WO2013007607A2 - Hair care composition - Google Patents

Hair care composition Download PDF

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WO2013007607A2
WO2013007607A2 PCT/EP2012/063173 EP2012063173W WO2013007607A2 WO 2013007607 A2 WO2013007607 A2 WO 2013007607A2 EP 2012063173 W EP2012063173 W EP 2012063173W WO 2013007607 A2 WO2013007607 A2 WO 2013007607A2
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composition
preferably
wt
hair
kit
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PCT/EP2012/063173
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French (fr)
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WO2013007607A3 (en )
Inventor
Stephen Norman Batchelor
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Unilever Plc
Unilever N.V.
Hindustan Unilever Limited
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/19Cosmetics or similar toilet preparations characterised by the composition containing inorganic ingredients
    • A61K8/22Peroxides; Oxygen; Ozone
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/19Cosmetics or similar toilet preparations characterised by the composition containing inorganic ingredients
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/30Cosmetics or similar toilet preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4906Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4926Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having six membered rings
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILET PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/06Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A61Q5/065Preparations for temporary colouring the hair, e.g. direct dyes
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/42Colour properties
    • A61K2800/43Pigments; Dyes
    • A61K2800/432Direct dyes
    • A61K2800/4322Direct dyes in preparations for temporarily coloring the hair further containing an oxidizing agent

Abstract

A non-oxidative hair colouring kit comprising: (i) a first composition comprising at least one metal ion in the form of a salt and/or complex in which the metal ion is Fe(II) Fe(III), or mixtures thereof; ii) a second composition comprising an aromatic heterocyclic compound wherein the ring containing the heteroatom of the aromatic heterocyclic compound, is substituted by a primary amino group or secondary amino group and an OH or alkoxy group, such that the amino group and the hydroxy/alkoxy groups are ortho to each other.

Description

HAIR CARE COMPOSITION

The present invention relates to kits and methods for colouring hair. There are many ways to dye hair. Oxidative dyeing involves the oxidation of an organic precursor with a water soluble peroxygen oxidising agent and the reaction of the oxidised precursor with an organic coupler molecule to form a colour.

Oxidative dying processes are known to dye hair and are sometimes enhanced by using metal catalysts. Oxidative colouring systems are known to damage the hair.

An alternative route to colouring hair is to form a polyphenol mordant with metal ions.

EP0327345 (Beecham) discloses a hair colouring shampoo containing an Fe(ll) salt and a second component is applied which contains a metal ligand including ortho substituted phenols.

Two part colouring systems in which in which one part comprises a metal salt are disclosed in WO2010/135237 (Advance Cosmetic Technologies) and

WO/2007/130777, WO 2000/29036 (Henkel).

We have found that metal based mordant dyes produce a blue hue. Thus, there remains a need for a dye using a metal ion mordant system that darkens the hair without imparting a strong blue shade.

The present invention describes such a system. Summary of the Invention

Accordingly the invention relates to a kit for colouring hair comprising a non- oxidative kit for colouring hair comprising:

(i) first composition comprising at least one metal ion in the form of a salt and/or complex in which the metal ion is Fe(ll) Fe(lll), or mixtures thereof; ii) a second composition comprising an aromatic heterocyclic compound wherein the ring containing the heteroatom of the aromatic heterocyclic compound, is substituted by a primary amino group or secondary amino group and an OH or alkoxy group, such that the amino group and the hydroxy/alkoxy groups are ortho to each other.

The invention also relates to a method of colouring hair by applying to the hair sequentially in any order the compositions of the kit described above.

A third aspect of the invention is a method to dye the hair in which the kit described above is used on successive occasions to gradually colour the hair.

Description of the Invention

Compositions of the invention are generally aqueous, i.e. they have water or an aqueous solution or a lyotropic liquid crystalline phase as their major component. Suitably, the composition will comprise from 50 to 98 %, preferably, from 60 to 90 % water by weight based on the total weight of the composition.

Compositions of the invention preferably, comprise less than 0.05 wt% of a water soluble peroxygen oxidising agent. Examples of water soluble peroxygen oxidising agent are sodium perborate, peracetic acid, hydrogen peroxide and sodium percarbonate. More preferably, the composition comprises less than 0.01 wt% of a water soluble peroxygen oxidising agent. More preferably, each composition comprise less than 0.005 wt% of the total composition of a water soluble peroxygen oxidising agent. Most preferably, the composition is devoid of water soluble peroxygen oxidising agent.. Compositions of the invention comprise less than 0.05 wt% of the total of each composition of compounds selected from an aromatic diamine, para substituted aminophenols and meta substituted aminophenols. Examples of aromatic diamines include p-phenylenediamine, N-substituted derivatives of p- phenylenediamine and its salts, heteroaromatic diamines,

methylphenylenediamines, their N-substituted derivatives and their salts

Toluene-2,5-diamine and its salts.

More preferably, the composition comprise less than 0.01 wt% of an aromatic diamine, para substituted aminophenols and meta substituted aminophenols. Most preferably, the composition is devoid of aromatic diamines, para substituted aminophenols and meta substituted aminophenols.

First Composition Metal Complex

Compositions of the invention comprise of at least one metal ion selected form Fe(ll), Fe(lll) or mixtures thereof, most preferably Fe(ll). Preferably, the level of metal is from 0.01 to 10 wt% of the total first composition, more preferably, the level of metal ion is from 0.1 wt% to 5 wt% of the total first composition, most preferably, from 0.2 wt% to 3 wt%.

The level of metal ion in the formulation may be determined by quantitative elemental analysis. For the avoidance of doubt, if the formulation contains 2 wt% of the complex

Figure imgf000005_0001

With molecular weight of 446.14, then it will contain 55.84/446.14*2 = 0.25wt% of Fe(ll) (2 decimal places.

The metal ion is preferably, present as a complex with a ligand. In the context of this invention a ligand is a molecule that contains more than one organic group, preferably, 2 to 4 groups, most preferably, 2 groups that co-ordinate with the metal ion. Groups for co-ordinating with the metal ion are COO", OH, ketones, esters, primary amines, secondary amines and tertiary amines, more preferably, COO", primary amines and OH, most preferably, COO" and OH. Organic acids are highly preferred. Polyphenols are not permitted as multidentate ligands. The ligand- metal complex may be pre-formed before addition to the shampoo for example iron (II) gluconate, iron (II) glutamate. The ligand metal complex may be formed in the composition by the addition of an iron salt and the ligand, for example FeC^ and sodium lactate. Preferably, the mole ratio of iron ion to ligand is from 1 :1 to 1 :4, more preferably, from 1 :1 .5 to 1 :2.5

Preferably, the metal ion is in the form of a complex that is soluble in aqueous solution at the pH of the formulation. Most preferably, the metal ion in the form of a complex has a solubility in demineralised water at the pH of the formulation of greater than 0.1 g/L.

The ability of a ligand to complex with a metal ion, Mn+, may be defined by its pMn+ value, wherein pMn+ = -logio[Mn+]free and the ligand concentration is 10"5 mol/L and the total metal ion concentration is 10"6 mol/L and [Mn+]free '\s the molar concentration of

uncomplexed metal ions. Preferably, the ligand used has a lower pMn+, than 2- Amino-3-hydroxypyridine. Preferably, the pMn+are greater than 8 more preferably, greater than 10. pMn+ values are most preferably, measured at pH=4 in de- mineralised water, with the chloride salt of the metal ion, most preferably, ferric chloride.

The ligand is not a polyamino carboxylic acid, and such ligands are preferably, present at weight % levels of less than 1 /30th of the main ligand, preferably, they are absent from the first composition. A polyamino carboxylic acid is a compound containing two or more amines connected through carbon atoms to two or more carboxylic acid groups. 2,2',2",2"'-(Ethane-1 ,2-diyldinitrilo)tetraacetic acid is a polyamino carboxylic acid. Diethylene triamine pentaacetic acid is a polyamino carboxylic acid. Ethylenediamine-/V,/V'-disuccinic acid is a polyamino carboxylic acid.

Most preferably, the ligands are selected from gluconate, tartrate, ascorbate, citrate and lactate Particularly preferred are gluconate, lactate or ascorbate.

Particularly, preferred is iron (II) gluconate and iron(ll) lactate, iron (II) tartrate, most preferably, iron (II) gluconate.

Preferably, the iron is only in a composition which further comprises a cleansing surfactant, such as a shampoo composition.

Surfactant Mix

Compositions of the first invention preferably, comprise surfactant. The surfactant may be anionic, non-ionic and or amphoteric/zwitterionic. Anionic Surfactants

Anionic surfactants may be present from 0.5 wt% to 45 wt%, more preferably, from 1 .5 to 20 wt% of the first composition. Suitable anionic cleansing surfactants are alkyl ether sulphates, alkyl sulphates, alkaryl sulphonates, alkanoyl isethionates, alkyl succinates, alkyl

sulphosuccinates, alkyl ether sulphosuccinates, N-alkyl sarcosinates, alkyl phosphates, alkyl ether phosphates, and alkyl ether carboxylic acids and salts thereof, especially sodium, magnesium, ammonium and mono-, di- and

triethanolamine salts. The alkyl and acyl groups generally contain from 8 to 18, preferably, from 10 to 16 carbon atoms and may be unsaturated. The alkyl ether sulphates, alkyl ether sulphosuccinates, alkyl ether phosphates and alkyl ether carboxylic acids and salts thereof may contain from 1 to 20 ethylene oxide or propylene oxide units per molecule.

Preferred anionic cleansing surfactants for use in shampoo compositions of the invention include sodium oleyl succinate, ammonium lauryl sulphosuccinate, sodium lauryl sulphate, sodium lauryl ether sulphate, sodium lauryl ether sulphosuccinate, ammonium lauryl sulphate, ammonium lauryl ether sulphate, sodium dodecylbenzene sulphonate, triethanolamine dodecylbenzene sulphonate, sodium cocoyi isethionate, sodium lauryl isethionate, lauryl ether carboxylic acid and sodium N-lauryl sarcosinate.

Particularly preferred anionic cleansing surfactants are sodium lauryl sulphate, sodium lauryl ether sulphosuccinate(n)EO, (where n is from 1 to 3), ammonium lauryl sulphate, ammonium lauryl ether sulphate(n)EO, (where n is from 1 to 3), sodium cocoyi isethionate and lauryl ether carboxylic acid (n) EO (where n is from 10 to 20). It is particularly preferred if the anionic surfactant comprises alkyl ether sulphates (AES), more preferably, lauryl ether sulphate, most preferred sodium lauryl ether sulfate (SLES). Preferably, the SLES has from 1 to 3 ethoxy groups. The fraction of AES surfactant in the surfactant mix (†AES) may be defined as

FAES = (Wt% AES surfactant) / (total wt% of all surfactants).

Preferably, the AES surfactant is the major surfactant component and†AES > 0.5, More preferably,†AES > 0.8.

The level of alkyl ether sulphate is preferably from 0.5 wt% to 25 wt% of the total first composition, more preferably, from 3 wt% to 18 wt%, most preferably, from 6 wt% to 15 wt% of the total first composition. Nonionic surfactant

Compositions of the invention may comprise nonionic surfactant, preferably, from 0 to 10 wt%, more preferably, from 0 to 5 wt%, most preferably, no nonionic surfactant is present.

Nonionic surfactants that can be included in shampoo compositions of the invention include condensation products of aliphatic (Cs - Cis) primary or secondary linear or branched chain alcohols or phenols with alkylene oxides, usually ethylene oxide and generally having from 6 to 30 ethylene oxide groups. Alkyl ethoxylates are particularly preferred. Most preferred are alkyl ethoxylates having the formula R-(OCH2CH2)nOH, where R is an alkyl chain of C12 to C15, and n is 5 to 9. Other suitable nonionic surfactants include mono- or di-alkyl alkanolamides. Examples include coco mono- or di-ethanolamide and coco mono- isopropanolamide. Further nonionic surfactants which can be included in shampoo compositions of the invention are the alkyl polyglycosides (APGs). Typically, the APG is one which comprises an alkyl group connected (optionally via a bridging group) to a block of one or more glycosyl groups. Preferred APGs are defined by the following formula:

Figure imgf000009_0001
wherein R is a branched or straight chain alkyl group which may be saturated or unsaturated and G is a saccharide group.

R may represent a mean alkyl chain length of from about C5 to about C20.

Preferably, R represents a mean alkyl chain length of from about Cs to about C12. Most preferably, the value of R lies between about 9.5 and about 10.5. G may be selected from C5 or Ce monosaccharide residues, and is preferably, a glucoside. G may be selected from the group comprising glucose, xylose, lactose, fructose, mannose and derivatives thereof. Preferably, G is glucose.

The degree of polymerisation, n, may have a value of from about 1 to about 10 or more. Preferably, the value of n lies from about 1 .1 to about 2. Most preferably, the value of n lies from about 1 .3 to about 1 .5.

Suitable alkyl polyglycosides for use in the invention are commercially available and include for example those materials identified as: Oramix NS10 ex Seppic; Plantaren 1200 and Plantaren 2000 ex Henkel. Other sugar-derived nonionic surfactants which can be included in compositions of the invention include the C10-C18 N-alkyl (Ci-Ce) polyhydroxy fatty acid amides, such as the C12-C18 N-methyl glucamides, as described for example in WO 92 06154 and US 5 194 639, and the N-alkoxy polyhydroxy fatty acid amides, such as C10-C18 N-(3-methoxypropyl) glucamide.

Mixtures of any of the foregoing anionic cleansing surfactants may also be suitable. Amphoteric/zwitterionic Surfactant

Amphoteric or zwitterionic surfactant can be included in an amount ranging from 0 to about 8 wt%, preferably from 1 wt% to 4 wt% of the total shampoo composition. Examples of amphoteric or zwitterionic surfactants include alkyi amine oxides, alkyi betaines, alkyi amidopropyl betaines, alkyi sulphobetaines (sultaines), alkyi glycinates, alkyi carboxyglycinates, alkyi amphoacetates, alkyi amphopropionates, alkylamphoglycinates, alkyi amidopropyl hydroxysultaines, acyl taurates and acyl glutamates, wherein the alkyi and acyl groups have from 8 to 19 carbon atoms. Typical amphoteric and zwitterionic surfactants for use in shampoos of the invention include lauryl amine oxide, cocodimethyl sulphopropyl betaine, lauryl betaine, cocamidopropyl betaine and sodium cocoamphoacetate.

It is particularly preferred if the shampoo composition comprises from 0.5 wt% to 3 wt% of a betaine.

A particularly preferred amphoteric or zwitterionic surfactant is cocoamidopropyl betaine. Mixtures of any of the foregoing amphoteric or zwitterionic surfactants may also be suitable. Preferred mixtures are those of cocoamidopropyl betaine with further amphoteric or zwitterionic surfactants as described above. A preferred further amphoteric or zwitterionic surfactant is sodium cocoamphoacetate.

The total amount of surfactant (including any co-surfactant, and/or any emulsifier) in a shampoo composition of the invention is generally from 1 w% to 50 %, preferably from 2 w% to 40 %, more preferably from 5 %to 25% by total weight surfactant based on the total weight of the composition.

Further Ingredients Cationic Polymers Cationic polymers are preferred ingredients in a shampoo composition of the invention for enhancing performance.

Suitable cationic polymers may be homopolymers which are cationically substituted or may be formed from two or more types of monomers. The weight average (Mw) molecular weight of the polymers will generally be between 100, 000 and 2 million daltons. The polymers will have cationic nitrogen containing groups such as quaternary ammonium or protonated amino groups, or a mixture thereof. If the molecular weight of the polymer is too low, then the conditioning effect is poor. If too high, then there may be problems of high extensional viscosity leading to stringiness of the composition when it is poured.

The cationic nitrogen-containing group will generally be present as a substituent on a fraction of the total monomer units of the cationic polymer. Thus, when the polymer is not a homopolymer it can contain spacer non-cationic monomer units. Such polymers are described in the CTFA Cosmetic Ingredient Directory, 3rd edition. The ratio of the cationic to non-cationic monomer units is selected to give polymers having a cationic charge density in the required range, which is generally from 0.2 to 3.0 meq/gm. The cationic charge density of the polymer is suitably determined via the Kjeldahl method as described in the US

Pharmacopoeia under chemical tests for nitrogen determination.

Suitable cationic polymers include, for example, copolymers of vinyl monomers having cationic amine or quaternary ammonium functionalities with water soluble spacer monomers such as (meth)acrylamide, alkyi and dialkyi (meth)acrylamides, alkyi (meth)acrylate, vinyl caprolactone and vinyl pyrrolidine. The alkyi and dialkyi substituted monomers preferably have C1 -C7 alkyi groups, more preferably C1 -3 alkyi groups. Other suitable spacers include vinyl esters, vinyl alcohol, maleic anhydride, propylene glycol and ethylene glycol. The cationic amines can be primary, secondary or tertiary amines, depending upon the particular species and the pH of the composition. In general secondary and tertiary amines, especially tertiary, are preferred.

Amine substituted vinyl monomers and amines can be polymerized in the amine form and then converted to ammonium by quaternization.

The cationic polymers can comprise mixtures of monomer units derived from amine- and/or quaternary ammonium-substituted monomer and/or compatible spacer monomers.

Suitable cationic polymers include, for example: cationic diallyl quaternary ammonium-containing polymers including, for example, dimethyldiallylammonium chloride homopolymer and copolymers of acrylamide and dimethyldiallylammoniunn chloride, referred to in the industry (CTFA) as Polyquaternium 6 and Polyquaternium 7, respectively; mineral acid salts of amino-alkyl esters of homo-and co-polymers of unsaturated carboxylic acids having from 3 to 5 carbon atoms, (as described in U.S. Patent 4,009,256); cationic polyacrylamides(as described in WO95/2231 1 ). Other cationic polymers that can be used include cationic polysaccharide polymers, such as cationic cellulose derivatives, cationic starch derivatives, and cationic guar gum derivatives.

Cationic polysaccharide polymers suitable for use in compositions of the invention include monomers of the formula:

A-O-[R-N+(R1)(R2)(R3)X"], wherein: A is an anhydroglucose residual group, such as a starch or cellulose anhydroglucose residual. R is an alkylene, oxyalkylene, polyoxyalkylene, or hydroxyalkylene group, or combination thereof. R1, R2 and R3 independently represent alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl, or alkoxyaryl groups, each group containing up to about 18 carbon atoms. The total number of carbon atoms for each cationic moiety (i.e., the sum of carbon atoms in R1, R2 and R3) is preferably, about 20 or less, and X is an anionic counterion.

Another type of cationic cellulose includes the polymeric quaternary ammonium salts of hydroxyethyl cellulose reacted with lauryl dimethyl ammonium-substituted epoxide, referred to in the industry (CTFA) as Polyquaternium 24. These materials are available from the Amerchol Corporation, for instance under the tradename Polymer LM-200.

Other suitable cationic polysaccharide polymers include quaternary nitrogen- containing cellulose ethers (e.g. as described in U.S. Patent 3,962,418), and copolymers of etherified cellulose and starch (e.g. as described in U.S. Patent 3,958,581 ).

A particularly suitable type of cationic polysaccharide polymer that can be used is a cationic guar gum derivative, such as guar hydroxypropyltrimethylammonium chloride (commercially available from Rhodia in their JAGUAR trademark series). Examples of such materials are JAGUAR C13S, JAGUAR C14, JAGUAR C15, JAGUAR C17 and JAGUAR C16 Jaguar CHT and JAGUAR C162. Mixtures of any of the above cationic polymers may be used.

Cationic polymer will generally be present in a shampoo composition of the invention at levels of from 0.01 % to 5%, preferably from 0.03 % to 1 %, more preferably from 0.05 % to 0.5% by total weight of cationic polymer based on the total weight of the composition.

Suspending Agent

Preferably, an aqueous shampoo composition of the invention further comprises a suspending agent. Suitable suspending agents are selected from polyacrylic acids, cross-linked polymers of acrylic acid, copolymers of acrylic acid with a hydrophobic monomer, copolymers of carboxylic acid-containing monomers and acrylic esters, cross-linked copolymers of acrylic acid and acrylate esters, heteropolysaccharide gums and crystalline long chain acyl derivatives. The long chain acyl derivative is desirably selected from ethylene glycol stearate, alkanolamides of fatty acids having from 16 to 22 carbon atoms and mixtures thereof. Ethylene glycol distearate and polyethylene glycol 3 distearate are preferred long chain acyl derivatives, since these impart pearlescence to the composition. Polyacrylic acid is available commercially as Carbopol 420, Carbopol 488 or Carbopol 493. Polymers of acrylic acid cross-linked with a polyfunctional agent may also be used; they are available commercially as Carbopol 910, Carbopol 934, Carbopol 941 and Carbopol 980. An example of a suitable copolymer of a carboxylic acid containing monomer and acrylic acid esters is Carbopol 1342. All Carbopol (trademark) materials are available from Lubrizol.

Suitable cross-linked polymers of acrylic acid and acrylate esters are Pemulen TR1 or Pemulen TR2. A suitable heteropolysacchande gum is xanthan gum, for example that available as Kelzan mu.

Mixtures of any of the above suspending agents may be used. Preferred is a mixture of cross-linked polymer of acrylic acid and crystalline long chain acyl derivative. Suspending agent will generally be present in a shampoo composition of the invention at levels of from 0.1 % to 10%, preferably, from 0.5 % to 6 %, more preferably, from 0.9 % to 4 % by total weight of suspending agent based on the total weight of the composition. Preferably, the shampoo composition has a pH of 2 to 8 measured using a calibrated pH meter, more preferably, from 3 to 6.5. Product form

It is preferred that the shampoo is stored in an air tight container such as a bottle closed with an air tight cap.

Second Composition

The second composition comprises an comprises an aromatic heterocyclic compound wherein the ring containing the heteroatom of the aromatic heterocyclic compound, is substituted by a primary amino group or secondary amino group and an OH or allkoxy group and these two groups are ortho to each other.

Preferably, the aromatic heterocyclic is substituted by a primary amino group (NH2) and an OH and these two groups are ortho to each other.

Preferably, the aromatic heterocyclic is a 6 membered ring and the heteroatom is N. Preferably, the aromatic heterocylic is selected from pyridine, quinoline, isoquinoline, pyrazine, quionxaline, acridine, pyrimidine, quinazoline, pyridazine, and cinnoline. More preferably, pyridine. Most preferably, 2-Amino-3- hydroxypyridine.

Other organic groups may be present on the aromatic rings, preferably, alkyl, ester, alkyl amides, halides, CN. The molecular weight of the aromatic heterocyclic compounds is preferably, less than 1000, more preferably, less than 500.

Preferably, the aromatic heterocyclic compounds is present from 0.01 to 5, more preferably, 0.05 to 2, most preferably 0.1 to 0.5wt%. The second composition may, in addition to heterocyclic compound, comprise additional polyphenols. Such combination gives an excellent black colouration to the hair. Additional polyphenols are preferably, selected from ethyl gallate, propyl gallate, catechin, epicatechin, catechin gallate, epicatechin gallate, gallocatechin, epigallocatechin, epigallocatechin gallate, curcumin, natural black 1 , natural black 2, natural red 24. More preferably, selected from natural black 1 , gallic acid and propyl gallate. When present the level of polyphenol is preferably, from 0.05 to 5wt%.

Preferably, the composition has a pH of 2 to 7 measured using a calibrated pH meter more preferably, 3 to 6. To avoid oxidation of the composition by air it is preferred that the composition is stored in an airtight container, preferably, a bottle closed with an air tight cap.

The composition contains water, preferably, as the dominate ingredient. Auxiliary ingredients may be present for example to increase the viscosity, perfume and help solubilise the juice etc. Solubilising ingredients include organic solvents and surfactants.

It is preferable, if the aminophenol containing composition is a conditioning composition, more preferably, a rinse off conditioning composition. Particularly preferred is a composition that is applied after shampooing.

If present in a conditioner composition comprising a protonating organic acid, the polyphenol is preferably, present at a higher molar concentration than the protonating organic acid. In this case the protonating organic acid does not include a polyphenol. Preferably, the water used to formulate all compositions has a French hardness of from 0 to 36 degrees, more preferably, 0 to 24 degrees, most preferably, from 0 to 2 degrees. Preferably, the water used to formulate all compositions contains less than 1 ppm of chlorine based bleaching agents such as chlorine dioxide or hypochlorite. Most preferably, less than 50ppb.

Conditioning Agents

Silicone Conditioning Agents

The compositions of the invention can contain, emulsified droplets of a silicone conditioning agent, for enhancing conditioning performance. Silicone conditioning agents may be present in the shampoo or conditioner.

Suitable silicones include polydiorganosiloxanes, in particular

polydimethylsiloxanes which have the CTFA designation dimethicone. Also suitable for use compositions of the invention (particularly shampoos and conditioners) are polydimethyl siloxanes having hydroxyl end groups, which have the CTFA designation dimethiconol. Also suitable for use in compositions of the invention are silicone gums having a slight degree of cross-linking, as are described for example in WO 96/31 188.

The viscosity of the emulsified silicone itself (not the emulsion or the final hair conditioning composition) is typically at least 10,000 est at 25 °C the viscosity of the silicone itself is preferably, at least 60,000 est, most preferably, at least 500,000 est, ideally at least 1 ,000,000 est. Preferably, the viscosity does not exceed 109 est for ease of formulation. Emulsified silicones for use in the shampoo compositions of the invention will typically have an average silicone droplet size in the composition of less than 30, preferably, less than 20, more preferably, less than 10 μητι, ideally from 0.01 to 1 μΐη . Silicone emulsions having an average silicone droplet size of≤ 0.15 μηη are generally termed microemulsions.

Emulsified silicones for use in the conditioner compositions of the invention will typically have an size in the composition of less than 30, preferably, less than 20, more preferably, less than 15. Preferably, the average silicone droplet is greater than 0.5 μητι, more preferably, greater than 1 μητι, ideally from 2 to 8 μηη.

Silicone particle size may be measured by means of a laser light scattering technique, for example using a 2600D Particle Sizer from Malvern Instruments. Examples of suitable pre-formed emulsions include Xiameter MEM 1785 and microemulsion DC2-1865 available from Dow Corning. These are emulsions /microemulsions of dimethiconol. Cross-linked silicone gums are also available in a pre-emulsified form, which is advantageous for ease of formulation. A further preferred class of silicones for inclusion in shampoos and conditioners of the invention are amino functional silicones. By "amino functional silicone" is meant a silicone containing at least one primary, secondary or tertiary amine group, or a quaternary ammonium group. Examples of suitable amino functional silicones include: polysiloxanes having the CTFA designation "amodimethicone". Specific examples of amino functional silicones suitable for use in the invention are the aminosilicone oils DC2-8220, DC2-8166 and DC2-8566 (all ex Dow Corning).

Suitable quaternary silicone polymers are described in EP-A-0 530 974. A preferred quaternary silicone polymer is K3474, ex Goldschmidt. Also suitable are emulsions of amino functional silicone oils with non ionic and/or cationic surfactant. Pre-formed emulsions of amino functional silicone are also available from suppliers of silicone oils such as Dow Corning and General Electric. Specific examples include DC939 Cationic Emulsion and the non-ionic emulsions DC2-7224, DC2-8467, DC2-8177 and DC2-8154 (all ex Dow Corning).

With some shampoos it is preferred to use a combination of amino and non amino functional silicones The total amount of silicone is preferably from 0.01 wt% to 10 %wt of the total composition more preferably, from 0.1 wt% to 5 wt%, most preferably, 0.5 wt% to 3 wt% is a suitable level, especially for a shampoo composition.

(ii) Non-silicone Oily Conditioning Components

Compositions according to the present invention may also comprise a dispersed, non-volatile, water-insoluble oily conditioning agent. Preferably, such non-silicone conditioning oily conditioning agents are present in conditioner compositions. By "insoluble" is meant that the material is not soluble in water (distilled or equivalent) at a concentration of 0.1 % (w/w), at 25°C.

Suitable oily or fatty materials are selected from hydrocarbon oils, fatty esters and mixtures thereof. Straight chain hydrocarbon oils will preferably, contain from about 12 to about 30 carbon atoms. Also suitable are polymeric hydrocarbons of alkenyl monomers, such as C2-C6 alkenyl monomers.

Specific examples of suitable hydrocarbon oils include paraffin oil, mineral oil, saturated and unsaturated dodecane, saturated and unsaturated tridecane, saturated and unsaturated tetradecane, saturated and unsaturated pentadecane, saturated and unsaturated hexadecane, and mixtures thereof. Branched-chain isomers of these compounds, as well as of higher chain length hydrocarbons, can also be used. Suitable fatty esters are characterised by having at least 10 carbon atoms, and include esters with hydrocarbyl chains derived from fatty acids or alcohols, Monocarboxylic acid esters include esters of alcohols and/or acids of the formula R'COOR in which R' and R independently denote alkyl or alkenyl radicals and the sum of carbon atoms in R' and R is at least 10, preferably at least 20. Di- and trialkyl and alkenyl esters of carboxylic acids can also be used.

Particularly preferred fatty esters are mono-, di- and triglycerides, more

specifically the mono-, di-, and tri-esters of glycerol and long chain carboxylic acids such as C1-C22 carboxylic acids. Preferred materials include cocoa butter, palm stearin, sunflower oil, soyabean oil and coconut oil.

The oily or fatty material is suitably present at a level of from 0.05 wt% to 10 wt%, preferably from 0.2 wt% to 5wt%, more preferably from about 0.5 wt%to 3 wt%. Cationic Conditioning Surfactants

Such conditioner compositions will typically comprise one or more conditioning surfactants which are cosmetically acceptable and suitable for topical application to the hair.

Suitable conditioning surfactants include those selected from cationic surfactants, used singly or in admixture. Preferably, the cationic surfactants have the formula N+R1 R2R3R4 wherein R1 , R2, R3 and R4 are independently (Ci to C30) alkyl or benzyl. Preferably, one, two or three of R1 , R2, R3 and R4 are independently (C4 to C30) alkyl and the other R1 , R2, R3 and R4 group or groups are (C1-C6) alkyl or benzyl. More preferably, one or two of R1, R2, R3 and R4 are independently (Ce to C30) alkyl and the other R1, R2, R3 and R4 groups are (C1 -C6) alkyl or benzyl groups. Optionally, the alkyl groups may comprise one or more ester (-OCO- or - COO-) and/or ether (-O-) linkages within the alkyl chain. Alkyl groups may optionally be substituted with one or more hydroxyl groups. Alkyl groups may be straight chain or branched and, for alkyl groups having 3 or more carbon atoms, cyclic. The alkyl groups may be saturated or may contain one or more carbon- carbon double bonds (eg, oleyl). Alkyl groups are optionally ethoxylated on the alkyl chain with one or more ethyleneoxy groups.

Suitable cationic surfactants for use in conditioner compositions according to the invention include cetyltrimethylammonium chloride, behenyltrimethylammonium chloride, cetylpyridinium chloride, tetramethylammonium chloride,

tetraethylammonium chloride, octyltrimethylammonium chloride,

dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octyldimethylbenzylammonium chloride, decyldimethylbenzylammonium chloride, stearyldimethylbenzylammonium chloride, didodecyldimethylammonium chloride, dioctadecyldimethylammonium chloride, tallowtrimethylammonium chloride, dihydrogenated tallow dimethyl ammonium chloride (eg, Arquad 2HT/75 from Akzo Nobel), cocotrimethylammonium chloride, PEG-2-oleammonium chloride and the corresponding hydroxides thereof. Further suitable cationic surfactants include those materials having the CTFA designations Quaternium-5, Quaternium- 31 and Quaternium-18. Mixtures of any of the foregoing materials may also be suitable. A particularly useful cationic surfactant for use in conditioners according to the invention is cetyltrimethylammonium chloride, available commercially, for example as GENAMIN CTAC, ex Hoechst Celanese. Another particularly useful cationic surfactant for use in conditioners according to the invention is

behenyltrimethylammonium chloride, available commercially, for example as GENAMIN KDMP, ex Clariant. Another example of a class of suitable cationic surfactants for use in the invention, either alone or together with one or more other cationic surfactants, is a

combination of (i) and (ii) below: (i) an amidoamine corresponding to the general formula (I):

Figure imgf000023_0001

in which R1 is a hydrocarbyl chain having 10 or more carbon atoms,

R2 and R3 are independently selected from hydrocarbyl chains of from 1 to 10 carbon atoms, and m is an integer from 1 to about 10; and

(ii) an acid.

As used herein, the term hydrocarbyl chain means an alkyl or alkenyl chain.

Preferred amidoamine compounds are those corresponding to formula (I) in which R1 is a hydrocarbyl residue having from about 1 1 to about 24 carbon atoms,

R2 and R3 are each independently hydrocarbyl residues, preferably, alkyl groups, having from 1 to about 4 carbon atoms, and m is an integer from 1 to about 4.

Preferably, R2 and R3 are methyl or ethyl groups.

Preferably, m is 2 or 3, i.e. an ethylene or propylene group.

Preferred amidoamines useful herein include stearamido-propyldimethylamine, stearamidopropyldiethylamine, stearamidoethyldiethylamine, stearamidoethyldinnethylannine, palmitamidopropyldinnethylannine, palmitamidopropyl-diethylannine, palmitamidoethyldiethylannine,

palmitamidoethyldinnethylannine, behenamidopropyldimethyl-annine,

behenamidopropyldiethylmine, behenamidoethyldiethyl-amine,

behenamidoethyldimethylannine, arachidamidopropyl-dimethylannine,

arachidamidopropyldiethylamine, arachid-amidoethyldiethylamine,

arachidamidoethyldimethylannine, and mixtures thereof.

Particularly preferred amidoamines useful herein are

stearamidopropyldimethylamine, stearamidoethyldiethylamine, and mixtures thereof.

Commercially available amidoamines useful herein include:

stearamidopropyldimethylamine with tradenames LEXAMINE S-13 available from Inolex (Philadelphia Pennsylvania, USA) and AMIDOAMINE MSP available from Nikko (Tokyo, Japan), stearamidoethyldiethylamine with a tradename

AMIDOAMINE S available from Nikko, behenamidopropyldimethylamine with a tradename INCROMINE BB available from Croda (North Humberside, England), and various amidoamines with tradenames SCHERCODINE series available from Scher (Clifton New Jersey, USA).

A protonating acid may be present. Acid may be any organic or mineral acid which is capable of protonating the amidoamine in the conditioner composition. Suitable acids useful herein include hydrochloric acid, acetic acid, tartaric acid, fumaric acid, lactic acid, malic acid, succinic acid, and mixtures thereof.

Preferably, the acid is selected from the group consisting of acetic acid, tartaric acid, hydrochloric acid, fumaric acid, lactic acid and mixtures thereof.

The primary role of the acid is to protonate the amidoamine in the hair treatment composition thus forming a tertiary amine salt (TAS) in situ in the hair treatment composition. The TAS in effect is a non-permanent quaternary ammonium or pseudo-quaternary ammonium cationic surfactant.

Suitably, the acid is included in a sufficient amount to protonate more than 95 mole% (293 K) of the amidoamine present.

In conditioners of the invention, the level of cationic surfactant will generally range from 0.01 % to 10 %, more preferably, 0.05 % to 7.5 %, most preferably, 0.1 % to 5 % by weight of the composition.

Conditioners of the invention will typically also incorporate a fatty alcohol. The combined use of fatty alcohols and cationic surfactants in conditioning

compositions is believed to be especially advantageous, because this leads to the formation of a lamellar phase, in which the cationic surfactant is dispersed.

Representative fatty alcohols comprise from 8 to 22 carbon atoms, more preferably 16 to 22. Fatty alcohols are typically compounds containing straight chain alkyl groups. Examples of suitable fatty alcohols include cetyl alcohol, stearyl alcohol and mixtures thereof. The use of these materials is also

advantageous in that they contribute to the overall conditioning properties of compositions of the invention.

The level of fatty alcohol in conditioners of the invention will generally range from 0.01 % to 10 %, preferably, from 0.1 % to 8 %, more preferably, from 0.2 % to 7 %, most preferably, from 0.3 % to 6 % by weight of the composition. The weight ratio of cationic surfactant to fatty alcohol is suitably from 1 : 1 to 1 :10, preferably, from 1 :1 .5 to 1 :8, optimally from 1 :2 to 1 :5. If the weight ratio of cationic surfactant to fatty alcohol is too high, this can lead to eye irritancy from the composition. If it is too low, it can make the hair feel squeaky for some consumers. Adjuncts

The compositions of the present invention may also contain adjuncts suitable for hair care. Generally such ingredients are included individually at a level of up to 2 wt%, preferably, up to 1 wt% of the total composition.

Suitable hair care adjuncts, include amino acids, sugars and ceramides and viscosity modifiers. Method of use

The method of colouring hair comprising the steps of applying to hair sequentially in any order a kit for colouring hair comprising:

(i) a first composition comprising at least one transition metal or aluminium ion in the form of a salt and/or complex

ii) a second composition comprising an aromatic heterocyclic compound

wherein the ring containing the heteroatom of the aromatic heterocyclic compound, is substituted by a primary amino group or secondary amino group and an OH or allkoxy group, such that the amino group and the hydroxy/alkoxy groups are ortho to each other.

Preferably, the compositions of the invention are applied to wet hair, necessitating the step of wetting the hair before application of the compositions of the invention. The method preferably comprises the step of rinsing hair between application of the first composition (i) and the second composition (ii). It is highly preferred if the hair is rinsed after application of both compositions of the invention.

In one embodiment of the invention the method described above is repeated a number of times to gradually colour the hair. Further conditioning and/or styling products may be applied as part of the colouring process.

The level of each composition applied to the head of hair is preferably from 5g to 100g.

Preferably, each composition remains on the hair for 5 to 600 seconds, more prefrablyl 0-300 seconds. Preferably, the water used to wet and rinse the hair has a French hardness of from 0 to 36 degrees, more preferably 0 to 24 degrees, most preferably, from 0 to 2 degrees.

Preferably, the water used to wet and rinse the hair contains less than 1 ppm of chlorine based bleaching agents such as chlorine dioxide or hypochlorite. Most preferably less than 50ppb

The invention will now be illustrated by the following non-limiting examples. Examples Experimental

0.7g Hair 50:50 grey human hair tresses were agitated in 5ml of demineralised water for 5 minutes (applicationl ). Hair was removed rinsed in demineralised water, then agitated for 5 minutes in 5ml of demineralised water containing 1wt% of the phenols listed below (application 2). The hair was removed rinsed in demineralised water and dried in air. The experiment was repeated using a 5ml solution of 5wt% of iron(ll) gluconate in application 1 . Following the experiment the colour of the hair was measured using a

reflectometer and expressed as the CIE L*a*b* values. The results are shown in the table below.

Figure imgf000028_0001

Treatment of the hair with iron(ll) then the 2-amino-3-hydroxypyridine leads to a darkening of the hair shown by the drop in the L* value compared to the control reference and the reference with 2-amino-3-hydroxypyridine but without Iron(ll) application.

Treatment of the hair with Iron(ll) then the 2-amino-3-hydroxypyridine does not lead to blueing of hair, as compared to treatment of the hair with iron(ll) then gallic acid. This is shown by the b* values, decreases in b* correspond to blueing.

Claims

A hair colouring kit comprising:
(i) a first composition comprising at least one metal ion in the form of a salt and/or complex in which the metal ion is Fe(ll) Fe(lll), or mixtures thereof;
ii) a second composition comprising an aromatic heterocyclic compound wherein the ring containing the heteroatom of the aromatic heterocyclic compound, is substituted by a primary amino group or secondary amino group and an OH or alkoxy group, such that the amino group and the hydroxy/alkoxy groups are ortho to each other;
in which in which each composition comprises less than 0.05 wt% of each total composition of a water soluble peroxygen oxidising agent.
A kit for colouring hair according to claim 1 in which both compositions comprise less than 0.05 wt% of the total compositions of hydrogen peroxide.
A kit according to any preceding claim in which both compositions comprise less than 0.05 wt% of an oxidising agent.
A kit according to claim 3 in which the compositions comprise less than 0.01 wt% of an oxidising agent.
A kit according to any preceding claim in which the metal is in the form of a complex comprising a ligand derived from an organic acid.
6. A kit as claimed in claim 6 in which the complex comprises a ligand of
gluconate, lactate or ascorbate.
7. A kit according to any preceding claim in which the primary amino group or secondary amino group of the heterocyclic compound is a primary amino group (NH2) and and the OH or allkoxy group is an OH group.
8. A kit according to any preceding claim in which the heterocyclic ring is
pyridine.
9. A kit according to claim 8 in which the heterocyclic compound is 2-amino-3- hydroxypyridine.
10. A kit according to any preceding claim in which the heterocyclic group is present from 0.01 to 5 wt% of the total second composition.
1 1 . A kit according to any preceding claim in which the level of metal
salt/complex is from 0.01 to 10 wt% of the total first composition
12. A kit according to any preceding claim in which the second composition further comprises a polyphenol selected from natural black 1 , gallic acid propyl gallate or mixtures thereof.
13. A kit according to any preceding claim in which the first composition further comprises a surfactant.
14. A kit according to claim 13 in which the surfactant comprises an alkyl ether sulphate.
15. A kit according to claim 13 or claim 14 in which the level of surfactant is from 5 wt% to 25 wt% of the total first composition.
16. A kit for according to any preceding claim in which the second composition further comprises a cationic surfactant
17. A method of colouring hair comprising the steps of applying to hair
sequentially in any order the compositions of the kit described above.
18. A method according to claim 17 which further comprises the step of rinsing the hair between application of the compositions of the kit.
19. A method to dye the hair in which the kit described in any preceding claim is used on successive occasions to gradually colour the hair.
PCT/EP2012/063173 2011-07-08 2012-07-05 Hair colouring kit WO2013007607A3 (en)

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US3962418A (en) 1972-12-11 1976-06-08 The Procter & Gamble Company Mild thickened shampoo compositions with conditioning properties
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