DE20011207U1 - Means for coloring human hair - Google Patents

Description

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A-24/OO-Ou.

Agents for coloring human hair

The present invention relates to a composition for dyeing human

Hair that results in hair coloring with increased color intensity. ;

It is generally known that hair dyes are divided into two categories: permanent hair dyes, which basically contain hair dye precursors which, together with oxidizing agents, develop the desired color on the hair depending on their composition; and semi-permanent hair dyes, which contain direct dyes which do not require any oxidizing agent to develop their coloring performance. Accordingly, the colors are less permanent than those achievable with permanent dyes.

These colour compositions based on direct dyes are usually applied either as tinting shampoos, as colour lotions or as tinting fixatives, or possibly as aerosol foam.

The direct dyes used are generally of a cationic nature; as another essential component, the compositions used as rinses also contain cationic surfactants, in particular quaternary ammonium salts.

However, the colour intensity and durability achievable with these compositions is not always satisfactory.

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It has now been found that hair coloring with improved color intensity and stability as well as great uniformity can be achieved if the coloring is carried out with a hair dye that

a) at least one direct cationic hair dye selected from

at least one compound of the general formula b)

R ¹ —&Ngr;®\— CH=NN-

&Ugr;&THgr; (I)

R ^s

^R3

V-N=N-/ \ —N

γθ;

(H)

and or

where R ¹ , R ² , R ³ and R ⁴ represent hydrogen, a CH ₃ or C ₂ H ₅ group

and R ⁵ is hydrogen, -OCH ₃ or -OC ₂ H ₅ ,

and or

- NH ₂ �U ^θ

(&Igr;&Pgr;) ,

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= N &mdash;</ \>&mdash;N&mdash; i Z)-NH ₂ &Ugr;&thetas; (IV)

I H

where R ¹ and R ² are -CH ₃ or -C ₂ H ₅

and Y" in all cases represent an anion

b) contains at least one amphoteric and/or zwitterionic surfactant.

Preferred dyes according to the abovementioned formulae are those corresponding to (I) in which R ¹ and R ² are a methyl group and R ⁵ is hydrogen or a methoxy group, corresponding to formula (II) in which R ¹ and R ² are methyl groups and R ³ and R ⁴ are hydrogen or a methyl group, and corresponding to formulas (III) and (IV) in which R ¹ and R ² are each a methyl group.

The anion Y" is preferably C ₂ H ₅ SO ₄ ', CH ₃ SO ₄ " or CP.

The proportion of these direct cationic dyes in the agents according to the invention is preferably about 0.001 to about 5, in particular about 0.05 to 1.5, especially about 0.1 to about 1 wt. %, calculated on the hair dye.

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In addition to the essential dyes of the general formulas (I) to (IV), other well-known synthetic and natural direct hair dyes can also be used.

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

The so-called "Arianor" dyes are preferred; cf. 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, C.l.-No: 56,059; Basic Brown 4, C.l. No. 21,010; Basic Brown 16, C.l. No. 12,250; Basic Brown 17, C.l. No. 12,251; Natural Brown 7, C.l.-No. 75,500; Basic Green 1, C.l. No. 42,040; Basic Red 2, C.l.-No. 50,240; Basic Red 22, C.l. No. 11,055;

Basic Red 76,
Basic Violet 1,
Basic Violet 3,
Basic Violet 10,
Basic Violet 14,
Basic Yellow 57,

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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.

Suitable amphoteric or zwitterionic surfactants within the scope of the invention are in particular alkylamidobetaines of the general formula

R ₁ I RC -N -(CH ₂ J _n -N ⁺ -

OH

_IR2

where R is a C ₈ -C ₁₈ alkyl group, e.g. a cocoalkyl radical; R-| and R2 are a lower C ₄ alkyl or hydroxyalkyl radical, in particular a methyl, ethyl and/or hydroxyethyl group; R3 is a COO" or -SO3~ group; and η is 1 to .

Betaines of the general formula

_R1

RN ⁺ -(CH ₂ J _n IR ₂

_-R3

where R, Ri, R2, R3 and η have the abovementioned meaning, are preferred.

> ft ft · · ·

-6-Such betaines are, for example, with the following formula

CH ₃ I

RC -N-(CH ₂ )nN©-CH ₂ -COO© II II

_OHCH3

and or

CH ₂ -CH ₂ -OH I RC- N-CH ₂ -CH ₂ -N©-CH ₂ C0O®

Ii &igr;&igr;

OH &eegr;

a sulfobetaine with the formula

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_CH3

R - N©- (CH ₂ )n - S0 ₃ © I
_CH3

and a betaine with the formula

_CH3

RN©-(CH ₂ )n-COO© I
_CH3

where R is a C ₈ -Ci ₈ alkyl group and η is 1 to 3.

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Commercial products such as "Tegobetaine®", "Dehytone®" such as "AB 30", "G" and "K", "Lonzaine®", "Varion® ¹¹ such as "ADG" and "CAS", "Lexaine®", "Chembetaine®", "Mirataine®", "Rewoteric®", "Schercotaine®", "Monteine LCQ®";""Alkateric® ¹¹ , "Amonyl®", "Amphosol®", "Cycloteric BET® ¹¹ , "Emcol® ¹¹ , "Empigen® ¹¹ , "Mackam® ¹¹ , "Monateric® ¹¹ , "Unibetaine®" and "Velvetex®" are particularly suitable.

Further preferred amphoteric or zwitterionic surfactants are selected from the group Cs-ds-alkylhydroxysulfobetaine, a carboxymethyl-Ce-Cia-alkylpolypropylamine and/or compounds of the formula

R - C - N - R ¹ - N - R ¹ - COOH, or

I I

OH (CH ₂ ) _n OH
R - C - N - R ¹ - N - R ¹ - SO ₃ H,

I I

OH (CH ₂ ) _n OH

wherein R is a C ₈ -C ₂₀ alk(en)yl group, preferably a C 8 -C 20 alkyl group, R ¹ is an optionally hydroxy-substituted, straight- or branched-chain alkylene group having 1 to 3 carbon atoms and η 1 to 3, or their water-soluble salts.

Preference is given to sodium caproamphoacetate, sodium caproamphopropionate, sodium caproamphohydroxypropylsulfonate, sodium cocoamphopropionate or acetate, sodium cocoamphohydroxypropylsulfonate, sodium isostearoamphoglycinate and also sodium carboxymethylmethylcocopolypropylamine of the formula

-N - CH ₂ - CH ₂ - CH ₂ -]&mdash; N-CH ₂ - COO Na

&Iacgr;^&eegr;&igr;

CH ₂ COONa CH ₂ COONa ,

·

·

see reported perforation data

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-8-where
R is a coconut alkyl radical and η is preferably 1 to 4.

The zwitterionic or amphoteric surfactants are preferably contained in an amount of 0.1 to 7.5 wt.%, in particular 0.25 to 5 wt.%, calculated on the total composition.

An optional component of the compositions according to the invention is an anionic, preferably water-soluble UV absorber, which is preferably used in an amount of 0.1 to 5, in particular 0.25 to 2.5% by weight, calculated on the total composition of the agent.

Particularly suitable water-soluble UV absorbers with anionic groups are, for example, 5-benzoyl-4-hydroxy-2-methoxybenzenesulfonic acid (benzophenone-4), its sodium salt (benzophenone-5) and 2,2'-dihydroxy-4,4'-dimethoxy-3,3'-disulfobenzophenone or its disodium salt (benzophenone-9) as well as phenylbenzimidazolesulfonic acid (Eusolex® 232); however, other water-soluble UV absorbers can also be used.

The preferred weight ratio of zwitterionic or amphoteric surfactant to anionic UV absorber, if present, is preferably about 1:1 to about 3:1.

The compositions according to the invention can also contain at least one cationic surfactant, in particular in an amount of 0.1 to 7.5, preferably 0.25 to 5, particularly preferably 0.5 to 2.5% by weight of the total composition.

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Suitable long-chain quaternary ammonium compounds which can be used as cationic surfactants alone or in a mixture with one another are in particular cetyltrimethylammonium chloride, dimethyldicetylammonium chloride, trimethylcetylammonium bromide, stearyltrimethylammonium chloride, dimethylstearylbenzylammonium chloride, benzyltetradecyldimethylammonium chloride, dimethyldihydrogenated tallow ammonium chloride, laurylpyridinium chloride, lauryldimethylbenzylammonium chloride, lauryltrimethylammonium chloride, tris(oligooxyethyl)alkylammonium phosphate, cetylpyridinium chloride, etc.

The quaternary ammonium salts disclosed in EP-A 472 107 are also well suited.

In principle, all quaternary ammonium compounds as listed in the "CTFA International Cosmetic Ingredient Dictionary", Fourth Ed. (1991), under the trivial name "quaternium" are suitable.

The composition can of course also contain the ingredients usually found in such conditioning agents; to avoid repetition, reference is again made to K. Schrader, "Grundlagen und Rezepturen der Kosmetika", 2nd edition (1989), pp. 722 - 771.

Non-ionic surfactants can also be used, especially in a mixture with cationic surfactants, for example amine oxides in an amount of about 0.25 to about 5, preferably about 0.5 to about 3.5% by weight, calculated on the total composition of the agent.

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Such amine oxides have long been part of the state of the art, for example C^-Cie-alkyldimethylamine oxides such as lauryldimethylamine oxide, C^-Cie-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.

Other suitable surfactants are the known C ₈ -C ₁₈ alkyl polyglucosides, in particular with a degree of polycondensation of 1.2 to 3.

The hair dyes according to the invention can contain the substances customary in such aqueous preparations.

These are, for example, synthetic or natural hair conditioning polymers, preferably in an amount of 0.1 to 2.5, in particular 0.25 to 1.5 wt.% of the total composition.

Suitable cationic polymers, in addition to the well-known quaternary cellulose derivatives of the "Polymer JR" type, are in particular quaternized homo- and copolymers of dimethyldiallylammonium chloride, as sold under the trade name "Merquat", quaternary vinylpyrrolidone copolymers, in particular with dialkylaminoalkyl(meth)acrylates, as known under the name "Gafquat", copolymers of vinylpyrrolidone and vinylimidazolinium methochloride, which are sold under the trade name "Luviquat", polyamino-polyamide derivatives, for example copolymers of adipic acid-dimethylaminohydroxypropyldiethylenetriamine, as sold under the name

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of the cationic polymers or in combination with them, _also known as cationic polymers. Suitable non-ionic
Polymers are mainly vinylpyrrolidone homo- and copolymers, especially vinylpyrrolidone itself, copolymers of vinylpyrrolidone and vinyl acetate, or terpolymers of vinylpyrrolidone, vinyl acetate and vinyl propionate.

as for example from the company RA<5i= > ^

" ^{ma BASF sold under the} trade name "Luviskol".

However, (Co,P _Olym erisate from the different Aoy, and
Me a _{cryl Acry|amid d M}

Me a _cryl

_{and bejspieiswejse} ^

Molecular weights of over 100,000, dimethylhydantoin-formaldehyde-ha.e etc.
ve« Of course, mixtures of different non-iomic polymers can also be used.

"Carotenes F" are sold, as well as bisquaternary ,long-chain amines

"end compounds of the urea compounds described in US Patent 4,157,388

S-ruWur, which is under _the trade name "Mirapo, A 15" in the hands, began". L

In this context, Veaviesen will also refer to the DE-OSen
25 21 960, 28 11 010, 30 44 738 and 32 17 059 mentioned cation actives
Polymers as well as the products described in EP-A 337 354 au, pages 3 to 7. E ₅ mixtures of different cationic _polymers can also be used.

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The colorants according to the invention can contain the additives customary in such compositions, the type and nature of which depends on the form in which the agent is applied. These are fats, fatty alcohols, emulsifiers, pH regulators, solvents and binding agents, solubilizers, preservatives, perfumes, etc.

Suitable fats and oils, which also include waxes, are in particular natural oils such as avocado oil, coconut oil, palm oil, sesame oil, peanut oil, sperm oil, 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.

Finally, amphoteric polymers are also suitable, for example those under the *....'

Copolymers of N-octylacrylamide, N-butylaminoethyl methacrylate and acrylic acid sold under the name "Amphomer ¹¹ ". .·*·*.

Other suitable hydrophobic components are in particular fatty alcohols, preferably those with about 8 to 22 carbon atoms in the molecule such as myristyl, cetyl, stearyl alcohol, wax alcohols and 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.

Porforetionsaoiu... «..«-■■-.

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These hydrophobic components are preferably contained in the compositions according to the invention in a total amount of about 0.5 to about 10, in particular about 1 to 7.5, especially about 1.5 to 5 wt.%, calculated on the total composition.

&bull; j &bull;&bull;&bull;&bull;if

: f

* I

A summary of the production of such agents can be found in the above-mentioned monograph by K. Schrader, pp. 798 to 815, especially pp. 804 ff.

The colorants according to the invention are in the form of an emulsion, dispersion or (optionally thickened, i.e. gel) solution and can also be formulated as an aerosol foam. These compositions and their preparation are basically known to the person skilled in the art and therefore do not require any further explanation.

The pH value of the hair dyes according to the invention is preferably about 3 to 8.5, in particular between 4 and 6.

The following examples describe the composition of the agents according to the invention.

Color rinses of the following composition were prepared by mixing the ingredients:

-14- example 1 Color conditioner Cetylstearyl alcohol 5.0 (wt.%) 1,2-Propanediol 1.5 Behentrimonium chloride 2.0 Di-Cia-Cis-alkyldimonium chloride 1.0 Cocoamidopropyl betaine 1.0 Sodium cocoamphoacetate 0.5 Henna extract 0.5 Compound of formula (II) 0.1 (R ¹ ,R ² ,R ³ =CH ₃ ; R ⁴ =H; V=CI") Methylparaben 0.2 Silicone oil 0.5 Perfume 0.3 Water to 100.0

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After application to human hair, a shiny, intense, uniform henna red color was obtained that was stable over four washes.

Replacing the compound of formula (II) with Basic Red 2 resulted in a less intense and uniform coloration, which began to fade after just two washes.

A similar negative effect was observed when cocoamidopropyl betaine and sodium cocoamphoacetate were replaced by 1.5% by weight of a non-ionic surfactant, namely laureth-12.

s.öerichtl. Perforation dotum H

Hyd roxyethylcell u lose ·* · la. 0.05 Cetylstearyl alcohol A-24/00 ·/··* -15- 1,2-Propanediol 0.05 Example 2 Cetyltrimethylammonium chloride q.s. Color conditioner Dicetyldimethylammonium chloride &bull; · ·&diams;
&bull; * ·
* · · 100.00 Methylparaben 1.00(wt.%) ^: ... _: ^: Dimethicone 1.25 ^: .*.. ^: Laurylhydroxysultain 3.00 Chamomile extract 0.20 Perfume oil 0.30 Compound of formula (I) 0.20 (R ¹ and R ² =CH ₃ ; R ⁵ =H; V=CH ₃ SO ₄ ") 0.20 Compound of formula (II) 1.00 (R ¹ ,R ² ,R ³ =CH ₃ ; R ⁴ =H; V=CI") 0.50 Basic Blue 99 0.30 Citric acid 0.02 Water ad

An expressive, shiny, evenly intense brown color was obtained.

Replacing lauryl hydroxysultaine resulted in hair coloring that was less wash-stable and paler.

Cetylstearyl alcohol 5.00 (wt.%) Di-C^-Cia-alkyldimonium chloride 2.00 -16- 1,2-Propanediol 1.50 BeisDiel 3 Ceteareth-20 1.00 Color conditioner Sodium cocoamphoacetate 1.30 Dye of the general formula (II) 0.01

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(R ¹ ,R ² ,R ³ ,R ⁴ =CH ₃ ; V=CI")

Dye of general formula (IV) 0.02

(R ¹ ,R ² =CH ₃ ; V=CI)

Methylparaben 0.20

Water ad 100,00

A subtle, even, shiny pearl color was achieved that remained virtually unchanged over three washes.

Replacing sodium cocoamphoacetate with the same amount of a nonionic surfactant (Laureth-12) resulted in a barely visible coloration.

Example 4 Color Conditioner

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Cocoamide or ropylbetaine 1.00(wt%) Compound of formula (II) 0.01 (R ¹ ,R ² ,R ³ and R ⁴ = CH ₃ ;,Y~=Cf) Compound of formula (IV) 0.02 (R ¹ and R ² = CH ₃ , Y~ = Cl) Ceteareth-20 1.00 Cetylstearyl alcohol 1.00 Dioleoylhydroxyethylmonium 2.00 methosulfat Benzophenone-4 0.50 Perfume 0.20 Methylparaben 0.20 Pyrrolidonecarboxylic acid 0.10 Citric acid 0.10 Water up to 100,00

The composition gave the hair a subtle, pearl-colored, shiny tint with excellent color stability.

Omission of cocoamidopropyl betaine resulted in a less intense coloration with reduced color stability.

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Example 5 Hair dye

Cetylstearyl alcohol 3.00

Compound of formula (III) 0.05 (R ¹ and R ² =CH ₃ ;r=CI")

Hydroxyethylcellulose 1.00 Trisodium carboxymethylcocopropylamine 0.80

Cetrimonium chloride 2.00

Benzophenone-9 0.50

Perfume 0.20

Preservatives q.s.

Water ad 100.0

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A strong, bright orange coloration was obtained. Replacement of the compound of formula (III) by the same amount of a conventional cationic direct orange dye resulted in a pale, less permanent coloration.

&bull;#

·

·

Claims (7)

1. Hair dyes containing a) at least one dye selected from a compound of the group


and or


wherein R ¹ , R ² , R ³ and R ⁴ represent hydrogen, a CH ₃ or C ₂ H ₅ group and R ⁵ represents hydrogen, -OCH ₃ or -OC ₂ H ₅ , and/or a compound selected from


and or


where R ¹ and R ² are -CH ₃ or -C ₂ H ₅ and Y ^- is an anion, and b) at least one amphoteric and/or zwitterionic surfactant. 2. Hair dye according to claim 1, containing a dye of the general formula (I) in which R ¹ and R ² are a methyl group, R ⁵ is hydrogen and Y ^- is a methosulfate group. 3. Hair dye according to claim 1, containing a dye of the general formula (I) in which R ¹ and R ² each represent a methyl group, R ⁵ represents a methoxy group and Y represents ^- Cl ^- . 4. Hair dye according to claim 1, containing a dye of the general formula (II), where R ¹ , R ² and R ³ each represent a methyl group, R ⁴ represents hydrogen and Y represents ^- Cl ^- . 5. Hair dye according to claim 1 containing a dye of the general formula (II), wherein R ¹ , R ² , R ³ and R ⁴ each represent a methyl group and Y ^- Cl ^- . 6. Hair dye according to claim 1, containing a dye of the general formula (III) and or (IV), wherein R ¹ and R ² each represent a methyl group and Y ^- Cl ^- . 7. Hair dye according to one or more of claims 1 to 6, containing cocoamidobetaine.