DE4418990A1 - Stabilisation of oxidn. dye precursor in aq. formulation - Google Patents

Abstract

The invention pertains to a method for stabilizing oxidation dye intermediates contained in an aqueous preparation using cyclodextrines.

Description

The invention relates to a method for stabilizing in an aqueous preparation pre-oxidation dye products with the help of cyclodextrins.

The so-called oxidation hair dye play a role in dyeing hair because of their intense colors and good dyeing technology Properties such as B. Lightfastness, washfastness and leveling ability to play a preferred role. Such hair dye contains ten oxidation dye precursors in an aqueous cosmetic Carrier. Developer compo as oxidation dye precursors components and coupler components. The developer components form under the influence of oxidizing agents or atmospheric acid fabric with each other or with coupling with one or more Coupler components from the actual dyes.

Certain oxidation dye precursors, however, have an aqueous Preparation stability problems during storage. this leads to inevitably to problems that the reproducibility of the achieved  Color tones affect the hair. Usually the stability of oxidation dye precursors through the application Sensitivity of antioxidants such as B. ascorbic acid or sodium sulfate fit increased. In European patent application EP 279 016 alternatively, powdery hair dye based on oxides tion dye precursors described, the oxidation dye precursors in the form of cyclodextrin inclusion complexes lie.

It has now surprisingly been found that the stability of Oxidation dye precursors in aqueous preparations simple addition of cyclodextrin can be increased without prior synthesized or formed a cyclodextrin inclusion compound should be.

The present invention relates to a method for stabilization lization of oxidation in an aqueous preparation dye precursors, characterized in that the aqueous addition preparation of a cyclodextrin in an amount of 0.1 to 10% by weight, preferably from 0.5 to 2.0 wt .-%, based on the total aqueous Preparation, is added.

Cyclodextrins are created when Bacillus breaks down starch macerans or Bacillus circulans under the influence of cyclodextrin glycosyltransferase. A distinction is made between 6, 7 or 8 glucose in constructed cyclodextrins (α-, β- or γ-cyclodextrins). No heres to cyclodextrins and their inclusion compounds see z. B. in "Angewandte Chemie, 1994, 106, pages 851-870".

The oxidation dye precursors are coupler and / or developer components, both in the form of the free base and in the form their inorganic or organic salts, e.g. B. the hydrochloride or hydrobromides can be used.  

Primary aromatic are usually used as developer components Amines with another one in the para or ortho position free or substituted hydroxy or amino group, diaminopyri dinderivate, heterocyclic hydrazones, 4-aminopyrazolone derivatives as well as 2,4,5,6-tetraaminopyrimidine and its derivatives. Special representatives are, for example, p-toluenediamine, 2,4,5,6- Tetraaminopyrimidine, p-aminophenol, N, N-bis (2-hydroxyethyl) -p-phe nylenediamine, 2- (2,5-diaminophenyl) ethanol, 2- (2,5-diaminophenoxy) ethanol, 1-phenyl-3-carboxyamido-4-amino-pyrazolon-5 and 4-amino-3- methylphenol.

Usually m-phenylenediamine derivatives, Naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophe nole used. Are particularly suitable as coupler substances α-naphthol, pyrogallol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinolmonomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-pyrazolone-5,2,4-dichloro- 3-aminophenol, 1,3-bis (2,4-diaminophenoxy) propane, 2-chloro resor cin, 2-chloro-6-methyl-3-aminophenol and 2-methylresorcinol.

The coupler and / or developer components are preferably out selects from the group p-toluenediamine, 1-naphthol, resorcinol.

Optionally, so-called direct dyes can also be used in the aqueous hair dye preparations may be included.

Usual direct dyes are e.g. B. nitrobenzene derivatives, Anthraquinone dyes, triphenylmethane dyes and azo dye fe. Representatives of these used in hair dyes and tints Dye classes are, for example, those among the international ones Designations or trade names HC Yellow 2, HC Yellow 4, Methyl  yellow, fluor yellow, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Cardinal Red, Red Y, Red X, Basic Red 76, HC Blue 2, Nitro blue, Disperse Blue 3, Basis Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Base Brown 16, Pikramin acid and Rodol 9 R, known compounds. Other suitable di rectifying dyes are, for example, the compounds 3-Ni tro-4-ethylaminobenzoic acid, 1,2,3,4-tetrahydro-6-nitroquinoxaline, 2-nitro-4-amino-4'-dimethylaminodiphenylamine-2'-carboxylic acid and 2-nitro-4-aminodiphenylamine-2'-carboxylic acid.

Developer components, coupler components and optional components direct dyes are in an amount of 0.01 to 5 Wt .-%, preferably 0.1 to 2 wt .-%, based on the total aq preparation, included.

It is not necessary that the coupler components, the developer components or the optional direct colors substances each represent uniform connections. Rather you can in the hair colorants according to the invention also mixtures various ner coupler components, developer components and direct pull Dyes are used.

The aqueous preparation is usually one for use on hair carrier suitable for the hair. Such carriers are e.g. B. Creams, emulsions, gels or surfactant-containing foaming solvents songs, e.g. B. shampoos, aerosols or other preparations that are suitable for use on the hair.

The water-containing carrier usually contains wetting and emulsifying agents agents such as anionic, nonionic or ampholytic surfactants, e.g. B. fatty alcohol sulfates, alkane sulfonates, α-olefin sulfonates, fat  alcohol polyglycol ether sulfates, alkyl glycosides, ethylene oxide plant products on fatty alcohols, on fatty acids, on alkylphenols Sorbitan fatty acid esters, on fatty acid partial glycerides and fatty acid alkanolamides; Thickeners, e.g. B. fatty alcohols, fatty acids, Paraffin oils, fatty acid esters and other fat components in emulsified ter form; water-soluble polymeric thickeners such as natural ones Gums, e.g. B. gum arabic, karaya gum, guar gum, locust beans bread kernel flour, linseed gums; biosynthetic gums, e.g. B. xanthan Gum and dextrans; synthetic gums, e.g. B. agar and algin, Starch fractions and derivatives such as amylose, amylopectin and dextri no; modified cellulose molecules, e.g. B. methyl cellulose, hydroxy alkyl cellulose and carboxymethyl cellulose; Clays such as B. bentonite or fully synthetic hydrocolloids, e.g. B. polyvinyl alcohol or Po lyvinylpyrrolidone; hair care additives such. B. water soluble cationic polymers, anionic polymers, nonionic polymers, amphoteric or zwitterionic polymers, pantothenic acid, vitamins, Plant extracts or cholesterol; pH adjusting agent, complexing agent and perfume oils and reducing agents to stabilize the content fabrics, e.g. B. ascorbic acid; finally, dyes can also be used Coloring the cosmetic preparations may be included.

The components of the water-containing carrier are used for the production the hair dye is used in the usual amounts for this purpose; e.g. B. are emulsifiers in concentrations of 0.5 to 30 wt .-% and thickeners in concentrations of 0.1 to 25% by weight of the entire colorant used.

The oxidative development of the coloring can basically be done with air oxygen. However, a chemical oxidant is preferred Onsmittel used, especially if in addition to the coloring Whitening effect on the hair is desired. Come as an oxidizer especially hydrogen peroxide or its addition products Urea, melamine or sodium borate and mixtures of these  Hydrogen peroxide addition products with potassium peroxide disulfate in Consideration.

The preparation of the oxidizing agent is expediently carried out prior to hair dyeing with the preparation from the oxidation Dye precursors mixed. The resultant use hair dye preparation should preferably have a pH in the range of Have 6 to 10. The use of hair is particularly preferred. Colorants in a weakly alkaline environment. The application tem temperatures can range between 15 and 40 ° C. To The hair dye becomes active after approx. 30 minutes removed by rinsing from the hair to be dyed. The washing up with a shampoo does not apply if a carrier that contains a lot of surfactants, e.g. B. a coloring shampoo was used.

The following examples are intended to illustrate the subject matter of the invention explain, but without restricting him to this.  

Examples of use

There were hair dye in the form of a hair dye cream emulsion following compositions prepared; Composition B and C are according to the invention, A is used for comparison:

The ingredients were mixed together in order. To The oxidation dye precursors and the inhibitor were added Cyclodextrin added, then with concentrated ammonia solution The pH of the emulsion was adjusted to 9.5, then was brought up with water 100 g filled up.

The oxidative development of the coloring was with 3% hydrogen peroxide solution carried out as an oxidation solution. For this, 100 g  50 g of hydrogen peroxide solution (3%) are added to the emulsion and mixed.

The coloring cream was standardized on approx. 5 cm long strands, 90% but not particularly pretreated human hair applied and left there for 30 minutes at 27 ° C. After completion During the dyeing process, the hair was rinsed with a normal hair detergent washed and then dried. It resulted a dark blue shade.

Stability of the oxidation dye precursors in the composition tongues A, B and C

To determine the stability of the oxidation dye precursors their content was measured in compositions A, B and C, after the compositions are at 45 ° C for 4 weeks closed tubes had been stored.

Measurement method: HPLC (injection volume 10 µl)

for 1-naphthol:
Nowapak C18, 150 _* 4 mm, 1.5 mL flow
Eluent: CH₃CN / buffer pH 6.7 (30:70), 23 ° C
Detection 234 nm

for p-toluenediamine sulfate:
Lichrosorb RP-8, 250 _* 4 mm, 1.0 mL flow
Eluent: CH₃CN / buffer pH 6.7 (8:92), 40 ° C
Detection 220 nm.

The results are shown in Table 1.  

Table 1

Decrease in the content of oxidation dye precursors (data in:% decrease)

It shows that the stabilizing effect of cyclodextrins ins in particular compared to p-toluenediamine sulfate.

Claims (2)

1. A method for stabilizing oxidation dye precursors in an aqueous preparation, characterized in that the aqueous preparation contains a cyclodextrin in an amount of 0.1 to 10% by weight, preferably 0.5 to 2.0% by weight. , based on the total aqueous preparation, is added. 2. The method according to claim 1, characterized in that the oxi dation dye intermediates coupler and developer components selected from the group of primary aromatic amines with another free one in the para or ortho position or substituted hydroxy or amino group, the diaminopyri dinderivate, the heterocyclic hydrazone, the 4-aminopyra zolone derivatives, the 2,4,5,6-tetraaminopyrimidines, the m-phenylene diamond derivatives, naphthols, resorcinols and resorcinols vate, the pyrazolones and the m-aminophenols.