DE20011145U1 - Hair dye - Google Patents

Description

_# · · · i 11"» · I Il '.

A-21/00-U Hair dyes

The invention relates to a water-based hair dye containing at least one direct hair dye.

Such hair dyes have been known for a long time.

They usually contain several anionic or cationic direct dyes and, unlike permanent hair dyes based on oxidation dye precursors, do not require prior development with oxidizing agents.

These direct-dyeing compositions are either applied together with surfactants as so-called tinting shampoos or, like the compositions according to the invention, as lotions, emulsions or thickened solutions, i.e. gels, to the hair.

The pH value of these hair dyes based on direct dyes is usually between about 3 and about 7.

Cationic direct hair dyes are usually used as direct dyes, although in principle the use of anionic dyes is also known and possible.

However, the use of anionic dyes does not achieve the color effect that is provided and required by cationic direct dyes.

It has now surprisingly been found that even with anionic direct dyes, a good hair coloring which is not inferior to that achieved with cationic direct dyes can be achieved when these are used in compositions with an unusually low pH value.

A-21/00 -2-

The invention therefore relates to a hair dye and the use thereof for dyeing human hair, which contains at least one anionic direct hair dye in an aqueous base and has a pH of at most 2.5, preferably less than 2, in particular between 1 and 2.

The anionic (acidic) direct hair dyes are usually used in an amount of about 0.005 to about 5, preferably about 0.05 to about 2.5, in particular about 0.1 to about 1% by weight, calculated on the total composition of the agent, which is available as a solution, dispersion, emulsion, gel or aerosol preparation for direct application.

Suitable anionic dyes that can be used include:

Acid Black 1, C.l.-No. 20,470;

Acid Blue 1, C.l. No. 42,045;

Food Blue 5, C.l. No. 42,051;

Acid Blue 9, C.l. No. 42,090;

Acid Blue 74, C.l.-No. 73,015;

Acid Red 18, C.l. No. 16,255;

Acid Red 27, C.l. No. 16,185;

Acid Red 87, C.l. No. 45,380;

Acid Red 92, C.l. No. 45,410;

Acid Orange 7, C.l.-No. 15,510;

Acid Violet 43, C.l.-No. 60,730;

Acid Yellowl, C.l.-No. 10,316;

Acid Yellow 23, C.l.-No. 19,140;

Acid Yellow 3, C.l.-No. 47,005;

Food Yellow No. 8, C.l.-No. 14,270;

D&C Brown No. 1, D&C Green No. 5, D&C Orange No. 4, D&C Orange No. 10, D&C Orange No. 11, D&C Red No. 21, D&C Red No. 27, D&C Red No. 33, D&C Yellow No. 7, D&C Yellow No. 8, FD&C Red No. 4, FD&C Yellow No. 6,

C.l.-No. 20,170 C.I. No. 61,570; C.l.-No. 15,510; C.i. No 45,425:1; C.l.-No. 45,425; C.l.-No. 45,380:2; C.l.-No. 45,410:1; C.l.-No. 17,200; C.l.-No. 45,350:1; C.l.-No. 45,350; C.l.-No. 14,700; C.l.-No. 15,985.

Vegetable dyes can also be used alone or in combination with synthetic
anionic direct dyes are used, for example henna (red or
black), Alkanna root, Laccaic acid (stick varnish), Indigo, Logwood powder,
Madder root and rhubarb root powder, etc.

The hair dye according to the invention can also contain surface-active substances
although it is not a tinting shampoo.

These can be anionic, non-ionic, cationic or amphoteric or zwitterionic.

Preferred are nonionic and cationic surfactants in an amount between about 0.5 and about 5% by weight, calculated on the total composition.

-A-

Suitable non-ionic surfactants are compounds from the class of alkylpolyglucosides
with the general formula

RO-(CH ₂ CH ₂ O) _n -Z _x ,

wherein R is an alkyl group having 8 to 20, preferably 10 to 14 carbon atoms, Z _{x is} a saccharide residue having 5 to 6 carbon atoms, n is a number from 0 to 10, and &khgr;
a number between 1 and 5, preferably 1.1 to 2.5.

Other suitable nonionic surfactants in the compositions according to the invention are C 10 -C ₂₂ fatty alcohol ethoxylates.

Particularly suitable Ci ₀ -C ₂₂ fatty alcohol ethers are the alkyl polyglycol ethers known under the trivial names "Laureth", "Myristeth", "Oleth", Ceteth", "Deceth", "Steareth" and "Ceteareth" according to the CTFA nomenclature with the addition of the number of ethylene oxide molecules, e.g. "Laureth-16":

The average degree of ethoxylation is between about 2.5 and about 25, preferably about 10 and about 20.

Other non-ionic surfactants that can also be used are, for example, the various sorbitan esters, such as polyethylene glycol sorbitan stearic acid esters, fatty acid polyglycol esters or mixed condensates of ethylene oxide and propylene oxide, such as those sold under the trade name "Pluronics®".

Other surfactants that can be used additionally are amine oxides.

-5-

Such amine oxides have long been part of the state of the art, for example Ci ₂ -Ci 8 -alkyldimethylamine oxides such as lauryldimethylamine oxide, C^-Cis-alkylamidopropyl or ethylamine oxides, Ci ₂ -Ci ₈ -alkyldi(hydroxyethyl) or -(hydroxypropyl)amine oxides, or also amine oxides with ethylene oxide and/or propylene oxide groups in the alkyl chain.

Suitable amine oxides are available, for example, under the names “Ammonyx®”,
"Aromox®", or "Genaminox®" in the trade.

Other optional surfactant components are fatty acid mono- and dialkanolamides, such as coconut fatty acid monoethanolamide and myristic fatty acid monoisopropanolamide.

Suitable amphoteric or zwitterionic surfactants are in particular the various known betaines such as fatty acid amidoalkylbetaines and sulfobetaines, for example laurylhydroxysulfobetaine; long-chain alkylamino acids such as cocoaminoacetate, cocoaminopropionate and sodium cocoaminopropionate and acetate have also proven to be suitable.

In some cases, betaines can have the structure

_CH2 - _CH2 -OH

R— n£-(CH^, -C00 ^e and R-CN-CH ₂ - CH ₂ -N®-CH ₂ COO ⁹

I I I

CH ₃ OHH

where R is a C ₈ -C ₁₈ alkyl group and η is 1 to 3,

·· &idigr;β-&idigr;* ·■>' tfi

-6-

Sulfobetaines of the structure

_CH3
R—&Ngr;^&Thetas; -(CH ₂ J _n -SO®

_CH3

where R is a Ca-C-ie-alkyl group and η is 1 to 3, and amidoalkylbetaines of the structure

_CH3

RC — N — (CH ₂ ) _n - IS— _CH2 - COO°

II. I I

oh Ch ₃

where R is a Ca-Cie alkyl group and η is 1 to 3.

Preference is given to fatty acid amidoalkyl betaines, in particular cocoamidopropyl betaine, and cocoamphoacetate and cocoamphopropionate, in particular their sodium salts. Particular preference is given to mixtures of cocoamidopropyl betaine and cocoamphoacetate, in particular in a weight ratio of 3:1 to 1:3, especially 2:1 to 1:1.

Suitable cationic surfactants are, for example, long-chain quaternary ammonium compounds, which can be used alone or in mixtures with one another, such as cetyltrimethylammonium chloride, dimethyldiethylammonium chloride, trimethylcetylammonium bromide, stearyltrimethylammonium chloride, dimethylstearylbenzylammonium chloride, benzyltetradecyldimethylammonium chloride, dimethyldi-

-7-

hydrogenated tallow ammonium chloride, laurylpyridinium chloride, lauryldimethylbenzylammonium chloride, behenyltrimethylammonium chloride, lauryltrimethylammonium chloride, tris-(oligooxy-ethyl)alkylammonium phosphate, cetylpyridinium chloride, etc. The quaternary ammonium salts disclosed in EP-A 472 107 are also very suitable.

Other suitable long-chain ammonium compounds are esterquats of the general formula (I)

^R3

[R' -CO -[EO] X-OCH ₂ CH ₂ -N-CH ₂ CH ₂ O-[EO] -COR ² ] Y"

^R4 (I)

in which R ¹ and R ² represent an optionally hydroxy-substituted C 8 -C 12 alkyl or alkenyl group, R ³ and R ⁴ represent a C 1 -C ₃ alkyl group or a group -CH 2 -CH ₂ -O-[EO] _Z H and x, y and z represent O to 5 and Y" represents an anion.

A particularly preferred compound of formula I within the scope of the invention is one in which the radicals R ¹ and R ² each represent an oleyl group or a C12-C18-alkyl group, the radical R ³ represents a methyl group and the radical R ⁴ represents a group -CH ₂ -CH ₂ -O-[EO] ₂ -H.

The anion Y" is preferably a halide such as Cl" or Br", a lower alkyl sulfate, e.g. methosulfate and ethosulfate, or an alkyl phosphate, but of course other radicals can also be used.

These compounds are known per se and are sold under the trade names "Schercoquat ^R ", "Dehyquart ^R F30" and "Tetranyl ^R ".

α-21/00 -8-

The use of these "esterquats" in hair care products is known per se and is described, for example, in WO-A 93/10748, WO-A 92/06899 and WO-A 94/16677.

Amidoquats of the general formula (II) are also suitable

R ¹ -C-N-CH ₂ CH ₂ -N ⁺ -CH ₂ CH ₂ -N - ^CR2

I I I I

OH R ⁴ HO

(&Pgr;)

in which R ¹ and R ² each represent an optionally hydroxy-substituted Ce-C ₂ 2-alkyl-
or alkenyl group, R ³ and R ⁴ represent a Ci-Ca-alkyl group or a group-CH ₂ -CH ₂ -O-[EO] _x -H,
and &khgr; stands for O to 5, Y" stands for an anion.

Of course, mixtures of the different surfactants can also be used, provided they are compatible with each other.

Another desirable component of the colorant compositions according to the invention is a C ₃ -C 6 alkanediol or its ether, in particular a mono-C 1 -C ₃ alkyl ether.

Preferred substances in this context are 1,2- and 1,3-propanediol,
1-Methoxypropanol(-2), 1-ethoxypropanol(-2), 1,3- and 1,4-butanediol, diethylene glycol
and its monomethyl and monoethyl ethers as well as dipropylene glycol and its monomethyl and monoethyl ethers.

The proportion of these diols is preferably between 0.5 and 30, preferably about 1 to about 15, in particular about 5 to about 10 wt.% of the colorant composition.

2**

*· 4

-9-

In addition to the C ₃ -C ₆ alkanediols or their ethers, monoalcohols such as ethanol, propanol-1, propanol-2 as well as polyalcohols such as glycerin and hexanetriol, ethyl carbitol, benzyl alcohol, benzyloxyethanol as well as propylene carbonate (4-methyl-1,3-dioxolan-2-one), N-alkylpyrrolidones and urea can also be used.

Other possible additional components are cationic, anionic, nonionic and amphoteric polymers, preferably in an amount of about 0.1 to about 5, in particular about 0.25 to 2.5 wt.% of the total composition of the colorant.

These products can also contain other care products such as oils and fats. Examples include sunflower oil, almond oil, peach oil, wheat germ oil, macadamia nut oil, evening primrose oil, jojoba oil, castor oil, or olive or soybean oil, lanolin and its derivatives, as well as mineral oils such as paraffin oil and Vaseline.

Synthetic oils and waxes include silicone oils, polyethylene glycols, etc.

Other suitable hydrophobic components are in particular fatty acid esters such as isopropyl myristate, palmitate, stearate and isostearate, oleyl oleate, isocetyl stearate, hexyl laurate, dibutyl adipate, dioctyl adipate, myristyl myristate, oleyl erucate, polyethylene glycol and polyglyceryl fatty acid esters such as PEG-7-glyceryl cocoate, cetyl palmitate, etc.

If the agents according to the invention are emulsions, they naturally contain the usual emulsifiers.

The hair dyes according to the invention preferably also contain thickeners. Examples of thickeners are the various cellulose derivatives such as hydroxyalkylcelluloses, e.g. hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, natural polysaccharides such as xanthan gum, guar gum and their alkoxylation products, synthetic polymers such as the various polyacrylic acids, etc., in amounts of about 0.3 to about 5% by weight, depending on the desired consistency of the composition.

The agents according to the invention can also contain long-chain fatty acids.
The fatty acids used are preferably those with 10 to 24, in particular 12 to 22 carbon atoms in an amount of about 0.5 to 15% by weight, in particular 1 to 10% by weight, based on the total composition. Behenic acid and stearic acid are particularly suitable; however, other fatty acids such as myristic acid, palmitic acid or oleic acid or mixtures of natural or synthetic fatty acids such as coconut fatty acid can also be used.

The viscosity of the agents according to the invention is preferably about 5000 to
about 60 000, in particular about 10 000 to 50 000, especially about 20 000 to
40 000 mPa.s at 2O ⁰ C, measured in a Brookfield rotational viscometer with a
Spindle no. 5 at 5rpm.

The acidic pH value of maximum 2.5, preferably less than 2, in particular 1 to 2, is adjusted by adding acid.

The following examples serve to illustrate the invention.

α-21/00 -11-

Example Dimethicone Copolyol 1 1.50 (wt.%) Ethanol 5.00 Propylene carbonate 25.00 Sodium hydroxide, 32% 0.20 Quaternary dimethylaminoethyl methacrylate 3.50 Homopolymer (Polyquatemium-37; 50% in a propylene glycol dicaprate dicaprylate PPG-1-Trideceth-6 mixture; Salcare ^R SC96) Acid Orange 7 (C.l. No. 15,510) 0.15 Acid Yellow 3 (C.l. No. 47,005) 0.10 Acid Violet 43 (C.l. No. 60,730) 0.25 Lactic acid, 90% '< to pH 1.8 Water up to 100,00

The composition was applied to wet hair. After about twenty minutes of exposure, the hair was washed, rinsed and dried. The result was shiny, medium-brown hair that was easy to comb and had a full feel and resilience. The color lasted for four washes.

An analogous staining with an identical product adjusted to a pH of 3.0 resulted in a significantly less intense and stable staining.

-12-

Example 2 1.50 (wt. %) Dimethicone Copolyol 5.00 Ethanol 26.00 Propylene carbonate 0.30 Sodium hydroxide, 32% 0.30 Perfume 2.50 Xanthan Gum (Keltrol ^R ) 0.18 D&C Orange 4 (C.l.-No 15,510) 0.48 Acid Violet 43 (C.l. No. 60,720) 0.08 D&C Yellow 10 (C.l.-No. 47,005) pH1.5 Lactic acid, 90% ad 100.00 Water ad

Following the procedure described in Example 1, a shiny violet-brown hair color was obtained which lasted for four washes.

This hair dye was clearly superior to one that was produced in an identical manner with the same composition but adjusted to pH 3.0 in terms of color intensity, stability and uniformity.

-13-

Example 3 1.00(wt%) Hydroxyethylcellulose 1.00 Decylglucoside 0.30 Perfume 11,50 Lactic acid, 90% 0.50 1,2-Propanediol 0.75 Ethanol 0.40 D&C Orange 4 (C.l.-No 15,510) 0.05 Rhodamine EB4 (C.l.-No. 45,100) up to 100,00 Water 1.9 PH value:

When the hair was dyed according to the procedure described in Example 1, a shiny copper-red color was achieved that remained stable over several washes.

Increasing the pH value to 3.5 resulted in a reduction in the intensity, stability, uniformity and gloss of the coloration.

9 V »· &diams; ·

-14-

Example 4 0.40 (wt.%) Cetrimonium chloride 0.40 1,2-Propanediol 0.10 Phenoxypropanol 0.40 Panthenol 0.30 Perfume 2.00 Xanthan Gum (Keltrol ^R ) 0.36 D&C Orange 4 (C.l.-No 15,510) 0.30 Alizarin Violet (C.l.-No. 60,730) 8.00 Citric acid up to 100,00 Water - 2.0 PH value:

The hair coloring resulted in a shiny reddish-brown tone that was still noticeable after five washes.

-15-

Example 5

Part A:

Steartrimonium chloride 0.22 (wt.%) Quaternary wheat protein hydrolysate 0.50 (Gluadin ^R W40) Hydroxyethylcellulose 1.50 Lactic acid 5.00 D&C Orange 4 (Cl-No. 15 510) 0.22 Alizarin Violet (Cl.-No.60 730) 0.04 Rhodamine EB 4 (C.l.-No. 45 100) 0.42 Water 82.10 PH value ~ 3.0 Part B:

H ₃ PO ₄ (85%) Water

1.7(wt%) 8.3

Parts A and B, which were kept separate in a two-component package until application to the hair, were mixed before application to the hair, resulting in a pH value of approximately 1.6.

The hair coloring resulted in a strong, shiny, intense, stable, evenly distributed violet tone.

The comparison staining with part A alone produced a much weaker

Color image.

Claims (3)

1. A water-based hair dye containing at least one direct anionic hair dye; the ready-to-use composition has a maximum pH of 2.5. 2. Hair dye according to claim 1, which has a pH of less than 2. 3. Hair dye according to claim 1 and 2, which has a pH between 1 and 2.