DE20003105U1 - Hair dye - Google Patents

Description

Hair dye

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.

On the one hand, they must be viscous enough to remain on the hair to ensure a sufficient coloring effect, but on the other hand, they must be completely and easily rinsed out of the hair after coloring is complete. Such compositions therefore usually contain a thickening agent. The number of substances proposed for this purpose is high, but they are not able to provide optimal effectiveness and compatibility with the direct dyes used.

This also applies to the colorants described in DE 34 23 349 C2, which contain xanthan gum as a thickener: their use is mainly limited to agents containing nitrobenzene derivatives as colorants.

The invention is therefore based on the task of creating a water-based hair dye which can be applied to the hair as a lotion, emulsion, solution, gel, suspension or, with the addition of propellants, as an aerosol composition, which has optimal rheological properties, remains stable over a long period of time and shows excellent coloring properties with both anionic and cationic direct hair dyes.

A-AlOO -2-

The solution to this problem consists in adding a polydimethyl or a polydiethylamino-C2-C3- _alkyl methacrylate polymer, which can preferably be quaternized, to such an agent.

This polymer is extremely compatible with both cationic and anionic dyes; the compositions are stable over a long period of time, even at acidic pH values, and produce intense, shiny hair colors. In addition, a hair conditioning effect is achieved, in particular improved wet and dry combability, looser feel, volume and elasticity; any roughness of the hair that sometimes occurs when hair is dyed repeatedly is avoided.

In addition, the colorings achieved with the hair dyes according to the invention are also extremely stable and remain virtually unchanged even after several hair washes.

Such polydimethylaminoethyl methacrylates or polydiethylaminoethyl or -aminopropyl methacrylates are obtained by polymerization of the corresponding monomers and are also available on the market, for example under the name "Polyquaternium 37", e.g. as a 50% dispersion in an organic medium, e.g. liquid fatty acid esters and/or fatty alcohols.

Particularly preferred is the use of a dimethylaminoethyl methacrylate homopolymer quaternized with methyl chloride or dimethyl or diethyl sulfate.

A-4/00 -3-

The proportion of dimethyl or polydiethylaminoethyl or propyl methacrylate polymers in the hair dyes according to the invention is about 0.25 to about 10, preferably about 0.5 to about 7.5, in particular about 1 to about 5 wt. %, calculated on the total composition of the agent.

In principle, it is possible but not necessary to add other known thickeners to the composition according to the invention, provided that they are compatible with its other components, in particular the cationic or anionic dyes at acidic pH values.

Such thickeners are known to the person skilled in the art and therefore do not require a list.

The proportion of direct dyes in the compositions according to the invention is variable and is between about 0.005 to about 5, preferably 0.01 to 2.5, in particular 0.1 to 1% by weight of the agent.

In principle, all cationic dyes proposed for this purpose can be used as direct hair dyes.

The so-called "Arianor" dyes are preferred; see K. Schrader, "Fundamentals and Recipes of Cosmetics", 2nd edition (1989), p. 811.

Particularly suitable basic (cationic) dyes are:

Basic Blue 6, C.l.-No. 51,175;

Basic Blue 7, C.l.-No. 42,595;

Basic Blue 9, C.l.-No. 52,015;

Basic Blue 26, C.l.-No. 44,045;

Basic Blue 41, C.l.-No. 11,154;

· ·*■

Basic Blue 99,
Basic Brown 4,
Basic Brown 16,
Basic Brown 17,
Natural Brown 7,
Basic Green 1,
Basic Red 2,
Basic Red 22,
Basic Red 76,
Basic Violet 1,
Basic Violet 3,
Basic Violet 10,
Basic Violet 14,
Basic Yellow 57,

C.l.-No. 56,059; C.l.-No. 21,010; C.l.-No. 12,250; C.l.-No. 12,251; C.l.-No. 75,500; C.l.-No. 42,040; C.l.-No. 50,240; C.l.-No. 11,055; C.l.-No. 12,245; C.l.-No. 42,535; C.l.-No. 42,555; C.l.-No. 45,170; C.l.-No. 42,510; C.l.-No. 12,719.

Of course, the use of corresponding direct plant dyes or anionic (acidic) direct hair dyes is also possible.

These are usually also 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 wt. %, calculated on the total composition of the agent, which is in the form of a solution, dispersion, emulsion, gel or aerosol preparation for direct application.

Suitable anionic dyes that can be used include:

Acid Black 1, Acid Blue 1, Food Blue 5, Acid Blue 9, Acid Blue 74, Acid Red 18, Acid Red 27, Acid Red 87, Acid Red 92, Acid Orange 7, Acid Violet 43, Acid Yellow 1, Acid Yellow 23, Acid Yellow 3, Food Yellow No. 8, 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. 20,470; C.I. No. 42,045; C.l.-No. 42,051; C.l.-No. 42,090; C.l.-No. 73,015; C.l.-No. 16,255; C.l.-No. 16,185; C.l.-No. 45,380; C.l.-No. 45,410; C.l.-No. 15,510; C.l.-No. 60,730; C.l.-No. 10,316; C.l.-No. 19,140; C.l.-No. 47,005; C.l.-No. 14,270; C.l.-No. 20,170 C.l.-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.

A-4/00 -6-

Vegetable dyes can also be used alone or in combination with synthetic direct dyes, for example henna (red or black), alkanet 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.

Suitable nonionic 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 radical having 5 to 6 carbon atoms, n is a number from 0 to 10, and x is 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 ₂ 2-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":

A-4/00 -7-

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.

Such amine oxides have long been part of the state of the art, for example C ₁₂ -C 18 -alkyldimethylamine oxides such as lauryldimethylamine oxide, C 1 -C 40 -alkylamidopropyl or ethylamine oxides, C ₁₂ -C ₁₈ -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.

A-4/00 -8-

In some cases, betaines can have the structure

_CH2 - _CH2 -OH

and R-C-N-CH ₂ -CH ₂ -N®-CH ₂ COO ⁹

I I I

CH ₃ OHH

where R is a Ce-C-is-alkyl group and η is 1 to 3, sulfobetaines of the structure

_CH3

I
where R is a C ₈ -Ci ₈ - R—n®— (CH ₂ ) _n -so® alkyl group and &eegr; 1 to 3

mean, I

^CH3

and amidoalkylbetaines of the ' structure

CH ₃ R-C - N — (CH ₂ ) _n - N/®-CH ₂ -COO ⁰

I I

oh Ch ₃

where R is a C ₈ -C ₁₈ alkyl group and η is 1 to 3. Preference is given to fatty acid amidoalkylbetaines, in particular cocoamidopropylbetaine, and cocoamphoacetate and cocoamphoacetate propionate, in particular their sodium salts. Particular preference is given to mixtures of cocoamidopropylbetaine and cocoamphoacetate, in particular in a weight ratio of 3:1 to 1:3, especially 2:1 to 1:1.

A-4/00 -9-

Suitable cationic surfactants are, for example, long-chain quaternary ammonium compounds which can be used alone or in a mixture with one another, such as cetyltrimethylammonium chloride, dimethyldistearylammonium chloride, trimethylcetylammonium bromide, stearyltrimethylammonium chloride, dimethylstearylbenzylammonium chloride, benzyltetradecyldimethylammonium chloride, dimethyldihydrogenated 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 ¹ -CO -[EO] -OCH ₂ CH ₂ -N-CH ₂ CH ₂ O-[EO] -COR ² ] Y"

^R (I)

in which R ¹ and R ² represent an optionally hydroxy-substituted C ₈ -C ₂₂ alkyl or alkenyl group, R ³ and R ⁴ represent a Ci-C ₃ alkyl group or a group -CH ₂ -CHb-O-[EO] ₂ H and x, y and ζ 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 Ci ₂ -Cia-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.

• · ♦ ·

V ·«

A-4/00 -10-

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 ".

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 -N - ^CR2
OH R ⁴ HO

Y'
(&Pgr;)

in which R ¹ and R ² each represent an optionally hydroxy-substituted Ce-C ₂₂ alkyl
or alkenyl group, R ³ and R ⁴ represent a Ci-C3-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, as long as they are compatible with each other.

Another desirable component of the colorant compositions according to the invention is a C3- _C6 alkanediol or its ether, in particular a mono- _CiC3 alkyl ether.

&igr;&igr;&igr;&igr;

A-4/00 -11-

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.

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 may also contain other care products such as oils and fats.
These include, for example, sunflower oil, almond oil, peach kernel 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.

t ·

A-4/00 -12-

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 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 5,000 to about 60,000, in particular about 10,000 to 50,000, especially about 20,000 to 40,000 mPa.s at 20 ^° C, measured in a Brookfield rotational viscometer with a spindle no. 5 at 5 rpm.

The pH value is in the acidic range between about 2 and 7, preferably 2.5 and 6, in particular about 3 and 5.5.

The following examples serve to illustrate the invention.

Example Dimethicone Copolyol 1 1.50 (wt.%) Ethanol 5.00 Propylene carbonate 25.00 Lactic acid, 90% 5.00 Sodium hydroxide, 32% 0.20 Quaternary dimethylaminoethyl methacrylate 3.50 Homopolymer (Polyquaternium-37;50% in a propylene glycol dicaprate dicaprylate / PPG-1-Trideceth-6 mixture; Salcare ^R SC96) Acid Orange 7 (C.l. No. 15510) 0.15 Acid Yellow 3 (C.l. No. 47005) 0.10 Acid Violet 43 (C.l. No. 60 730) 0.25 Water ad 100.00 PH value: 3.0 Viscosity at 20 ⁰ C in rotational viscosity meters to Brookfield (Spindle No. 5, 5rpm): -33 000 mPa.s

The composition was subjected to a four-month storage test at 40 ⁰ C. No instability or precipitation occurred and the product did not differ from the starting product.

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.

&phgr; ·«

-14-

Example Dimethicone Copolyol 2 1.50(wt%) Ethanol 5.00 Propylene carbonate 26.00 Lactic acid, 90% 5.00 Sodium hydroxide, 32% 0.30 Perfume 0.30 Quaternary polydimethylaminoethylamino 3.50 methacrylate homopolymer (Polyquaternium-37; 50% in paraffin oil and PPG-1 Trideceth-6; Salcare ^R SC95) D&C Orange 4 (C.l.-No 15 510) 0.18 Acid Violet 43 (C.l. No. 60 720) 0.48 D&C Yellow 10 (C.l.-No. 47005) 0.08 Water ad 100.00 PH value: 3.0 Viscosity at 20 ⁰ C in rotational viscosity meters to Brookfield (Spindle No. 5, 5rpm): -36 000 mPa.s

The composition remained stable after 4 months of storage at 40 ⁰ C. Following the procedure described in Example 1, a shiny violet-brown hair color was obtained which lasted for four washes; the hair was easy to comb with elasticity and full grip.

-15-

Example 3 4.60 (wt.%) Vinylpyrrolidone/vinyl acetate copolymer
(Luviskol ^R VA64W) 3.50 Quaternary polydimethylaminoethylamino ethyl methacrylate homopolymer (Polyquaternium-37; 50% in propylene glycol dicaprylate/dicaprate/ PPG-1 Trideceth-6; Salcare^SC96) 0.30 Perfume 0.10 Phenoxyethanol 0.50 1,2-Propanediol 0.75 Ethanol 0.10 Basic Blue 99 (C.I. No. 56 059) 0.18 Basic Brown 16 (C.l.-No. 12 250) 0.32 Basic Brown 17 (C.l.-No. 12 251) 0.36 Basic Yellow 57 (C.l. No. 12 719) 100.00 Water ad 5.8 PH value: Viscosity at 20 ⁰ C in rotational viscosity meters to Brookfteld -15 000mPa.s (Spindle No. 5, 5rpm):

The composition remained stable after four months of storage at 4O ⁰ C.

When the hair was dyed according to the method described in Example 1, a shiny gold color was achieved which was stable over several washes. The hair had excellent conditioning properties.

-16-

Example Polyquaternium-6 4 0.60 (wt.%) Cetrimonium chloride 0.80 1,2-Propanediol 0.40 Phenoxypropanol 0.10 Perfume 0.30 Quaternary polydimethylaminoethylamino 6.00 ethyl methacrylate homopolymer (Polyquaternium-37; 50%) Basic Blue 99 (C.l.-No 56059) 0.04 Basic Brown 16 (C.l. No. 12250) 0.36 HC Red 3 0.17 HC-Yellow 5 0.33 Water ad 100.00 PH value: 6.5 Viscosity at 20 ⁰ C in rotational viscosity meters to Brookfield (Spindle No. 5, 5rpm): -12 000 mPa.s

The composition remained completely stable after four months of storage at 40°C.

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

An additional significant hair conditioning effectiveness was achieved.

Claims (4)

1. Water-based hair dyes containing (a) at least one direct hair dye; and b) at least one optionally quaternized dimethyl or diethylamino C ₂ -C ₃ alkyl methacrylate polymer. 2. Hair dye according to claim 1, containing 0.25 to 10 wt.% of the dimethyl or diethylamino C ₂ -C ₃ alkyl methacrylate polymer. 3. Hair dye according to claim 1 or 2, containing a quaternary polydimethylaminoethyl homopolymer. 4. Hair dye according to one or more of claims 1 to 3, which has a pH value between 2 and 6.5.