis R4 ein Halogenatom ist, als eine färbende Komponente in OxidationshaarfarbemittelnR 3 and R 4 represent a hydrogen, halogen atom, a C 1-4 alkyl, C 1 . 4 -alkoxy or hydroxy-C ^ alkyl group, a hydroxy, nitro, amino group, which can be substituted by C ^ - alkyl groups, or C ^ -acyl group, both of which together can form a fused aromatic ring, mean with with the proviso that at least one of the radicals R 1 to R 4 is a halogen atom, as a coloring component in oxidation hair colorants
Noch ein weiterer Gegenstand der vorliegenden Erfindung betrifft ein Verfahren zum Farben von keratinhaltigen Fasern, insbesondere menschlichen Haaren, worin ein Farbemittel, enthaltend A) mindestens ein Benzofurazan mit der Formel I oder dessen N-Oxid,Yet another object of the present invention relates to a process for coloring keratin-containing fibers, in particular human hair, in which a colorant comprising A) at least one benzofurazane with the formula I or its N-oxide,
Figure imgf000019_0002
Figure imgf000019_0002
(l)(L)
in der R1 ein Wasserstoffatom oder Halogena.om ist, R2 ein Wasserstoffatom, eine Nitro, Sulfo-, Sufonat- oder Sulfonamidgruppe, in der der Stickstoff durch C^-Alkyl- oder Hydroxyalkylgruppen, die auch zusammen mit dem Stickstoffatom einen heterocyclischen Ring bilden können, substituiert sein kann, ist,in which R 1 is a hydrogen atom or halogen atom, R 2 is a hydrogen atom, a nitro, sulfo, sulfonate or sulfonamide group in which the nitrogen can be substituted by C 1-4 alkyl or hydroxyalkyl groups, which together with the nitrogen atom can also form a heterocyclic ring,
R3 und R4 ein Wasserstoff-, Halogenatom, eine C^-Alkyl-, C1 4-Alkoxy- oder Hydroxy-C, 4-alkylgruppe, eine Hydroxy-, Nitro-, Aminogruppe, die durch C,_4- Alkylgruppen substituiert sein kann, oder C, 4-Acylgruppe, wobei auch beide gemeinsam einen ankondensierten aromatischen Ring bilden können, bedeuten mit der Maßgabe, dass mindestens einer der Reste R1 bis R4 ein Halogenatom ist, undR 3 and R 4 are a hydrogen, halogen atom, a C 1-4 alkyl, C 1 4 -alkoxy or hydroxy-C, 4- alkyl group, a hydroxy, nitro, amino group, which is substituted by C, _ 4 - alkyl groups can be substituted, or C, 4- acyl group, both of which can also together form a fused-on aromatic ring, with the proviso that at least one of the radicals R 1 to R 4 is a halogen atom, and
B) mindestens eine Verbindung mit primärer oder sekundärer Aminogruppe oder Hy- droxygruppe, ausgewählt aus primären oder sekundären aliphatischen oder aromatischen Ammen, stickstoffhaltigen heterocyclischen Verbindungen, aromatischen Hydroxyverbindungen, Aminosäuren, aus 2 bis 9 Aminosäuren aufgebauten Oh- gopeptiden und/oder mindestens eine CH-aktive Verbindung, sowie übliche kosmetische Inhaltsstoffe, auf die keratinhaltigen Fasern aufgebracht, einige Zeit, üblicherweise ca 30 Minuten, auf der Faser belassen und anschließend wieder ausgespult oder mit einem Shampoo ausgewaschen wirdB) at least one compound with a primary or secondary amino group or hydroxy group, selected from primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, aromatic hydroxy compounds, amino acids, from 2 to 9 amino acids built-up peptides and / or at least one CH- active compound, as well as common cosmetic ingredients, applied to the keratin fibers, left on the fiber for some time, usually about 30 minutes, and then rinsed out or washed out with a shampoo
Die Benzofurazane der Formel I oder deren N-Oxide und die Verbindungen der Komponente B können entweder gleichzeitig auf das Haar aufgebracht werden oder aber auch nacheinander, wobei es unerheblich ist, welche der beiden Komponenten zuerst aufgetragen wird Die fakultativ enthaltenen Ammonium- oder Metallsalze können dabei der ersten oder der zweiten Komponente zugesetzt werden Zwischen dem Auftragen der ersten und der zweiten Komponente können bis zu 30 Minuten Zeitabstand hegen Auch eine Vorbehandlung der Fasern mit der Salzlosung ist möglichThe benzofurazanes of the formula I or their N-oxides and the compounds of component B can either be applied to the hair simultaneously or else in succession, it being irrelevant which of the two components is applied first. The optionally contained ammonium or metal salts can may be added to the first or the second component Between the application of the first and the second component there may be a time interval of up to 30 minutes. A pretreatment of the fibers with the salt solution is also possible
Die Benzofurazane der Formel I oder deren N-Oxide und die Verbindungen der Komponente B können entweder getrennt oder zusammen gelagert werden, entweder in einer flussigen bis pastosen Zubereitung (wassπg oder wasserfrei) oder als trockenes Pulver Werden die Komponenten in einer flussigen Zubereitung zusammen gelagert, so sollte diese zur Verminderung einer Reaktion der Komponenten weitgehend wasserfrei sein Bei der getrennten Lagerung werden die reaktiven Komponenten erst unmittelbar vor der Anwendung miteinander innig vermischt Bei der trockenen Lagerung wird vor der Anwendung üblicherweise eine definierte Menge warmen (30 bis 80°C) Wassers hinzugefügt und eine homogene Mischung hergestellt. The benzofurazanes of the formula I or their N-oxides and the compounds of component B can either be stored separately or together, either in a liquid to pasty preparation (water or water-free) or as a dry powder If the components are stored together in a liquid preparation, this should be largely water-free to reduce a reaction of the components. When stored separately, the reactive components are only intimately mixed with one another immediately before use Usually a defined amount of warm (30 to 80 ° C) water is added to the application and a homogeneous mixture is produced.
BeispieleExamples
Herstellung einer FärbelösungPreparation of a coloring solution
Es wurde je eine Aufschlammung von 5 mmol eines Benzofurazans der Formel I, ggf. 5 mmol eines Oxidanonsfarbstoffvorproduktes der Komponente B und 5 mmol Natπumacetat und einen Tropfen einer 20-%ιgen Fettalkylethersulfat-Losung in 50 ml Wasser bei 50°C hergestellt. Die Aufschlammungen wurden nach Abkühlen auf 30°C miteinander vermischt und mit verdünnter NaOH oder Salzsaure auf einen pH-Wert von 9 eingestelltA slurry of 5 mmol of a benzofurazane of the formula I, optionally 5 mmol of an oxidanone dye precursor of component B and 5 mmol of sodium acetate and a drop of a 20% strength fatty alkyl ether sulfate solution in 50 ml of water at 50 ° C. were prepared. The slurries were mixed together after cooling to 30 ° C. and adjusted to a pH of 9 with dilute NaOH or hydrochloric acid
In diese Farbemischung wurde bei 30°C 30 Minuten lang eine Strähne zu 90% ergrauten, nicht vorbehandelten Menschenhaares eingebracht Die Strähne wurde dann 30 Sek mit lauwarmem Wasser gespult, mit warmer Luft getrocknet und anschließend ausgekämmtA strand of 90% gray, untreated human hair was introduced into this color mixture at 30 ° C. for 30 minutes. The strand was then rinsed with lukewarm water for 30 seconds, dried with warm air and then combed out
Die jeweiligen Farbnuancen und Farbtiefen sind in der nachfolgenden Tabelle 1 wiedergegebenThe respective color shades and color depths are shown in Table 1 below
Die Farbtiefe wurde dabei nach folgender Skala bewertetThe color depth was rated on the following scale
keine oder eine sehr blasse Ausfarbungno or a very pale color
(+) schwache Intensität(+) weak intensity
+ mittlere Intensität+ medium intensity
+(+) mittlere bis starke Intensität+ (+) medium to strong intensity
++ starke Intensität++ strong intensity
++(+) starke bis sehr starke Intensität++ (+) strong to very strong intensity
+++ sehr starke Intensität Tabelle 1+++ very strong intensity Table 1
Ausfärbungen mit 7-Chlor-5-nitrobenzofurazanColorings with 7-chloro-5-nitrobenzofurazan
Figure imgf000023_0001
Figure imgf000023_0001

Claims

Patentansprücheclaims
1. Mittel zum Färben von keratinhaltigen Fasern, insbesondere menschlichen Haaren, enthaltend als färbende Komponente mindestens ein Benzofurazan mit der Formel I oder dessen N-Oxid,1. agent for dyeing keratin-containing fibers, in particular human hair, containing at least one benzofurazane with the formula I or its N-oxide as the coloring component,
Figure imgf000024_0001
Figure imgf000024_0001
(D(D
in der R ein Wasserstoffatom oder Halogenatom ist,in which R is a hydrogen atom or halogen atom,
R2 ein Wasserstoffatom, eine Nitro, Sulfo-, Sufonat- oder Sulfonamidgruppe, in der der Stickstoff durch C^-Alkyl- oder Hydroxyalkylgruppen, die auch zusammen mit dem Stickstoff atom einen heterocyclischen Ring bilden können, substituiert sein kann, ist,R 2 is a hydrogen atom, a nitro, sulfo, sulfonate or sulfonamide group, in which the nitrogen can be substituted by C 1-4 alkyl or hydroxyalkyl groups, which together with the nitrogen atom can also form a heterocyclic ring,
R3 und R4 ein Wasserstoff-, Halogenatom, eine C,_4-Alkyl-, C,.4-Alkoxy- oder Hydroxy-C^-alkylgruppe, eine Hydroxy-, Nitro-, Aminogruppe, die durch C,^- Alkylgruppen substituiert sein kann, oder C1.4-Acylgruppe, wobei auch beide gemeinsam einen ankondensierten aromatischen Ring bilden können, bedeuten mit der Maßgabe, dass mindestens einer der Reste R1 bis R4 ein Halogenatom ist.R 3 and R 4 are hydrogen, halogen, C, _ 4 alkyl, C ,. 4 -alkoxy or hydroxy-C ^ alkyl group, a hydroxy, nitro, amino group which may be substituted by C, ^ - alkyl groups, or C 1 . 4 -acyl group, both of which can together form a fused aromatic ring, with the proviso that at least one of the radicals R 1 to R 4 is a halogen atom.
Mittel nach Anspruch 1 , dadurch gekennzeichnet, dass als Verbindungen mit der Formel I 7-Chlor-4-nιtrobenzofurazan, 7-Fluor-4-nιtrobenzofurazan, 7-Chlor- benzofurazan-4-sulfonsaure, Ammoniumsalz, 7-Fluor-benzofurazan-4-sulfonsaure, Ammoniumsalz, 7-Chlor-benzofurazan-4-sulfonamιd, 7-Chlor-4-morpholinosulfonyl-, 7-Chlor-4-dιmethylamιno-sulfonyl-, 7-Fluor-4-dimethylamιnosulfonylbenzofurazan, 5- Fluor-benzofuroxan, 5-Chlor-benzofuroxan, 7-Chlor-benzofuroxan, 4,6- Dichlorbenzofuroxan, 5-Chlorbenzofurazan sowie deren beliebigen Gemische eingesetzt werden. Mittel nach einem der Ansprüche 1 bis 2, dadurch gekennzeichnet, dass die Benzofurazane der Formel I oder deren N-Oxide in einer Menge von 0,03 bis 65 mmol, insbesondere von 1 bis 40 mmol, bezogen auf 100 g des gesamten Farbemittels, enthalten sindAgent according to claim 1, characterized in that as compounds with the formula I 7-chloro-4-nitrobenzofurazane, 7-fluoro-4-nitrobenzofurazane, 7-chloro-benzofurazane-4-sulfonic acid, ammonium salt, 7-fluoro-benzofurazane-4 -sulfonic acid, ammonium salt, 7-chloro-benzofurazan-4-sulfonamide, 7-chloro-4-morpholinosulfonyl-, 7-chloro-4-dimethylamino-sulfonyl, 7-fluoro-4-dimethylaminosulfonylbenzofurazane, 5-fluoro-benzofuroxane, 5 -Chlorobenzofuroxan, 7-chloro-benzofuroxane, 4,6-dichlorobenzofuroxane, 5-chlorobenzofurazane and any mixtures thereof. Agent according to one of claims 1 to 2, characterized in that the benzofurazanes of the formula I or their N-oxides in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the total colorant are
Mittel nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass es zusätzlich mindestens eine Verbindung mit primärer oder sekundärer Aminogruppe oder Hydroxygruppe, ausgewählt aus primären oder sekundären aromatischen Ammen, stickstoffhaltigen heterocyclischen Verbindungen und aromatischen Hydroxyverbindungen, Aminosäuren, aus 2 bis 9 Aminosäuren aufgebauten Oli- gopeptiden und/oder mindestens eine CH-aktive Verbindung, enthaltAgent according to one of claims 1 to 3, characterized in that it additionally contains at least one compound having a primary or secondary amino group or hydroxy group, selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds, amino acids, from 2 to 9 amino acids - Contains gopeptides and / or at least one CH-active compound
Mittel nach Anspruch 4, dadurch gekennzeichnet, dass die weitere Verbindung ausgewählt ist aus primären oder sekundären Ammen aus der Gruppe, bestehend aus N-(2-Hydroxye- thyl)-N-ethyl-, N-(2-Methoxyethyl-), 2,3-, 2,4-, 2,5-Dιchlor-p-phenylendιamιn, 2-Chlor- p-phenylendiamin, N,N-Bιs-(2-hydroxyethyl)-p-phenylendιamιn, 2,5-Dιhydroxy-4- morpholinoanilin-dihydrobromid, 2-, 3-, 4-Amιnophenol, o-, m-, p-Phenylendiamin, 2,4-Dιamιnophenoxyethanol, 2-(2,5-Dιamιnophenyl)-ethanol, 2,5-Dιamιnotoluol, - phenol, -phenethol, 4-Methylamιno-, 3-Amιno-4-(2'-hydroxyethyloxy)-, 3,4-Methylen- diamino-, 3,4-Methylendιoxyanιlιn, 3-Amιno-2,4-dιchlor-, 4-Methylamιno-, 2-Methyl-5- amino-, 3-Methyl-4-amιno-, 2-Methyl-5-(2-hydroxyethylamιno)-, 2-Methyl-5-amιno-4- chlor-, 6-Methyl-3-amιno-2-chlor-, 5-(2-Hydroxyethylamιno)-4-methoxy-2-methyl-, 4- Amιno-2-amιnomethyl-phenol, 2-Hydroxymethyl-4-amιnophenol, 2-Agent according to claim 4, characterized in that the further compound is selected from primary or secondary nurses from the group consisting of N- (2-hydroxyethyl) -N-ethyl-, N- (2-methoxyethyl-), 2nd , 3-, 2,4-, 2,5-Dιchlor-p-phenylene diamine, 2-chloro-p-phenylene diamine, N, N-Bιs- (2-hydroxyethyl) -p-phenylene diamine, 2,5-dihydroxy-4 - Morpholinoaniline dihydrobromide, 2-, 3-, 4-aminophenol, o-, m-, p-phenylenediamine, 2,4-diminophenoxyethanol, 2- (2,5-diminophenyl) ethanol, 2,5-diminotoluene, - phenol, phenethol, 4-methylamino, 3-amino-4- (2'-hydroxyethyloxy) -, 3,4-methylene-diamino-, 3,4-methylene-dioxyaniline, 3-amino-2,4-dichloro, 4-methylamino, 2-methyl-5-amino, 3-methyl-4-amino, 2-methyl-5- (2-hydroxyethylamino) -, 2-methyl-5-amino-4-chloro, 6 -Methyl-3-amino-2-chloro, 5- (2-hydroxyethylamine) -4-methoxy-2-methyl-, 4-amino-2-amino-methyl-phenol, 2-hydroxymethyl-4-amino-phenol, 2-
Dιethylamιnomethyl-4-amιnophenol, 2-Dιmethylamιnomethyl-4-amιnophenol, 2,6- Dιchlor-4-amιnophenol, 1 ,3-Dιamιno-2,4-dιmethoxybenzol, 2-, 3-, 4- Aminobenzoesaure, -phenylessigsaure, 2,3-, 2,4-, 2,5-, 3,4-, 3,5-Dιamιnoben- zoesaure, 4-, 5-Amιnosalιcylsaure, 3-Amιno-4-hydroxy-, 4-Amιno-3-hydroxy- benzoesaure, 2-, 3-, 4-Amιnobenzolsulfonsaure, 3-Amιno-4-hydroxybenzolsul- fonsaure, 4-Amιno-3-hydroxynaphthalιn-sulfonsaure, 6-Amιno-7-hydroxynaphthalιn- 2-sulfonsaure, 7-Amιno-4-hydroxynaphthalιn-2-sulfonsaure, 4-Amιno-5- hydroxynaphthalιn-2,7-dιsulfonsaure, 3-Amιno-2-naphthoesaure, 3-Amιπophthal- saure, 5-Amιπoιsophthalsaure, 1 ,3,5-, 1 ,2,4-Trιamιnobenzol, 1 ,2,4,5-Tetraamιno- benzol-tetrahydrochloπd, 2,4,5-Tπamιnophenol-trιhydrochloπd, Pentaaminobenzol- pentahydrochloπd, Hexaaminobenzol-hexahydrochloπd, 2,4,6-Trιamιnoresorcιn-trι- hydrochloπd, 4,5-Dιamιnobrenzcatechιnsulfat, 4,6-Dιamιnopyrogallol-dιhydrochlorιd, 3,5-Dιamιno-4-hydroxybrenzcatechιn-sulfat, aromatische Nitnie, Nitrogruppen-haltige Aminoverbindungen, wie 3-Amιπo-6-methylamιno-2-nιtro-pyπdιn, Pikraminsaure, 1- (2(3)-Nιtro-4-amιno)-phenylazo-2-hydroxy-7-trιmethylammonιumnaphthalιn-chlorιd, 1-Hydroxy-2-amιno-4,6-dιnιtro-benzol, 1-Amιno-2-nιtro-4-bιs-(2-hydroxyethyl)-amιno- benzol, 1-Amιno-2-(2-hydroxyethyl)-amιno-5-nιtro-benzol (HC Yeilow Nr 5), 1- Amιno-2-nιtro-4-(2-hydroxyethyl)-amιnobenzol (HC Red Nr 7), 2-Chloro-5-nιtro-N- hydιoxyethyl-1 ,4-phenylendιamιn, 1-(2-Hydroxyethyl)-amιno-2-nιtro-4-amιno-benzol (HC Red Nr 3), 4-Amιno-3-nιtrophenol, 4-Amιno-2-nιtrophenol, 6-Nιtro-o-toluιdιn, 1- Amιno-3-methyl-4-(2-hydroxyethyl)-amιno-6-nιtrobenzol (HC Violet Nr 1), 1-Amιno- 2-nιtro-4-(2,3-dιhydroxypropyl)-amιno-5-chlorobenzol an (HC Red Nr 10), 4-Amιno- 2-nιtrodιphenyl-amιno-2'-carbonsaure (2-(4-Amιno-2-nιtroanιlιno)-benzoesaure), 6- Nιtro-2,5-dιamιnopyrιdιn, 2-Amιno-6-chloro-4-nιtrophenol, 2-Amιno-6-chloro-4-nιtro- phenol, 1-Amιno-2-(3-nιtrophenylazo)-7-phenylazo-8-naphthol-3,6-dιsulfonsaure, Dinatnumsalz (Acid blue Nr 29), 1-Amιno-2-(2-hydroxy-4-nιtrophenylazo)-8- naphthol-3,6-dιsulfonsaure, Dinatnumsalz (Palatinchrome green), 1-Amιno-2-(3- chlor-2-hydroxy-5-nιtrophenylazo)-8-naphthol-3,6-dιsulfonsaure, DinatnumsalzDιethylamιnomethyl-4-amιnophenol, 2-Dιmethylamιnomethyl-4-amιnophenol, 2,6- Dιchlor-4-amιnophenol, 1, 3-Dιamιno-2,4-dιmethoxybenzene, 2-, 3-, 4-aminobenzoic acid, -phenylacetic acid, 2 , 3-, 2,4-, 2,5-, 3,4-, 3,5-dιamιnoben- zoic acid, 4-, 5-amιnosalιcyl acid, 3-amino-4-hydroxy-, 4-amino-3-hydroxy - Benzoic acid, 2-, 3-, 4-amino-benzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 4-amino-3-hydroxynaphthalene-sulfonic acid, 6-amino-7-hydroxynaphthalene-2-sulfonic acid, 7-amino-4 -hydroxynaphthalιn-2-sulfonic acid, 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid, 3-amino-2-naphthoic acid, 3-amino phthalic acid, 5-amino-phthalic acid, 1, 3.5, 1, 2, 4-trιamιnobenzol, 1, 2,4,5-tetraamιno- benzene-tetrahydrochloπd, 2,4,5-tπamιnophenol-trιhydrochloπd, pentaaminobenzene-pentahydrochloπd, hexaaminobenzene-hexahydrochloπd, 2,4,6-trιamιnoresorcιn-trι- hydrochloπd, 4,5-dιamatechronol 5-Dιamιno-4-hydroxybrenzcatechιn sulfate, aromatic nitrous oxide, nitro group-containing amino compounds, such as 3-amino-6-methylamino-2-nιtro-pyπdιn, picramic acid, 1- (2 (3) -nιtro-4-amιno) - phenylazo-2-hydroxy-7-trιmethylammonιumnaphthalιn-chlorιd, 1-hydroxy-2-amino-4,6-dιnιtro-benzene, 1-amino-2-nιtro-4-bιs- (2-hydroxyethyl) amino-benzene, 1-amino-2- (2-hydroxyethyl) amino-5-nitro-benzene (HC Yeilow No. 5), 1- amino-2-nitro-4- (2-hydroxyethyl) amino-benzene (HC Red No. 7), 2-chloro-5-nitro-N-hydιoxyethyl-1, 4-phenylenediamine, 1- (2-hydroxyethyl) -amιno-2-nitro-4-amino-benzene (HC Red No. 3), 4-amino-3- non-troenol, 4-amino-2-non-troenol, 6-non-o-toluene, 1-amino-3-methyl-4- (2-hydroxyethyl) -amino-6-non robenzol (HC Violet No. 1), 1-Amιno- 2-nιtro-4- (2,3-dιhydroxypropyl) -amιno-5-chlorobenzene (HC Red No. 10), 4-Amιno- 2-nιtrodιphenyl-amιno-2 '-carboxylic acid (2- (4-amino-2-non-ionic) -benzoic acid), 6- non-2,5-diminopyridic, 2-amino-6-chloro-4-non-trophenol, 2-amino-6-chloro-4 -nιtro- phenol, 1-amino-2- (3-nιtrophenylazo) -7-phenylazo-8-naphthol-3,6-disulfonic acid, dinate salt (acid blue No. 29), 1-amino-2- (2-hydroxy- 4-nιtrophenylazo) -8- naphthol-3,6-disulfonic acid, dinate salt (Palatinchrome green), 1-amino-2- (3-chloro-2-hydroxy-5-nonrophenylazo) -8-naphthol-3,6-disulfonic acid , Dinate salt
(Gallion), 4-Amιno-4'-nιtrostιlben-2,2'-dιsulfonsaure, Dinatnumsalz, 2,4-Dιamιno- 3',5'-dιnιtro-2'-hydroxy-5-methyl-azobenzol (Mordant brown 4), 4'-Amιno-4- nιtrodιphenylamιn-2-sulfonsaure 4'-Amιno-3'-nιtrobenzophenon-2-carbonsaure 1 - Amιno-4-nιtro-2-(2-nιtrobenzylιdenamιno)-benzol, 2-[2-(Dιethylamιno)-ethylamιno]-5- nitroanihn, 3-Amιno-4-hydroxy-5-nιtrobenzolsulfonsaure, (Hydrat), 3-Amιno-3'- nitrobiphenyl, 3-Amιno-4-nιtro-acenaphthen, 2-Amιno-1-nιtronaphthalιn, 5-Amιno-6- nιtrobenzo-1 ,3-dιoxol, Aniline, insbesondere Nitrogruppen-haltige Aniline, wie 4- Nitroanihn, 2-Nιtroanιlιn, 1 ,4-Dιamιno-2-nιtrobenzol, 1 ,2-Dιamιno-4-nιtrobenzol, 1- Amιno-2-methyl-6-nιtrobenzol, 4-Nιtro-1 ,3-phenylendιamιn, 2-Nιtro-4-amιno-1-(2-hy- droxyethylamιno)-benzol, 2-Nιtro-1 -amιno-4-[bιs-(2-hydroxyethyl)-amιno]-benzol, 4- Amιno-2-nιtrodιphenylamιn-2'-carbonsaure, 2-Amιno-6-chlor-4-nιtropheπol, 1-Amιno- 5-chlor-4-(2-hydroyethylamιno)-2-nιtrobenzol, Aniline, insbesondere Nitrogruppen- haltige Aniline, wie 4-Nιtroanιlιn, 2-Nιtroanιlιn, 1 ,4-Dιamιno-2-nιtrobenzol, 1 ,2- Dιamιno-4-nιtrobenzol, 1-Amιno-2-methyl-6-nιtrobenzoi, 4-Nιtro-1 ,3-phenylendιamιn, 2-Nιtro-4-amιno-1-(2-hydroxyethylamιno)-benzol, 2-Nιtro-1-amιno-4-[bιs-(2- hydroxyethyl)-amιno]-benzol 4-Amιno-2-nιtrodιphenylamιn-2'-carbonsaure, 2- Amιno-6-chlor-4-nιtrophenol, l-Amιno-5-chlor-4-(2-hydroyethylamιno)-2-nιtrobenzol, aromatische Aniline bzw Phenole mit einem weiteren aromatischen Rest wie 4,4'- Diaminostilben-dihydrochloπd, 4,4'-Dιamιnostιlben-2,2'-dιsulfonsaure, Na-Salz, 4,4'- Diaminodiphenylmethan, -sulfid, -sulfoxid, -amin, 4,4'-Dιamιnodιphenyiamιn-2-sulfon- saure, 4,4'-Dιamιnobenzophenon, -diphenylether, 3,3',4,4'-Tetraamιnodιphenyl-tetra- hydrochloπd, 3,3',4,4'-Tetraamιno-benzophenon, 1 ,3-Bιs-(2,4-dιamιnophenoxy)-pro- pan-tetrahydrochlond, 1 ,8-Bιs-(2,5-dιamιnophenoxy)-3,6-dιoxaoctan-tetrahydrochlo- πd, 1 ,3-Bιs-(4-amιnophenylamιno)-propan, -2-propanol, 1 ,3-Bιs-[N-(4-amιnophenyl)- 2-hydroxyethylamιno]-2-propanol, N,N-Bιs-[2-(4-amιnophenoxy)-ethyl]methylamιn- tnhydrochlorid, stickstoffhaltigen heterocyclischen Verbindungen ausgewählt aus der Gruppe, bestehend aus 2-, 3-, 4-Amιno-, 2-Amιno-3-hydroxy-, 2 6-Dιamιno-, 2,5-Dιamιno-, 2,3-Dιa- mino-, 2-Dιmethylamιno-5-amιno-, 3-Amιno-2-methylamιno-6-methoxy-, 2,3-Dιa- mιno-6-methoxy-, 3,5-Dιamιno-2,6-dιmethoxy-, 2,4,5-Tπamιno-, 2,6-Dιhydroxy-3,4- dimethylpyπdin, 4,5,6-Tπamιno-, 2-Hydroxy-4,5,6-trιamιno-, 4-Hydroxy-2,5,6- tπamino-, 2,4,5,6-Tetraamιno-, 2-Methylamιno-4,5,6-trιamιno-, 2,4-, 4,5-Dιamιno-, 2- Amιno-4-methoxy-6-methyl-pyrιmιdιn, 2,3,4-Trιmethylpyrrol, 2,4-Dιmethyl-3-ethyl- pyrrol, 3,5-Dιamιnopyrazol, -1 ,2,4-trιazol, 3-Amιno-, 3-Amιno-5-hydroxypyrazol, 2-, 3-, 8-Amιnochιnolιn, 4-Amιno-chιnaldιn, 2-, 6-Amιnonιcotιnsaure, 5-Amιnoιsochιnolιn, 5-, 6-Amιnoιndazol, 5-, 7-Amιno-benzιmιdazol, -benzothiazol, 2,5-Dιhydroxy-4- morpholinoanihn sowie Indol- und Indolindenvaten, wie 4-, 5-, 6-, 7-Amιnoιndol, 4- 5- , 6-, 7-Hydroxyιndol, 5,6-Dιhydroxyιndol, 5,6-Dιhydroxyιndolιn, 4-Hydroxyιndolιn und die in DE-U 1-299 08 573 offenbarten Hydroxypynmidine, sowie jeweils aus den mit vorzugsweise anorganischen Sauren gebildeten physiologisch vertraglichen Salzen dieser Verbindungen, aromatischen Hydroxyverbindungen ausgewählt aus der Gruppe, bestehend aus 2-, 4-, 5-Methylresorcιn, 2,5-Dιmethylresorcιn, Resorcin, 3-Methoxyphenol, Brenzkate- chin, Hydrochmon, Pyrogallol, Phloroglucin, Hydroxyhydrochinon, 2-, 3-, 4-Methoxy-, 3-Dιmethylamιno-, 2-(2-Hydroxyethyl)-, 3,4-Methylendιoxyphenol, 2,4-, 3,4-Dιhydro- xybenzoesaure, -phenylessigsaure, Gallussäure, 2/ ,6-Tπhydroxybenzoesaure, - acetophenon, 2-, 4-Chlorresorcιn, 1-Naphthol, 1 ,5-, 2,C-, 2,7-Dιhydroxynaphthalιn, 6- Dιmethylamιno-4-hydroxy-2-naphthalιnsulfonsaure, 3,6-Dιhydroxy-2,7-naphthalιn- sulfonsaure, Aminosauren ausgewählt aus der Gruppe Arginin, Histidin, Tyrosin, Phenylalanin, DOPA (Dihydroxyphenylalanin), Ornithin, Lysm und Tryptophan, Oligopeptid ausgewählt aus Glutathion oder die in den Hydroiysaten von Kollagen, Keratin, Casein, Elastin, Sojaprotein, Weizengluten oder Mandelprotein enthaltene Oligopeptide(Gallion), 4-amino-4'-nitro-benzene-2,2'-disulfonic acid, dinate salt, 2,4-dimino-3 ', 5'-diminro-2'-hydroxy-5-methyl-azobenzene (Mordant brown 4th ), 4'-Amιno-4-nιtrodιphenylamιn-2-sulfonic acid 4'-Amιno-3'-nιtrobenzophenon-2-carboxylic acid 1 - Amιno-4-nιtro-2- (2-nιtrobenzylιdenamιno) -benzene, 2- [2- (Dιethylamιno) -ethylamιno] -5-nitroanihn, 3-amino-4-hydroxy-5-nitrobenzenesulfonic acid, (hydrate), 3-amino-3'-nitrobiphenyl, 3-amino-4-nitro-acenaphthene, 2-amino- 1-Nιtronaphthalιn, 5-Amιno-6-nιtrobenzo-1, 3-dιoxol, anilines, in particular nitro group-containing anilines, such as 4-nitroanihn, 2-Nιtroanιlιn, 1, 4-Dιamιno-2-nιtrobenzol, 1, 2-Dιamι -4-nitrobenzene, 1-amino-2-methyl-6-nitrobenzene, 4-nitro-1, 3-phenylenediamine, 2-nitro-4-amino-1- (2-hydroxyethylamino) -benzene, 2-nitro -1 -amιno-4- [bιs- (2-hydroxyethyl) -amιno] -benzene, 4- Amιno-2-nιtrodιphenylamιn-2'-carboxylic acid, 2-Amιno-6-chloro-4-nιtropheπol, 1-Amιno- 5-chloro-4- (2-hydroyethylamιno) -2-nιtr topzole, anilines, especially nitro group-containing anilines, such as 4-nitroanil, 2-nitroanil, 1,4-dimin-2-nitrobenzene, 1,2-dimin-4-nitrobenzene, 1-amino-2-methyl-6-n , 4-nitro-1, 3-phenylenediamine, 2-nitro-4-amino-1- (2-hydroxyethylamino) -benzene, 2-nitro-1-amino-4- [bιs- (2- hydroxyethyl) -amιno] -benzene 4-amino-2-nontrodiphenylamine-2'-carboxylic acid, 2- amino-6-chloro-4-nontrophenol, l-amino-5-chloro-4- (2-hydroethylamino) -2- nitrobenzene, aromatic anilines or phenols with a further aromatic radical such as 4,4'-diaminostilbene dihydrochloride, 4,4'-diminostilbene-2,2'-disulfonic acid, sodium salt, 4,4'-diaminodiphenylmethane, sulfide, - sulfoxide, amine, 4,4'-diminodiphenyiamine-2-sulfonic acid, 4,4'-diminobenzophenone, diphenyl ether, 3,3 ', 4,4'-tetraaminodiphenyl-tetra-hydrochloride, 3,3', 4 , 4'-tetraamine-benzophenone, 1,3-bis (2,4-diminophenoxy) -pro- pan-tetrahydrochloride, 1,8-bis- (2,5-diminophenoxy) -3,6-dimoxoctane-tetrahydrochlo- πd, 1, 3-Bιs- (4-amιnophenylamιno) -propane, -2-propanol, 1, 3-Bιs- [N- (4-amιnophenyl) - 2-hydroxyethylamιno] -2-propanol, N, N-Bιs - [2- (4-aminophenoxy) ethyl] methylamine tn hydrochloride, nitrogen-containing heterocyclic compounds selected from the group consisting of 2-, 3-, 4-amino, 2-amino-3-hy droxy-, 2 6-Dιamιno-, 2,5-Dιamιno-, 2,3-Dιa- mino-, 2-Dιmethylamιno-5-amιno-, 3-Amιno-2-methylamιno-6-methoxy-, 2,3 -Dιa- mιno-6-methoxy-, 3,5-Dιamιno-2,6-dιmethoxy-, 2,4,5-Tπamιno-, 2,6-Dιhydroxy-3,4-dimethylpyπdin, 4,5,6- Tπamιno-, 2-hydroxy-4,5,6-trιamιno-, 4-hydroxy-2,5,6- tπamino-, 2,4,5,6-tetraamιno-, 2-methylamιno-4,5,6- trιamιno-, 2,4-, 4,5-Dιamιno-, 2-Amιno-4-methoxy-6-methyl-pyrιmιdιn, 2,3,4-trιmethylpyrrole, 2,4-dimethyl-3-ethyl-pyrrole, 3rd , 5-Dιamιnopyrazol, -1, 2,4-trιazol, 3-Amιno-, 3-Amιno-5-hydroxypyrazole, 2-, 3-, 8-Amιnochιnolιn, 4-Amιno-chιnaldιn, 2-, 6-Amιnonιcotιnsaure, 5-Amιnoιsochιnolιn, 5-, 6-Amιnoιndazol, 5-, 7-Amιno-benzιmιdazol, -benzothiazol, 2,5-Dιhydroxy-4- morpholinoanihn as well as indole and indolinden derivatives, such as 4-, 5-, 6-, 7- Amιnoιndol, 4- 5-, 6-, 7-Hydroxyιndol, 5,6-Dιhydroxyιndol, 5,6-Dιhydroxyιndolιn, 4-Hydroxyιndolιn and the hydroxypynmidines disclosed in DE-U 1-299 08 573, and each from the physiologically acceptable salts of these compounds formed with preferably inorganic acids, aromatic hydroxy compounds selected from the group consisting of 2-, 4-, 5-methylresorcιn, 2,5-dimethylresorcιn, resorcinol, 3-methoxyphenol, pyrocatechol, hydrochmon, Pyrogallol, phloroglucin, hydroxyhydroquinone, 2-, 3-, 4-methoxy-, 3-dimethylamino, 2- (2-hydroxyethyl) -, 3,4-methylenedoxoxyphenol, 2,4-, 3,4-dihydrooxybenzoic acid, -phenylacetic acid, gallic acid, 2 /, 6-Tπhydroxybenzoesaure, - acetophenone, 2-, 4-chloro-resorcinol, 1-naphthol, 1, 5-, 2, C-, 2,7-dihydroxynaphthalene, 6- dimethylamino-4-hydroxy 2-naphthalenesulfonic acid, 3,6-dihydroxy-2,7-naphthalenesulfonic acid, Amino acids selected from the group arginine, histidine, tyrosine, phenylalanine, DOPA (dihydroxyphenylalanine), ornithine, Lysm and tryptophan, oligopeptide selected from glutathione or those contained in the hydrolyzates of collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein
CH-aktiven Verbindungen ausgewählt aus der Gruppe, bestehend aus 1 ,2,3,3-Te- tramethyl-3H-ιndolιumιodιd, 1 ,2,3,3-Tetramethyl-3H-ιndolιum-p-toluolsulfonat,CH-active compounds selected from the group consisting of 1, 2,3,3-tetramethyl-3H-ιndolιumιodιd, 1, 2,3,3-tetramethyl-3H-ιndolιum-p-toluenesulfonate,
1 ,2,3,3-Tetramethyl-3H-ιndolιum-methansulfonat, Fischersche Base (1 ,3,3-Trιme- thyl-2-methylenιndolιn), 2,3-Dιmethyl-benzothιazolιumιodιd, 2,3-Dιmethyl-benzothιa- zolium-p-toluolsulfonat, 1 ,2-Dιmethyl-naphtho[1 ,2-d]thιazolιum-p-toluolsulfonat, 1- Ethyl-2-methyl-naphtho[1 ,2-d]thιazolιum-p-toluolsulfonat, Rhodanin, Rhodanιn-3-es- sigsaure, 1-Ethyl-2-chιπaldιnιum-ιodιd, 1 ,4-Dιmethylchιnolιnιum-ιodιd, 1-Methyl-2- chinaldinium-iodid, 1 ,4-Dιmethylchιnolιnιum-ιodιd, Barbitursaure, Thiobarbitursaure, 1 ,3-Dιmethylthιobarbιtursaure, 1 ,3-Dιethylthιobarbιtursaure, Diethylthiobarbitursaure, Oxindol, 3-lndoxylacetat, Cumaranon und 1-Methyl-3-phenyl-2-pyrazolιnon1, 2,3,3-tetramethyl-3H-ιndolιum methanesulfonate, Fischer's base (1, 3,3-trιme-methyl-2-methylenιndolιn), 2,3-dimethyl-benzothιazolιumιodιd, 2,3-dimethyl-benzothιa- zolium p-toluenesulfonate, 1, 2-dimethylnaphtho [1, 2-d] thιazolιum p-toluenesulfonate, 1-ethyl-2-methylnaphtho [1, 2-d] thιazolιum p-toluenesulfonate, rhodanine, Rhodanιn-3-es- sigsaure, 1-ethyl-2-chιπaldιnιum-ιodιd, 1, 4-Dιmethylchιnolιnιum-ιodιd, 1-methyl-2-quinaldinium-iodide, 1, 4-Dιmethylchιnolιnιum-ιobiture, barbed 3-dimethylthio-carbonic acid, 1, 3-dimethylthio-carbonic acid, diethylthiobarbituric acid, oxindole, 3-indoxy acetate, coumaranone and 1-methyl-3-phenyl-2-pyrazolionone
Mittel nach Anspruch 5, dadurch gekennzeichnet, dass die weitere Verbindung ausgewählt ist aus der Gruppe bestehend aus N-(2-Hydroxyethyl)-N-ethyl-, 2-Chlor- p-phenylendiamm, N,N-Bιs-(2-Hydroxyethyl)-p-phenylendιamιn, 4-Amιnophenol, p- Phenylendiamin, 2-(2,5-Dιamιnophenyl)-ethanol, 2,5-Dιamιnotoluol, 3,4-Methylendι- oxyani n, 2-Amιno-4-(2-hydroxyethylamιno)-anιsol, 2-(2,4-Dιamιnophenoxy)-ethanol, 3-Amιno-2,4-dιchlor-, 2-Methyl-5-amιno-, 3-Methyl-4-amιno-, 2-Methyl-5-(2-hydro- xyethylamino)-, 2-Methyl-5-amιno-4-chlor-, 6-Methyl-3-amιno-2-chlor-, 2-Amιnome- thyl-4-amιnophenol, 2-Dιethylamιnomethyl-4-amιnophenol, 2-Dιmethylamιnomethyl- 4-amιnophenol, 2,6-Dιchlor-4-amιnophenol, 2-Hydroxymethyl-4-amιnophenol, 3,4- Methylendioxyphenol, 3,4-Dιamιnobenzoesaure, 2,5-Dιamιπo-, 2-Dιmethylamιno-5- amino-, 3-Amιno-2-methylamιno-6-methoxy-, 2,3-Dιamιno-6-methoxy-, 3,5-Dιamιno- 2,6-dιmethoxy-, 2,6-Dιhydroxy-3,4-dιmethylpyπdιn, 2-Hydroxy-4,5,6-trιamιno-, 4-Hy- droxy-2,5,6-trιamιno-, 2,4,5,6-Tetraamιno-, 2-Methylamιno-4,5,6-trιamιno-pyrιmιdιn, 3,5-Dιamιnopyrazol, 3-Amιno-5-hydroxypyrazol, 5,6-Dιhydroxyιπdol und 5,6-Dιhy- droxyindolin, ß-Alanin, L-Prolm, L-Lysin, DL-Tyrosin sowie jeweils aus den vorzugsweise mit anorganischen Sauren gebildeten physiologisch vertraglichen Salzen dieser Verbindungen Mittel nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass es Farbverstarker ausgewählt aus der Gruppe bestehend aus Pipe din, Pιpeπdιn-2-car- bonsaure, Pιpeπdιn-3-carbonsaure, Pιpeπdιn-4-carbonsaure, Pyndin, 2-Hydroxypyrι- din, 3-Hydroxypyrιdιn, 4-Hydroxypyπdιn, Imidazol, 1-Methylιmιdazol, Histidin, Pyrroh- din, Prolin, Pyrrolidon, Pyrrolιdon-5-carbonsaure, Pyrazol, 1 ,2,4-Trιazol, Piperazidin oder deren beliebigen Gemischen enthaltAgent according to claim 5, characterized in that the further compound is selected from the group consisting of N- (2-hydroxyethyl) -N-ethyl, 2-chloro-p-phenylenediamine, N, N-Bιs- (2-hydroxyethyl ) -p-phenylenediamine, 4-aminophenol, p-phenylenediamine, 2- (2,5-diminophenyl) ethanol, 2,5-diminotoluene, 3,4-methylenedoxyani n, 2-amino-4- (2- hydroxyethylamιno) -anιsol, 2- (2,4-diminophenoxy) ethanol, 3-amino-2,4-dichloro, 2-methyl-5-amino, 3-methyl-4-amino, 2-methyl 5- (2-hydro-xyethylamino) -, 2-methyl-5-amino-4-chloro, 6-methyl-3-amino-2-chloro, 2-amino-methyl-4-amino-phenol, 2-dimethylamino-methyl -4-aminophenol, 2-dimethylamino-4-aminophenol, 2,6-dichloro-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 3,4-methylenedioxyphenol, 3,4-diminobenzoic acid, 2,5-diminophenol, 2-Dimethylamιno-5-amino-, 3-Amιno-2-methylamιno-6-methoxy-, 2,3-Dιamιno-6-methoxy-, 3,5-Dιamιno- 2,6-dimethoxy-, 2,6- Dιhydroxy-3,4-dimethylpyπdιn, 2-hydroxy-4,5,6-trιamι no-, 4-hydroxy-2,5,6-trιamιno-, 2,4,5,6-tetraamιno-, 2-methylamιno-4,5,6-trιamιno-pyrιmιdιn, 3,5-diminopyrazole, 3 -Amιno-5-hydroxypyrazole, 5,6-Dιhydroxyιπdol and 5,6-Dιhy- hydroxyindoline, ß-alanine, L-Prolm, L-lysine, DL-tyrosine and in each case from the physiologically acceptable salts of these compounds preferably formed with inorganic acids Agent according to one of claims 1 to 6, characterized in that there are color enhancers selected from the group consisting of pipe din, Pιpeπdιn-2-car- bonsaure, Pιpeπdιn-3-carbonsaure, Pιpeπdιn-4-carbonsaure, Pyndin, 2-hydroxypyrι- din, 3-hydroxypyrιdιn, 4-hydroxypyrπdιn, imidazole, 1-methylιmιdazol, histidine, pyrrodine, proline, pyrrolidone, pyrrolidone-5-carboxylic acid, pyrazole, 1, 2,4-trιazole, piperazidine or any mixtures thereof
Mittel nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass es direkt ziehende Farbstoffe aus der Gruppe der Nitrophenylendiamine, Nitroaminophenole, Anthrachinone oder Indophenole vorzugsweise in einer Menge von 0,01 bis 20 Gew -% bezogen auf das gesamte Farbemittel, enthaltAgent according to one of claims 1 to 7, characterized in that it contains direct dyes from the group of nitrophenylenediamines, nitroaminophenols, anthraquinones or indophenols, preferably in an amount of 0.01 to 20% by weight, based on the total colorant
Mittel nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass Ammonium- oder Metallsalze ausgewählt aus der Gruppe der Formiate, Carbonate, Halo- genide, Sulfate, Butyrate, Valenate, Capronate, Acetate, Lactate, Glykolate, Tartrate, Citrate, Gluconate, Propionate, Phosphate und Phosphonate von Alkalimetallen, wie Kalium, Natrium oder Lithium, Erdalkalimetallen, wie Magnesium, Calcium, Strontium oder Barium, oder von Aluminium, Mangan, Eisen, Kobalt, Kupfer oder Zink, zugegeben werdenAgent according to one of claims 1 to 8, characterized in that ammonium or metal salts selected from the group of formates, carbonates, halogenides, sulfates, butyrates, valenates, capronates, acetates, lactates, glycolates, tartrates, citrates, gluconates, Propionates, phosphates and phosphonates of alkali metals, such as potassium, sodium or lithium, alkaline earth metals, such as magnesium, calcium, strontium or barium, or of aluminum, manganese, iron, cobalt, copper or zinc, can be added
Mittel nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass es Oxidationsmittel, insbesondere H202, in einer Menge von 0,01 bis 6 Gew -%, bezogen auf die Aπwendungslosung, enthaltAgent according to one of claims 1 to 9, characterized in that it contains oxidizing agents, in particular H 2 0 2 , in an amount of 0.01 to 6% by weight, based on the application solution
Mittel nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass es anionische, zwittenoπische oder nichtionische Tenside enthaltAgent according to one of claims 1 to 10, characterized in that it contains anionic, zwittenoπische or nonionic surfactants
Verwendung von Benzofurazanen mit der Formel I oder deren N-Oxiden,Use of benzofurazanes with the formula I or their N-oxides,
R1R1
R3 >R3>
R2R2
(I) in der R1 ein Wasserstoffatom oder Halogenatom ist,(I) in which R 1 is a hydrogen atom or halogen atom,
R2 ein Wasserstoffatom, eine Nitro, Sulfo-, Sufonat- oder Sulfonamidgruppe, in der der Stickstoff durch C^-Alkyl- oder Hydroxyalkylgruppen, die auch zusammen mit dem Stickstoffatom einen heterocyclischen Ring bilden können, substituiert sein kann, ist,R 2 is a hydrogen atom, a nitro, sulfo, sulfonate or sulfonamide group in which the nitrogen can be substituted by C 1-4 alkyl or hydroxyalkyl groups, which together with the nitrogen atom can also form a heterocyclic ring,
R3 und R4 ein Wasserstoff-, Halogenatom, eine C^-Alkyl-, C^-Alkoxy- oder Hydroxy-C, 4-alkylgruppe, eine Hydroxy-, Nitro-, Aminogruppe, die durch C^- Alkylgruppen substituiert sein kann, oder C, 4-Acylgruppe, wobei auch beide gemeinsam einen ankondensierten aromatischen Ring bilden können, bedeuten mit der Maßgabe, dass mindestens einer der Reste R bis R4 ein Halogenatom ist, als eine färbende Komponente in OxidationshaarfarbemittelnR 3 and R 4 are a hydrogen, halogen atom, a C 1-4 alkyl, C 1-4 alkoxy or hydroxy-C, 4- alkyl group, a hydroxy, nitro or amino group which can be substituted by C 1-4 alkyl groups , or C, 4- acyl group, both of which together can form a fused-on aromatic ring, with the proviso that at least one of the radicals R to R 4 is a halogen atom, as a coloring component in oxidation hair colorants
13. Verfahren zum Farben von keratinhaltigen Fasern, insbesondere menschlichen Haaren, worin ein Farbemittel, enthaltend A) mindestens ein Benzofurazan mit der Formel I oder dessen N-Oxid13. A process for coloring keratin-containing fibers, in particular human hair, in which a colorant comprising A) at least one benzofurazane with the formula I or its N-oxide
Figure imgf000030_0001
Figure imgf000030_0001
in der R1 ein Wasserstoffatom oder Halogenatom ist,in which R 1 is a hydrogen atom or halogen atom,
R2 ein Wasserstoffatom, eine Nitro, Sulfo-, Sufonat- oder Sulfonamidgruppe, in der der Stickstoff durch C^-Alkyl- oder Hydroxyalkylgruppen, die auch zusammen mit dem Stickstoffatom einen heterocyclischen Ring bilden können, substituiert sein kann, ist, R3 und R4 ein Wasserstoff-, Halogenatom, eine C^-Alkyl-, C^-Alkoxy- oder Hydroxy-C^-alkylgruppe, eine Hydroxy-, Nitro-, Aminogruppe, die durch C^-Alkylgruppen substituiert sein kann, oder C^-Acylgruppe, wobei auch beide gemeinsam einen ankondensierten aromatischen Ring bilden können, bedeuten mit der Maßgabe, dass mindestens einer der Reste R1 bis R4 ein Halogenatom ist, und B) mindestens eine Verbindung mit primärer oder sekundärer Aminogruppe oder Hydroxygruppe, ausgewählt aus primären oder sekundären aromatischen Ami- nen, stickstoffhaltigen heterocyclischen Verbindungen und aromatischen Hy- droxyverbindungen, Aminosäuren, aus 2 bis 9 Aminosäuren aufgebauten Oli- gopeptiden und/oder mindestens eine CH-aktive Verbindung, sowie übliche kosmetische Inhaltsstoffe, auf die keratinhaltigen Fasern aufgebracht, einige Zeit, üblicherweise ca. 30 Minuten, auf der Faser belassen und anschließend wieder ausgespült oder mit einem Shampoo ausgewaschen wird. R 2 is a hydrogen atom, a nitro, sulfo, sulfonate or sulfonamide group, in which the nitrogen can be substituted by C 1-4 alkyl or hydroxyalkyl groups, which together with the nitrogen atom can also form a heterocyclic ring, R 3 and R 4 is a hydrogen, halogen atom, a C 1-4 alkyl, C 1-4 alkoxy or hydroxy-C 1-4 alkyl group, a hydroxy, nitro or amino group which can be substituted by C 1-4 alkyl groups, or C ^ -Acyl group, both of which together form a fused aromatic ring can form, with the proviso that at least one of the radicals R 1 to R 4 is a halogen atom, and B) at least one compound having a primary or secondary amino group or hydroxyl group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds, amino acids, oligopeptides composed of 2 to 9 amino acids and / or at least one CH-active compound, as well as usual cosmetic ingredients, applied to the fibers containing keratin, leave on the fiber for some time, usually about 30 minutes and then rinsed out or washed out with a shampoo.
PCT/EP2000/012821 1999-12-24 2000-12-15 Agent for colouring fibres containing keratin WO2001047485A1 (en)

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WO2002022094A1 (en) * 2000-09-15 2002-03-21 Wella Aktiengesellschaft Use of 4-nitro-2,1,3-benzoxadiazol derivatives as dyes in colouring agents for keratin fibres
WO2002022093A1 (en) * 2000-09-15 2002-03-21 Wella Aktiengesellschaft Agent and method for colouring keratin fibres
JP2006241111A (en) * 2005-03-04 2006-09-14 Univ Nihon New benzofuroxan and its synthesis method

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FR2910278A1 (en) * 2006-12-26 2008-06-27 Oreal Composition for dyeing human keratin fibers, e.g. dyeing and lightening human hair, contains surfactant and fused heterocyclic dye, e.g. (1,2,5)-oxadiazolo-(3,4-c)-pyridine derivative
FR2910277A1 (en) * 2006-12-26 2008-06-27 Oreal Composition for dyeing human hair or skin, contains at least one thickener and at least one special aromatic-heterocyclic direct dye in a cosmetically-acceptable medium

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WO1991007394A1 (en) * 1989-11-22 1991-05-30 Bristol-Myers Squibb Company Benzoxazine dyes
EP0684035A1 (en) * 1994-05-26 1995-11-29 L'oreal Keratineous fibres oxidation dyeing composition containing a derivative of paraphenylenediamine and a 6-hydroxy 1,4-benzoxazine
WO1999013850A1 (en) * 1997-09-17 1999-03-25 The Procter & Gamble Company Hair care compositions comprising optical brighteners and stability enhancing agents

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WO1991007394A1 (en) * 1989-11-22 1991-05-30 Bristol-Myers Squibb Company Benzoxazine dyes
EP0684035A1 (en) * 1994-05-26 1995-11-29 L'oreal Keratineous fibres oxidation dyeing composition containing a derivative of paraphenylenediamine and a 6-hydroxy 1,4-benzoxazine
WO1999013850A1 (en) * 1997-09-17 1999-03-25 The Procter & Gamble Company Hair care compositions comprising optical brighteners and stability enhancing agents

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Publication number Priority date Publication date Assignee Title
WO2002022094A1 (en) * 2000-09-15 2002-03-21 Wella Aktiengesellschaft Use of 4-nitro-2,1,3-benzoxadiazol derivatives as dyes in colouring agents for keratin fibres
WO2002022093A1 (en) * 2000-09-15 2002-03-21 Wella Aktiengesellschaft Agent and method for colouring keratin fibres
US6749645B2 (en) 2000-09-15 2004-06-15 Wella Aktiengesellschaft Use of 4-nitro-2,1,3,-benzoxadiazole derivatives as dyes in coloring agents for keratin fibres
US6773463B2 (en) 2000-09-15 2004-08-10 Wella Aktiengesellschaft Agent and method for dyeing keratin fibers
JP2006241111A (en) * 2005-03-04 2006-09-14 Univ Nihon New benzofuroxan and its synthesis method

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