AU744100B2

AU744100B2 - Use of ester quaternaries as emulsifiers for producing preparations for coloring keratin fibers

Info

Publication number: AU744100B2
Application number: AU76521/98A
Authority: AU
Inventors: Jacqueline Lawrence; Francis Mcloughlin; Roger Pengilly
Original assignee: Cognis Deutschland GmbH and Co KG; Warner-Jenkinson Europe Ltd
Current assignee: BASF Personal Care and Nutrition GmbH; Warner-Jenkinson Europe Ltd
Priority date: 1997-09-04
Filing date: 1998-05-02
Publication date: 2002-02-14
Anticipated expiration: 2018-05-02
Also published as: EP0994691A1; CA2303209A1; GB2328954A; DE59804905D1; ES2181225T3; AU7652198A; GB9718821D0; GB2328954B; KR20010023659A; CN1269714A; EP0994691B1; WO1999011227A1; ATE220891T1; JP2001514198A

Abstract

There is disclosed the use of esterquats (ie quaternised fatty acid esters of alkanolamines, e.g. ethanolamines and 2,3-dihydroxypropylamines, and especially triethanolamines) as emulsifiers for hair dyes for the production of formulations for colouring keratin fibres. Improved dye absorption by the hair is achieved and, at the same time, improved softness is imparted to the hair during colouring, when esterquats are included in the hair colouring formulation. Suitable esterquats are those of formulae (I),(II) and (III) as defined in claims 2,3 and 4 respectively.

Description

1 The Use of Esterquats as Emulsifiers for the Production of Formulations for Colouring Keratin Fibres Field of the Invention This invention relates to the use of esterquats as emulsifiers for the production of hair colouring formulations and to a process for colouring keratin fibres in which hair dyes and emulsifiers of the esterquat type are used.

Prior Art Synthetic hair colourants can be divided into three groups, namely: substantive temporary colourants, semipermanent colourants and permanent colourants. However, natural hair colourants cannot readily be assigned to any of these three groups. Whether a temporary, semipermanent or permanent hair colour is to obtained with individual dyes also depends inter alia on the formulation in which it is incorporated and on how the formulations are applied.

The colour obtainable with temporary substantive hair colourants is merely a temporary change of the existing hair colour. Accordingly, it must be easy to wash out with shampoos. It is produced by the simple deposition of the dyes on the surface of the hair. Accordingly, this colouring treatment should not be followed by a rinsing step. Because of this, the dyes used must have the following properties: poor affinity for hair keratin, easy removability by washing with a shampoo, adequate fastness to light and high fastness to rubbing to avoid soiling clothes and pillows. Azo dyes, triphenylmethane dyes, anthraquinone dyes or indamine dyes and leuco derivatives thereof are generally used for this purpose.

Semipermanent hair colourants provide the hair with more pronounced and permanent colours which are capable of withstanding washing 5 or 6 times. This is achieved by the use of dyes which have a high affinity for keratin and which penetrate relatively deeply into the hair fibres. These colourants perform various functions. Eg, they add reflexes to a natural colour, hide grey hair and eliminate the yellow tinge from grey or white hair. The substantive dyes suitable for this purpose are largely nonionic or cationic and have a relatively low molecular weight and poor solubility in water.

Important representatives are the nitrophenyldiamines from which many other hair dyes can be produced by substitution reactions. The nitro dyes also include the nitroaminophenols which depending on the position of their nitro and amino group on the phenol ring give colours ranging from yellow through orange to red. Azo dyes or quinone imine dyes containing quaternary ammonium groups have a high affinity for hair keratin. Although they do not colour as intensively as nitro dyes, they do give colours in all shades.

Finally, permanent hair colours are highly resistant to washing, light and other hair treatment methods. In their case, the dyes are formed directly on and in the hair by chemical reactions to which the uncoloured intermediate products or precursors are subjected. These reactions include oxidation reactions and coupling reactions or condensations which are produced by hydrogen peroxide in the presence of ammonia or monoethanolamine. Hydrogen peroxide is preferably used as the oxidising agent because not only does it initiate the colour-forming process, it also destroys the melanin .i4 pigments in the hair and, in doing so, bleaches the hair. Besides the true oxidation hair dyes, there 4U, are also the self-oxidising dyes which are actually oxidised by atmospheric oxygen. The oxidation C08163 dyes are divided according to their nature into the oxidation bases (developers or primary intermediates) and the colour modifiers (couplers or secondary intermediates). Oxidation bases are aromatic compounds which are nucleus-substituted by at least two electron donor groups, preferably amino and/or hydroxy groups, and which are therefore readily oxidised. Important representatives of these bases are the isomeric ortho- and para-phenyldiamines, aminophenols and dihydroxybenzenes.

The couplers, too, are generally aromatic compounds which contain amino and/or hydroxy groups, but in the meta-position.

The hair dyes may be applied to the hair in various forms. In the most simple case, they may be aqueous or aqueous-alcoholic lotions which are diluted just before application and then applied to the hair. There are also the conditioning lotions which, in addition to the dyes, also contain above all cationic polymers and, accordingly, also have a hair-care effect. The same also applies to foam aerosols. A typical formulation for semipermanent colouring is the tinting shampoo whereas permanent hair colourants are generally applied as cremes or gels. However, in the production of shampoos, cremes and gels in particular, problems are involved on the one hand in stably emulsifying the dye together with hair-care additives and, on the other hand, in ensuring rapid deposition on the keratin fibres.

In this connection, a process for colouring cotton in which esterquats based on tall oil fatty acid are used is known from Russian patent application SU 956.668.

Accordingly, the complex problem addressed by the present invention was to provide emulsifiers for hair dyes with which it would be possible to prepare emulsions that would neither separate nor change viscosity even in the event of prolonged storage or under the effect of heat. In addition, the formulations obtainable with these emulsifiers would lead to improved dye absorption in the hair and would also have a hair-care effect, ie. in particular would improve feel, shine and combability.

Description of the Invention The present invention relates to the use of esterquats as emulsifiers for hair dyes for the production of formulations for colouring keratin fibres.

It has surprisingly been found that not only are esterquats capable of permanently emulsifying hair dyes without the formulations changing viscosity, the use of these cationic surfactants as emulsifiers also facilitates absorption of the dye by the keratin fibres. Another advantage is that a pleasant softness and shine is imparted to the hair during colouring and static charging between the fibres is reduced. Accordingly, not only the required colouring effect, but also a hair-care effect is obtained through the use according to the invention.

Esterquats "Esterquats" are generally understood to be quaternised fatty acid triethanolamine ester salts.

They are known compounds which may be obtained by the relevant methods of preparative organic chemistry, c/f. International patent application WO 91/01295 (Henkel), in which triethanolamine is partly esterified with fatty acids in the presence of hypophosphorous acid, air is passed through the reaction mixture and the whole is then quaternised with dimethyl sulfate or ethylene oxide. Overviews of this subject have been published, eg, by R. Puchta et al. in Tens. Surf. Det., 30, 186 (1993), by M.

C08163 Brock in Tens. Surf. Det., 30, 394 (1993), by R. Lagerman et al. in J. Am. Oil Chem. Soc., 71, 97 (1994) and by I. Shapiro in Cosm. Toil. 109, 77 (1994).

The quaternised fatty acid triethanolamine ester salts correspond to formula

R

4 1 NE)oR2] xe 0 o)R 3

(I)

in which R 1 CO is an acyl group containing 6 to 22 carbon atoms R 2 and R 3 independently of one another represent hydrogen or have the same meaning as R 1 CO, R 4 is an alkyl group containing 1 to 4 carbon atoms or a (CH2CH20)qH group, m, n and p together stand for 0 or numbers of 1 to 12, q is a number of 1 to 12 and X is halide, alkyl sulfate or alkyl phosphate. Typical examples of esterquats which may be used in accordance with the present invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachic acid, behenic acid and erucic acid and the technical mixtures thereof obtained, eg, in the pressure hydrolysis of natural fats and oils. Technical C 12 /18 cocofatty acids and, in particular, partly hydrogenated C 161 8 tallow or palm oil fatty acids and C16/18 fatty acid cuts rich in elaidic acid are preferably used. To produce the quaternised esters, the fatty acids and the triethanolamine may be used in a molar ratio of 1.1:1 to 3:1. With the performance properties of the esterquats in mind, a ratio of 1.2:1 to 2.2:1 and preferably 1.5:1 to 1.9:1 has proved to be particularly advantageous. The preferred esterquats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C16/18 tallow or palm oil fatty acid (iodine value 0 to 40). In performance terms, quaternised fatty acid triethanolamine ester salts corresponding to formula in which R 1 CO is an acyl group containing 16 to 18 carbon atoms,

R

2 has the same meaning as R 1 CO, R 3 is hydrogen, R 4 is a methyl group, m, n and p stand for 0 and X stands for methyl sulfate, have proved to be particularly advantageous.

Besides the quaternised fatty acid triethanolamine ester salts, other suitable esterquats are quaternised ester salts of fatty acids with diethanolalkyamines corresponding to formula (II):

R

4 iR O O~O o (II) in which R 1 CO is an acyl group containing 6 to 22 carbon atoms, R 2 is hydrogen or has the same meaning as R 1 CO, R 4 and R5 independently of one another are alkyl groups containing 1 to 4 carbon atoms, m and n together stand for 0 or numbers of 1 to 12 and X stands for halide, alkyl sulfate or alkyl phosphate.

Finally, another group of suitable esterquats are the quaternised ester salts of fatty acids with 1,2-dihydroxypropyl dialkylamines corresponding to formula (III): oR2 0 O R6 R (111) C08163 in which R 1 CO is an acyl group containing 6 to 22 carbon atoms, R 2 is hydrogen or has the same meaning as R 1 CO, R 4

R

6 and R 7 independently of one another are alkyl groups containing 1 to 4 carbon atoms, m and n together stand for 0 or numbers of 1 to 12 and X stands for halide, alkyl sulfate or alkyl phosphate.

So far as the choice of the preferred fatty acids and the optimal degree of esterification are concerned, the examples mentioned for also apply to the esterquats corresponding to formulae (II) and (III). The esterquats are normally marketed in the form of 50 to 90wt% solutions in alcohol which may readily be diluted as required with water. However, it is also possible to use mixtures of esterquats with fatty alcohols which are commercially available in the form of flakes and of which the 1o production is described in DE-C1 43 08 794 (Henkel). The esterquats may be used in quantities of 0.1 to 5wt% and are preferably used in quantities of 1 to 3wt%, based on the formulations.

Hair dyes Dyes suitable for the use according to the invention are, eg, substantive dyes, eg from the group of nitrophenylenediamines, nitroaminophenols, anthraquinones or indophenols, such as eg the compounds known under the international names or trade names of HC Yellow 2, HC Yellow 4, Basic Yellow 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, Basic Brown 17, picramic acid and Rodol 9 R and also 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, (N-2,3-dihydroxypropyl-2-nitro-4-trifluoromethyl)aminobenzene and 4-N-ethyl-1,4-bis-(2'-hydroxyethyl amino)-2-nitrobenzene hydrochloride. In addition, naturally occurring dyes, eg henna red, henna neutral, henna black, camomile blossom, sandalwood, black tea, buckthom bark, sage, logwood, madder root, catechu, sedre and alkanet may also be used.

In addition to substantive dyes, oxidation dyes consisting of primary and secondary intermediates may also be used. The primary intermediates used include, eg, primary aromatic amines containing another free or substituted hydroxy or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6tetraaminopyrimidine and derivatives thereof. Special representatives are inter alia ptoluylenediamine, p-aminophenol, N,N-bis-(2-hydroxyethyl)-p-phenylenediamine, 2-(2,5-diamino phenoxy)-ethanol, 1-phenyl-3-carboxyamido-4-amino-5-pyrazolone and 4-amino-3-methylphenol, 2- (2-hydroxyethyl)-1,4-aminobenzene and 2,4,5,6-tetraaminopyrimidine. The secondary intermediates used are generally m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and pyridine derivatives. Suitable secondary intermediates are, in particular, 1-naphthol, pyrogallol, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-5pyrazolone, 2,4-dichloro-3-aminophenol, 1,3-bis-(2,4-diaminophenoxy)-propane, 2-chlororesorcinol, 2chloro-6-methyl-3-aminophenol, 2-methyl resorcinol, 2,5-dimethyl resorcinol, 2,6-dihydroxypyridine and 2,6-diaminopyridine.

C08163 a; Other suitable dye components can be found in the Colipa List published by the Industrieverband K6rperpflege und Waschmittel, Frankfurt. The hair dyes may be used in quantities of 0.001 to 1wt% and are preferably used in quantities of 0.3 to 0.7wt%, based on the formulations.

Other auxiliaries and additives In one particularly simple embodiment of the invention, the formulations for colouring keratin fibres only contain oils besides the hair dyes, the esterquat emulsifiers and water. However, the formulations may also be made up, eg, in the form of tinting or colouring shampoos which may contain other ingredients typical of the particular nature of the formulation, such as eg mild surfactants, coemulsifiers, superfatting agents, pearlescent waxes, stabilisers, consistency regulators, thickeners, cationic polymers, silicone compounds, biogenic agents, antidandruff agents, film formers, preservatives, hydrotropes, solubilisers, UV filters, perfume oils, dyes and the like.

Typical examples of suitable mild surfactants, ie. surfactants particularly compatible with the skin, are fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, monoalkyl and/or dialkyl sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, ether carboxylic acids, alkyl oligoglucosides, fatty acid glucamides, alkylamidobetaines and/or protein fatty acid condensates (preferably based on wheat proteins).

Suitable oils are, eg, Guerbet alcohols based on fatty alcohols containing 6 to 18 and preferably 8 to 10 carbon atoms, esters of linear C6-22 fatty acids with linear C6-22 fatty alcohols, esters of branched C6-13 carboxylic acids with linear C6- 22 fatty alcohols, esters of linear C6-22 fatty acids with branched alcohols, more particularly 2-ethyl hexanol, esters of linear and/or branched fatty acids with polyhydric alcohols (eg propylene glycol, dimer diol or trimer triol) and/or Guerbet alcohols, triglycerides based on C6-10 fatty acids, liquid mono-/di-/triglyceride mixtures based on C6-1s fatty acids, esters of C6-22 fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, more particularly benzoic acid, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear C6-22 fatty alcohol carbonates, Guerbet carbonates, esters of benzoic acid with linear and/or branched C6-22 alcohols (eg Finsolv® TN), dialkyl ethers, ring-opening products of epoxidised fatty acid esters with polyols, silicone oils and/or aliphatic or naphthenic hydrocarbons. The quantity of oils in the formulations is typically from 10 to 70wt% and preferably from 25 to Suitable co-emulsifiers are, eg, nonionic surfactants from at least one of the following groups: products of the addition of 2 to 30mol of ethylene oxide and/or 0 to 5mol of propylene oxide to linear fatty alcohols containing 8 to 22 carbon atoms, to fatty acids containing 12 to 22 carbon atoms and to alkylphenols containing 8 to 15 carbon atoms in the alkyl group;

C

1 2/18 fatty acid monoesters and diesters of products of the addition of 1 to 30mol of ethylene oxide to glycerol; glycerol monoesters and diesters and sorbitan monoesters and diesters of saturated and unsaturated fatty acids containing 6 to 22 carbon atoms and ethylene oxide adducts thereof; alkyl mono- and oligoglycosides containing 8 to 22 carbon atoms in the alkyl group and ethoxylated analogues thereof; adducts of 15 to 60mol of ethylene oxide with castor oil and/or hydrogenated castor oil; C08163 polyol esters and, in particular, polyglycerol esters such as, eg, polyglycerol polyricinoleate or polyglycerol poly-12-hydroxystearate. Mixtures of compounds from several of these classes are also suitable; products of the addition of 2 to 15mol of ethylene oxide to castor oil and/or hydrogenated castor oil; partial esters based on linear, branched, unsaturated or saturated C6/ 2 2 fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (eg sorbitol), alkyl glucosides (eg methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (eg cellulose); 1o trialkyl phosphates and mono-, di- and/or tri-PEG-alkyl phosphates; wool wax alcohols; (11) polysiloxane/polyalkyl polyether copolymers and corresponding derivatives; (12) mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE-PS 11 65 574 and/or mixed esters of fatty acids containing 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol, and (13) polyalkylene glycols.

The addition products of ethylene oxide and/or propylene oxide with fatty alcohols, fatty acids, alkylphenols, glycerol monoesters and diesters and sorbitan monoesters and diesters of fatty acids or with castor oil are known, commercially available products. They are homologue mixtures of which the average degree of alkoxylation corresponds to the ratio between the quantities of ethylene oxide and/or propylene oxide and substrate with which the addition reaction is carried out. C12/18 fatty acid monoesters and diesters of addition products of ethylene oxide with glycerol are known as refatting agents for cosmetic formulations from DE-PS 20 24 051.

Cs/18 alkyl mono- and oligoglycosides, their production and their use as surfactants are known from the prior art. They are produced in particular by reaction of glucose or oligosaccharides with primary alcohols containing 8 to 18 C atoms. So far as the glycoside component is concerned, both monoglycosides, in which a cyclic sugar unit is attached to the fatty alcohol by a glycoside linkage, and oligomeric glycosides with a degree of oligomerisation of preferably up to about 8 are suitable.

The degree of oligomerisation is a statistical mean value on which a homologue distribution typical of such technical products is based.

Zwitterionic surfactants may also be used as emulsifiers. Zwitterionic surfactants are surfaceactive compounds which contain at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as the N-alkyl-N,N-dimethyl ammonium glycinates, eg cocoalkyl dimethyl ammonium glycinate, N-acylaminopropyl-N,N-dimethyl ammonium glycinates, eg cocoacylaminopropyl dimethyl ammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines containing 8 to 18 carbon atoms in the alkyl or acyl group and cocoacylaminoethyl hydroxyethyl carboxymethyl glycinate. The fatty acid amide derivative known by the CTFA name of Cocamidopropyl Betaine is particularly preferred. Other suitable emulsifiers are ampholytic 40 urfactant. Ampholytic surfactants are surface-active compounds which, in addition to a C8/1 alkyl or surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a 08,18 alkyl or C08163 acyl group, contain at least one free amino group and at least one -COOH or -SO 3 H group in the molecule and which are capable of forming inner salts. Examples of suitable ampholytic surfactants are N-alkyl glycines, N-alkyl propionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropyl glycines, N-alkyl taurines, N-alkyl sarcosines, 2alkylaminopropionic acids and alkylaminoacetic acids containing around 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and C12/1 8 acyl sarcosine.

The superfatting agents used may be such substances as, eg, lanolin and lecithin and polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides, the latter also serving as foam stabilisers.

Suitable pearlescent waxes are, eg, alkylene glycol esters, particularly ethylene glycol distearate; fatty acid alkanolamides, especially cocofatty acid diethanolamide; partial glycerides, especially stearic acid monoglyceride; esters of polybasic, optionally hydroxysubstituted carboxylic acids with fatty alcohols containing 6 to 22 carbon atoms, especially long-chain esters of tartaric acid; fatty compounds, eg fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates which contain a total of at least 24 carbon atoms, especially laurone and distearyl ether; fatty acids, such as stearic acid, hydroxystearic acid or behenic acid, ring opening products of olefin epoxides containing 12 to 22 carbon atoms with fatty alcohols containing 12 to 22 carbon atoms and/or polyols containing 2 to 15 carbon atoms and 2 to 10 hydroxyl groups; and mixtures thereof.

Suitable consistency regulators are, above all, fatty alcohols containing 12 to 22 and preferably 16 to 18 carbon atoms and, in addition, partial glycerides. These substances are preferably used in combination with alkyl oligoglucosides and/or fatty acid-N-methyl glucamides of the same chain length and/or polyglycerol poly-12-hydroxystearates. Suitable thickeners are, eg, polysaccharides, more particularly xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, relatively high molecular weight polyethylene glycol monoesters and diesters of fatty acids, polyacrylates (eg Carbopols® [Goodrich] or Synthalens® [Sigma]), polyacrylamides, polyvinyl alcohol and polyvinyl pyrrolidone, surfactants such as, eg, ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as, eg, pentaerythritol or trimethylol propane, narrow-range fatty alcohol ethoxylates or alkyl oligoglucosides and electrolytes such as sodium chloride and ammonium chloride.

Suitable cationic polymers are, eg, cationic cellulose derivatives such as, eg, the quaternised hydroxyethyl cellulose available under the name of Polymer JR 400® from Amerchol, cationic starch, copolymers of diallyl ammonium salts and acrylamides, quaternised vinyl pyrrolidone/vinyl imidazole polymers such as, eg, Luviquat@ (BASF), condensation products of polyglycols and amines, quaternised collagen polypeptides such as, eg, Lauryldimonium Hydroxypropyl Hydrolyzed Collagen (Lamequat®L Grinau), quatemised wheat polypeptides, polyethyleneimine, cationic silicone polymers such as, eg, Amidomethicone, copolymers of adipic acid and dimethyl aminohydroxypropyl diethylenetriamine (Cartaretine®, Sandoz), copolymers of acrylic acid with dimethyl diallyl ammonium l= loride (Merquat@ 550, Chemviron), polyaminopolyamides as described, eg, in FR-A 2252840 and c~ slinked water-soluble polymers thereof, cationic chitin derivatives such as, eg, quaternised C08163 chitosan, optionally in microcrystalline distribution, condensation products of dihaloalkyls such as, eg, dibromobutane with bis-dialkylamines such as, eg, bis-dimethylamino-1,3-propane, cationic guar gum such as, eg, Jaguar@ CBS, Jaguar® C-17, Jaguar@ C-16 of Celanese, quatemised ammonium salt polymers such as, eg, Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 of Miranol.

Suitable silicone compounds are, eg, dimethyl polysiloxanes, methyl phenyl polysiloxanes, cyclic silicones and amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine- and/or alkyl-modified silicone compounds which may be both liquid and resin-like at room temperature. Typical examples of fats are glycerides while suitable waxes are inter alia beeswax, carnauba wax, candelilla wax, montan wax, paraffin wax or microwaxes, optionally in combination with hydrophilic waxes, eg cetostearyl alcohol, or partial glycerides. Suitable stabilisers are metal salts of fatty acids such as, eg, magnesium, aluminium and/or zinc stearate. Biogenic agents in the context of the invention are, eg, tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts and vitamin complexes. Suitable antidandruff agents are climbazol, octopirox and zinc pyrethion. Typical film formers are, eg, chitosan, microcrystalline chitosan, quaternised chitosan, polyvinyl pyrrolidone, vinyl pyrrolidone/vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives, collagen, hyaluronic acid and salts thereof and similar compounds.

Suitable swelling agents for aqueous phases include montmorillonites, clay minerals, Pemulen and alkyl-modified Carbopol types (Goodrich).

In the context of the invention, UV filters are organic compounds which are capable of absorbing ultraviolet rays and of releasing the energy absorbed in the form of longer wave radiation, eg heat. Typical examples are 4-aminobenzoic acid and esters and derivatives thereof (eg 2ethylhexyl-p-dimethylaminobenzoate or p-dimethylaminobenzoic acid octyl ester), methoxycinnamic acid and derivatives thereof (eg 4-methoxycinnamic acid-2-ethylhexyl ester), benzophenones (eg oxybenzone, 2-hydroxy-4-methoxybenzophenone), dibenzoyl methanes, salicylate esters, 2-phenyl acid, 1-(4-tert.butylphenyl)-3-(4'-methoxyphenyl)-propane-1,3-dione, methyl)-benzylidenebornan-2-one, methylbenzylidene camphor and the like. Other suitable UV filters are finely disperse metal oxides and salts, eg titanium dioxide, zinc oxide, iron oxide, aluminium oxide, cerium oxide, zirconium oxide, silicates (talcum) and barium sulfate. The particles should have an average diameter of less than 100nm, preferably from 5 to 50nm and more preferably from 15 to They may be spherical in shape although ellipsoidal particles or other non-spherical particles may also be used. Besides the two above-mentioned groups of primary light filters, secondary light filters of the antioxidant type, which interrupt the photochemical reaction chain initiated when UV radiation penetrates into the skin, may also be used. Typical examples of these secondary light filters are Superoxid-Dismutase, tocopherols (vitamin E) and ascorbic acid (vitamin C).

In addition, hydrotropes such as, eg, ethanol, isopropyl alcohol or polyols may be used to improve flow behaviour. Suitable polyols preferably contain 2 to 15 carbon atoms and at least two hydroxyl groups. Typical examples are Z glycerol; C08163 9 alkylene glycols such as, eg, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and polyethylene glycols having an average molecular weight of 100 to 1000 dalton; technical oligoglycerol mixtures with a degree of self-condensation of 1.5 to 10 such as, eg, technical diglycerol mixtures with a diglycerol content of 40 to methylol compounds such as, in particular, trimethylol ethane, trimethylol propane, trimethylol butane, pentaerythritol and dipentaerythritol; lower alkyl glucosides, particularly those containing 1 to 8 carbon atoms in the alkyl group, eg methyl and butyl glucoside; sugar alcohols containing 5 to 12 carbon atoms such as, eg, sorbitol or mannitol; sugars containing 5 to 12 carbon atoms such as, eg, glucose or sucrose and aminosugars such as, eg, glucamine.

Suitable preservatives are, eg, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid.

Examples of perfume oils include the extracts of blossoms (lavender, rose, jasmine, neroli), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, coriander, caraway, juniper), fruit peel (bergamot, lemon, orange), roots (nutmeg, angelica, celery, cardamon, costus, iris, calmus), woods (sandalwood, pockwood, cedarwood, rosewood), herbs and grasses (tarragon, lemon grass, sage, thyme), needles and branches (spruce, fir, pine, dwarf pine), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials, eg musk, civet and beaver, may also be used. Suitable synthetic and semisynthetic perfume oils are Ambroxan, eugenol, isoeugenol, citronellal, hydroxycitronellal, geraniol, citronellol, geranyl acetate, citral, ionone and methyl ionone.

The total percentage content of auxiliaries and additives may be from 1 to 50wt% and is preferably from 5 to 40wt%, based on the particular formulation. The formulations may be prepared by standard cold or hot processes and are preferably produced by the phase inversion temperature method.

Finally, the present invention also relates to a process for colouring keratin fibres in which human hair is contacted with formulations which contain esterquats as emulsifiers in addition to oxidation or substantive hair dyes.

Examples Example 1 An emulsion containing 33.3g of Dehyquart® AU-46 (methyl-quaternised dipalm oil fatty acid triethanolamine ester, methyl sulfate salt, Pulcra Barcelona), 9g of Cs818 alkyl glucoside, 9g of colloidal silica, 3g of ammonium chloride, aqueous ammonia solution to 100g (pH10.5) was prepared by mixing at 70 0 C. 7.5mmol of a primary intermediate (N,N'-bis-(4-aminophenyl)-piperidine) and of a secondary intermediate (resorcinol) were then stirred into the emulsion at 200C.

Oxidative development was then carried out with hydrogen peroxide. The hair colour obtained was dark blond.

C08163 Example 2 An emulsion containing 33.3g of Dehyquart® AU-46, 9g of 08/18 alkyl glucoside, 9g of colloidal silica, 3g of ammonium chloride, aqueous ammonia solution to 100g (pHiOS5) was prepared as in Example 1. 7.5mmol of 2,4,5,6-tetraaminopyridine and 7.5mmol of 2,6-bis-(2-hydroxyethylamino)toluene were stirred into the PIT emulsion at 20 0 C. Oxidative development was again carried out with hydrogen peroxide. The hair colour obtained was deep red.

Examples 3 to The following hair colouring creme emulsions were then "cold"-prepared on the basis of these Examples (water to lO0wt%): creme base of Example 1 or 2 primary intermediate secondary intermediate Na2SO3 (inhibitor) 1 .Owt%

(NH

4 2 S0 4 1 .Owt% conc. ammonia solution to pHlO The components were mixed in the above order. After addition of the oxidation dye precursors and the inhibitor, the pH of the emulsion was first adjusted to 10 with concentrated ammonia solution, after which the emulsion was made up with water to 100g. Oxidative development of the colour was carried out with hydrogen peroxide solution as the oxidising solution. To this end, 50g of hydrogen peroxide solution 3 or were added to and mixed with 1O0g of the emulsion. The colouring creme was applied to approximately 5cm long tresses of standardised, 90% grey but not specially pretreated human hair and left thereon for 30 minutes at 3200. After the colouring process, the hair was rinsed, washed with a standard shampoo and then dried. The colours listed in Table 1 were obtained: Table I -Hair Colours Secondary Intermediate Primary Intermediate Substantive Dye c[H202] Colour 2,6-bis-(2-hydroxyethylamino)- 2,4,5,6-tetraamino-pyrimidine 3 Deep red 2,6-bis-(2-hydroxyethylamino)- 4-hydroxy-2,5,6- 3 Madder red toluene triaminopyrimidine 2,6-bis-(2-hydroxyethylamino)- 2-dimethylamino-4,5,6- 3 Brown-red toluene triaminopyrimidine 2,6-bis-(2-hydroxyethylamino)- 2-methylamino-4,5,6- 3 Red toluene thaminopyri-midine 2,6-bis-(2-hydroxyethylamino)- 2-piperidyl-4,5,6- 3 Madder red toluene tharninopyrimidine 2,6-bis-(2-hydroxyethylamino)- 2-morpholino-4,5,6- 3 Madder red toluene triaminopyimidine 2-morpholino-4,5,6- 2,4,5-tetraamino-pyhmidine 3 Copper red triaminopyrimidine 2,7dihydroxynaphthalene______________ 2,6-bis-(2-hydroxyethylamino)- 2-(2-hydroxyethyl)-1,4- 1 Violet toluene diaminobenzene 2,6-bis-(2-hydroxyethylamino)- 2-(2-hydroxyethyl)-1,4- 9 Violet toluene diaminobenzene 2,6-bis-(2-hydroxyethylamino)- 2,4,5,6-tetraaminopyrimidine 1 Grey-ruby toluene 2,5-diaminotoluene 2,6-bis-(2-hydroxyethylamino)- 2,4,5,6-tetraaminopyrimidine 9 Deep \toluene 2,5-diaminotoluene R~t -13 C081 63 2,6-bis-(2-hydroxyethylamino)- 2-dimethylamino-4,5,6- 4-(3'-trimethylammonium 1 Cinnabar toluene triaminopyrimidine phenylazo)-1 -phenyl-3chloride 2,6-bis-(2-hydroxyethylamino)- -2-dimethylamino-4,5,6- 4-(3'-trimethylammonium 9 Orange-red toluene triaminopyrimidine phenyiazo)-1-phenyl-3- Imethylpyrazolone chloride C08163

Claims

1. The use of esterquats as emulsifiers for hair dyes for the production of formulations for colouring keratin fibres.

2. The use claimed in claim 1, characterised in that esterquats corresponding to formula R 4 0 0 .^oVR3 OoR X (I) in which RICO is an acyl group containing 6 to 22 carbon atoms R 2 and R 3 independently of one another represent hydrogen or have the same meaning as RICO, R 4 is an alkyl group containing 1 to 4 carbon atoms or a (CH2CH20)qH group, m, n and p together stand for 0 or numbers of 1 to 12, q is a number of 1 to 12 and X is halide, alkyl sulfate or alkyl phosphate, are used.

3. The use claimed in claim 1, characterised in that esterquats corresponding to formula (II): R 4 o (II) in which R 1 CO is an acyl group containing 6 to 22 carbon atoms, R 2 is hydrogen or has the same meaning as RICO, R 4 and R 5 independently of one another are alkyl groups containing 1 to 4 carbon is1 atoms, m and n together stand for 0 or numbers of 1 to 12 and X stands for halide, alkyl sulfate or alkyl phosphate, are used.

4. The use claimed in claim 1, characterised in that esterquats corresponding to formula (III): nOR X 0 R i w c (Ill) S" 20 in which RiCO is an acyl group containing 6 to 22 carbon atoms, R 2 is hydrogen or has the same meaning as RICO, R 4 R 6 and R 7 independently of one another are alkyl groups containing 1 to 4 carbon atoms, m and n together stand for 0 or numbers of 1 to 12 and X stands for halide, alkyl sulfate or alkyl phosphate, are used.

The use claimed in any one of claims 1 to 4, characterised in that the esterquats are used in quantities of 0.1 to 5wt%, based on the formulations.

6. The use claimed in any one of claims 1 to 5, characterised in that substantive hair dyes or oxidation hair dyes are used.

7. The use claimed in any one of claims 1 to 6, characterised in that the hair dyes are used in quantities of 0.001 to 1wt%, based on the formulation.

8. The use claimed in any one of claims 1 to 7, characterised in that oils selected from the RA group consisting of Guerbet alcohols based on fatt alcohols containing 6 to 18 carbon atoms, esters S9f linear C6-22 fatty acids with linear C 6 -22 fatty alcohols, esters of branched C6-13 carboxylic acids with UbC/497442response linear C6-22 fatty alcohols, esters of linear C6-22 fatty acids with branched alcohols, esters of linear and/or branched fatty acids with polyhydric alcohols and/or Guerbet alcohols, triglycerides based on Ci-1o fatty acids, liquid mono-/di-/triglyceride mixtures based on Cse-i fatty acids, esters of C6-22 fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear C6-22 fatty alcohol carbonates, Guerbet carbonates, esters of benzoic acid with linear and/or branched C6-22 alcohols, dialkyl ethers, ring-opening products of epoxidised fatty acid esters with polyols, silicone oils and/or aliphatic or naphthenic hydrocarbons are additionally used.

9. The use claimed in claim 8, characterised in that the oils are used in quantities of 10 to 70wt%, based on the formulations.

A hair dye for the production of formulations for colouring keratin fibres containing as emulsifier at least one esterquat corresponding to formula (II) or (III): R4 o R (I) in which RICO is an acyl group containing 6 to 22 carbon atoms R 2 and R 3 independently of one 15 another represent hydrogen or have the same meaning as R 1 CO, R 4 is an alkyl group containing 1 to 4 carbon atoms or a (CH2CH20)qH group, m, n and p together stand for 0 or numbers of 1 to 12, q is a number of 1 to 12 and X is halide, alkyl sulfate or alkyl phosphate; S* R 4 OR o (II) in which R 1 CO is an acyl group containing 6 to 22 carbon atoms, R 2 is hydrogen or has the same 20 meaning as R 1 CO, R 4 and R 5 independently of one another are alkyl groups containing 1 to 4 carbon atoms, m and n together stand for 0 or numbers of 1 to 12 and X stands for halide, alkyl sulfate or alkyl phosphate; R R O R6 OR xe 0 (111) in which RiCO is an acyl group containing 6 to 22 carbon atoms, R 2 is hydrogen or has the same meaning as RICO, R 4 R 6 and R 7 independently of one another are alkyl groups containing 1 to 4 carbon atoms, m and n together stand for 0 or numbers of 1 to 12 and X stands for halide, alkyl sulfate or alkyl phosphate.

11. The hair dye claimed in claim 10, wherein the esterquats are present in quantities to provide of 0.1 to 5wt%, based on the formulations.

12. The hair dye claimed in claim 10 or claim 11, wherein substantive hair dyes or oxidation hair dyes are used. UbC/497442response 14

13. The hair dye claimed in any one of claims 10 to 12, used in quantities of 0.001 to lwt%, based on the formulation.

14. The hair dye claimed in any one of claims 10 to 13, wherein oils selected from the group consisting of Guerbet alcohols based on fatty alcohols containing 6 to 18 carbon atoms, esters of linear C6-22 fatty acids with linear C 6 -22 fatty alcohols, esters of branched C6- 13 carboxylic acids with linear C&-22 fatty alcohols, esters of linear C622 fatty acids with branched alcohols, esters of linear and/or branched fatty acids with polyhydric alcohols and/or Guerbet alcohols, triglycerides based on C6-io fatty acids, liquid mono-/di-/triglyceride mixtures based on C618 fatty acids, esters of C6-22 fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear C6-22 fatty alcohol carbonates, Guerbet carbonates, esters of benzoic acid with linear and/or branched Cr,22 alcohols, dialkyl ethers, ring-opening products of epoxidised fatty acid esters with polyols, silicone oils and/or aliphatic or naphthenic hydrocarbons are additionally used.

The hair dye claimed in claim 14, wherein the oils are used in quantities of 10 to based on the formulations.

16. A hair dye, substantially as hereinbefore described with reference to any one of the S. examples.

17. A formulation for colouring keratin fibres containing at least one hair dye and at least one esterquat as emulsifier. 20

18. The formulation claimed in claim 17, wherein the esterquat corresponds to formula S. R 4 O O NOO Xe 0 0R (I) in which RICO is an acyl group containing 6 to 22 carbon atoms R 2 and R 3 independently of one another represent hydrogen or have the same meaning as RICO, R 4 is an alkyl group containing 1 to S4 carbon atoms or a (CH2CH20)qH group, m, n and p together stand for 0 or numbers of 1 to 12, q is a S 25 number of 1 to 12 and X is halide, alkyl sulfate or alkyl phosphate.

19. The formulation claimed in claim 17, wherein the esterquat corresponds to formula (II): e R 4 o (II) in which RICO is an acyl group containing 6 to 22 carbon atoms, R 2 is hydrogen or has the same meaning as RICO, R 4 and R s independently of one another are alkyl groups containing 1 to 4 carbon atoms, m and n together stand for 0 or numbers of 1 to 12 and X stands for halide, alkyl sulfate or alkyl phosphate.

The formulation claimed in claim 17, wherein the esterquat corresponds to formula (III): UbC/497442response RO S R 6 [R 1 O .A N R X o (III) in which R1CO is an acyl group containing 6 to 22 carbon atoms, R 2 is hydrogen or has the same meaning as R 1 CO, R 4 R 6 and R 7 independently of one another are alkyl groups containing 1 to 4 carbon atoms, m and n together stand for 0 or numbers of 1 to 12 and X stands for halide, alkyl sulfate or alkyl phosphate.

21. The formulation claimed in any one of claims 17 to 20, wherein the esterquats are present in quantities of 0.1 to 5wt%, based on the formulations.

22. The formulation claimed in any one of claims 17 to 21, wherein substantive hair dyes or oxidation hair dyes are used.

23. The formulation claimed in any one of claims 17 to 22, wherein the hair dyes are used in quantities of 0.001 to 1wt%, based on the formulation.

24. The formulation claimed in any one of claims 17 to 23, wherein oils selected from the group consisting of Guerbet alcohols based on fatty alcohols containing 6 to 18 carbon atoms, esters of linear C6-22 fatty acids with linear C6-22 fatty alcohols, esters of branched C6-13 carboxylic acids with 15 linear C6-22 fatty alcohols, esters of linear C6-22 fatty acids with branched alcohols, esters of linear and/or branched fatty acids with polyhydric alcohols and/or Guerbet alcohols, triglycerides based on C6-io fatty acids, liquid mono-/di-/triglyceride mixtures based on C6-18 fatty acids, esters of C-22 fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear C6-22 fatty alcohol carbonates, Guerbet carbonates, esters 20 of benzoic acid with linear and/or branched C-22 alcohols, dialkyl ethers, ring-opening products of epoxidised fatty acid esters with polyols, silicone oils and/or aliphatic or naphthenic hydrocarbons are additionally used.

25. The formulation claimed in claim 24, wherein the oils are used in quantities of 10 to ol 70wt%, based on the formulations. 25 29. A formulation for colouring keratin fibres, said formulation being substantially as hereinbefore described with reference to any one of the examples. Dated 4 September 2001 COGNIS DEUTSCHLAND GMBH WARNER-JENKINSON EUROPE LTD. Patent Attorneys for the ApplicantlNominated Person SPRUSON FERGUSON UbC/497442response