WO2013107771A1 - Hair care composition - Google Patents

Hair care composition Download PDF

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WO2013107771A1
WO2013107771A1 PCT/EP2013/050748 EP2013050748W WO2013107771A1 WO 2013107771 A1 WO2013107771 A1 WO 2013107771A1 EP 2013050748 W EP2013050748 W EP 2013050748W WO 2013107771 A1 WO2013107771 A1 WO 2013107771A1
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composition
wt
preferably
preceding
kit
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PCT/EP2013/050748
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French (fr)
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Michael James Cooke
Robert George Riley
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Unilever Plc
Unilever N.V.
Hindustan Unilever Limited
Conopco, Inc., D/B/A Unilever
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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
    • A61K8/30Cosmetics or similar toilet preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37Esters of carboxylic acids
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/02Cosmetics or similar toilet preparations characterised by special physical form
    • A61K8/0241Containing particulates characterized by their shape and/or structure
    • A61K8/027Fibers; Fibrils
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/02Cosmetics or similar toilet preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/044Suspensions
    • 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
    • A61K8/33Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36Carboxylic acids; Salts or anhydrides thereof
    • A61K8/365Hydroxycarboxylic acids; Ketocarboxylic acids
    • 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
    • A61K8/96Cosmetics or similar toilet preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/97Cosmetics or similar toilet preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
    • 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
    • A61K2800/80Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/88Two- or multipart kits
    • A61K2800/884Sequential application
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILET PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/02Preparations for cleaning the hair
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILET PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/12Preparations containing hair conditioners

Abstract

A kit for colouring hair, comprising: (i) a first aqueous composition comprising a) at least 0.01 wt% of a metal ion in the form of a salt and/or complex in which the metal is selected from the group consisting of iron, copper, zinc, aluminium, manganese and mixtures thereof; and b) a suspending agent comprising at least 0.1 wt%, of the total composition citrus fibre that has been mechanically pulped and swollen in water. (ii) a second aqueous second composition, which comprises at least 0.01 wt% of a polyphenol

Description

Hair Care Composition

The present invention relates to hair colouring compositions. Polyphenol compound mordanted with metal ions have been known to dye human hair for many years. Colouring compositions containing metal salts are described in EP0327345 (Beecham) WO2010/135237, (Advance Cosmetic Technologies); WO2007/130777and WO2000/29036 (Henkel). However we have found that compositions comprising metal salts, such as iron, are frequently unstable on storage, especially in shampoo compositions containing cross linked polyacrylates as suspending agents.

The present invention mitigates the problem of instability, in particular phase separation, sedimentation and rancid odour, of colourant compositions comprising iron.

Summary of the Invention Accordingly the present invention provides a kit for colouring hair, comprising:

(i) a first aqueous shampoo composition comprising

a) at least 0.01 wt% of a metal ion in the form of a salt and/or complex in which the metal is selected from the group consisting of iron, copper, zinc, aluminium, manganese and mixtures thereof; and

b) a suspending agent comprising at least 0.1 wt%, of the total

composition citrus fibre that has been mechanically pulped and swollen in water.

(ii) a second aqueous second composition, which comprises at least 0.01 wt% of a polyphenol selected from the group consisting of gallic acid, methyl gallate, ethyl gallate, propyl gallate and mixtures thereof. Also described is a method of colouring hair comprising the steps of applying to hair sequentially in any order:

(i) a first aqueous composition comprising

a) at least 0.01 wt% of a metal ion in the form of a salt and/or complex in which the metal is selected from the group consisting of iron, copper, zinc, aluminium, manganese and mixtures thereof; and

b) a suspending agent comprising at least 0.1 wt%, of the total composition citrus fibre that has been mechanically pulped and swollen in water.

(ii) a second aqueous second composition, which comprises at least 0.01 wt% of a polyphenol

Description of the Invention

Metal Salt/Complex

Shampoo compositions of the invention comprise at least one metal ion in the form of a salt and/or complex in which the metal ion is selected from iron, copper, zinc aluminium or manganese. The level of metal ion is from 0.01 wt% to 5 wt% of the total shampoo composition more preferably 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 imgf000003_0001
With molecular weight of 446.14, then it will contain 55.84/446.14*2 = 0.25wt% of Fe(ll) (2 decimal places). If the formulation contained 1wt% of the salt FeCI2 then the it will contain 55.84/126.75*1 = 0.44wt% of Fe(ll) 2 decimal places. The metal ion is preferably selected from Fe(ll), Fe(lll) and Cu(ll), most preferably Fe(ll).

The metal ion is present as a salt or as a complex with a ligand. Simple salts include sulphates and halides, for instance Fe(ll)SO4 and mixed salts, for instance Fe(ll) ammonium sulphate. It is preferred if the metal is 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", tertiary amines and OH, most preferably COO" and OH. 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. 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 salt and/or complex that is soluble in aqueous solution at the pH of the formulation. Most preferably the metal ion in the form of a salt and/or 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+ = -logwf^kee and the ligand concentration is 10"5 mol/L and the total metal ion concentration is 10"6 mol/L and M"+7free is the molar concentration of uncomplexed metal ions. Preferably, the ligand used has a lower pMn+, than gallic acid. 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.

Polyamino carboxylic acids are preferably present at weight % levels of less than 1 /30th of the main ligand, preferably they are absent from the shampoo. 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 (EDTA) 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 are iron (II) gluconate and iron (II) lactate, most preferably iron (II) gluconate.

Pulped Citrus Fibre Suspending Agent

Compositions of the invention comprise at least 0.1 wt%, of the total first composition, preferably at least 0.15 wt%, more preferably at least 0.2 wt% of citrus fibre that has been mechanically pulped and swollen in water. Most preferably the composition comprises 0.16 to 0.35 wt% of the total composition of pulped citrus fibre. Citrus fibre is derived from citrus fruit; advantageously it comprises the peel of lemons and/or limes. The citrus fruit peel is pulped by subjecting it to high shear and the pulped material is referred to as pulped citrus fibre. Such pulped fibres are capable of absorbing and binding at least 15 times its own weight of water, preferably at least 20 times and even up to 30 times.

The suspending agent is a pulped citrus fibre which has undergone a mechanical treatment comprising a step of high intensity mixing in water and which material has consequently absorbed at least 15 times its own dry weight of water, preferably at least 20 times its own weight, in order to swell it. It may be derived by an

environmentally friendly process from a fruit processing waste stream. This makes it more sustainable than conventional suspending agents. Furthermore, it requires no additional chemicals to aid its dispersal and it can be made as a structured premix to allow process flexibility.

Citrus fruits are preferred as the source of the fibre because they have a large amount of peel that can provide material with the desired water absorbing capacity. The most preferred fruits are lemons and limes because the natural pH of the resulting mechanical pulp is about 3.5, which allows use of potassium sorbate at low levels as an effective preservative for the premix before it is dispersed into the detergent liquid.

In a preferred process, the citrus fibre is mechanically pulped by processing it to make a premix preferably in combination with preservative. This is done by adding dried powdered citrus fibre to at least 15 times its own weight of water and dispersing it under very high shear to further break up the citrus fibres and to begin the process of hydration, or swelling. The mechanically treated citrus fibre is left in contact with the water for sufficient time for it to swell due it being fully hydrated. This can be several hours. We have found it advantageous that pulped citrus fibre is kept separate from surfactant until it is fully swollen. This avoids the possibility for the surfactant to compete with the citrus pulp fibre for the water. Something that becomes more of a problem as the total surfactant concentration increases. This premix pulp swelling process seems to become especially advantageous when surfactant level in the composition is 25 wt% or higher. The very high shear may be provided by a high intensity mixer such as a Silverson mixer, or, less preferably, by means of a High-pressure homogeniser. The homogeniser is less preferred because it can suffer from blockage problems with citrus fibre.

The amount of pulped citrus fibre in the premix is preferably from 1 to 5 wt%. More preferably from 2 to 4 wt%. Depending on the processing equipment used there may be a practical upper limit of from 3.3 to 3.5 wt% as it is advantageous that there is excess water in order to fully hydrate the pulped citrus fibre.

It is preferable if the composition comprises less than 0.2 wt% of the composition of a polyacrylic acid based suspending agent, more preferably less than 0.1 wt%, most preferably less than 0.05 wt%.

Polyphenol The polyphenol containing composition is preferably an at least 0.01 wt% of polyphenol in an aqueous polyphenol solution. The polyphenol composition preferably comprises from 0.05 wt% to 10 wt% of the total composition, more preferably 0.3 wt% to 3 wt% of polyphenol.

Wherein the aqueous polyphenol solution has a pH preferably of 2 to 7 measured using a calibrated pH meter more preferably 3 to 6.

The polyphenol is selected from gallic acid, methyl gallate, ethyl gallate , propyl gallate and mixtures thereof. Propyl gallate is particularly preferred. Preferably, the polyphenols are extracted from a natural source. Preferably, they do not contain any active oxidase enzymes and have been heat treated to destroy any enzyme activity. To avoid oxidation of the polyphenols by air it is preferred that the composition is stored in an airtight container, preferably a bottle closed with an air tight cap.

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

It is preferable if the polyphenol 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

Product Form Compositions of the invention are typically "rinse-off compositions to be applied to the hair and then rinsed away. Shampoo Composition

The first composition comprising a metal salt/citrus fibre is preferably a shampoo composition. Shampoo 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. Anionic Cleansing Surfactant

Shampoo compositions according to the invention will generally comprise one or more anionic cleansing surfactants which are cosmetically acceptable and suitable for topical application to the hair.

Examples of suitable anionic cleansing surfactants are the alkyl sulphates, alkyl ether 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. Typical 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 dodecyl benzene sulphonate, sodium cocoyi isethionate, sodium lauryl isethionate, lauryl ether carboxylic acid and sodium N-lauryl sarcosinate. Preferred anionic cleansing surfactants are sodium lauryl sulphate, sodium lauryl ether sulphate(n)EO, (where n is from 1 to 3), 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).

Mixtures of any of the foregoing anionic cleansing surfactants may also be suitable.

The total amount of anionic cleansing surfactant in shampoo compositions of the invention generally ranges from 0.5 % to 45%, preferably from 1 .5 % to 35%, more preferably from 5 % to 20 % by total weight anionic cleansing surfactant based on the total weight of the composition.

Further Ingredients

Optionally, a shampoo composition of the invention may contain further ingredients as described below to enhance performance and/or consumer acceptability.

Co-surfactant The composition can include co-surfactants, to help impart aesthetic, physical or cleansing properties to the composition. An example of a co-surfactant is a nonionic surfactant, which can be included in an amount ranging from 0.5 % to 8%, preferably from 2 % to 5% by weight based on the total weight of the composition.

For example, representative 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. Other representative 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, 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 imgf000011_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 C2o- Preferably R represents a mean alkyl chain length of from about C8 to about Ci2. Most preferably the value of R lies between about 9.5 and about 10.5. G may be selected from C5 or C6 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 Ci0-Ci8 N- (3-methoxypropyl) glucamide. A preferred example of a co-surfactant is an amphoteric or zwitterionic surfactant, which can be included in an amount ranging from 0.5% to about 8%, preferably from 1 % to 4% by weight based on the total weight of the composition.

Examples of amphoteric or zwitterionic surfactants include alkyl amine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sulphobetaines (sultaines), alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates, alkyl amphopropionates, alkylamphoglycinates, alkyl amidopropyl hydroxysultaines, acyl taurates and acyl glutamates, wherein the alkyl 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 cocoa mphoacetate.

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 % to 50%, preferably from 2 % to 40%, more preferably from 10 % to 25% by total weight surfactant based on the total weight of the composition.

Cationic Deposition Polymer

Cationic polymers are preferred ingredients in a shampoo composition of the invention for enhancing deposition 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, alkyl and dialkyl (meth)acrylamides, alkyl (meth)acrylate, vinyl caprolactone and vinyl pyrrolidine. The alkyl and dialkyl substituted monomers preferably have C1 -C7 alkyl groups, more preferably C1 -3 alkyl 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 dimethyldiallylammonium 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, arylalkyi, alkoxyalkyi, 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 0.05 to 1 %, more preferably from 0.08 to 0.5% by total weight of cationic polymer based on the total weight of the composition. Conditioner Compositions

One part of the kit may be a conditioner for the treatment of hair (typically after shampooing) and subsequent rinsing. Such conditioner compositions preferably comprise the polyphenol. 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 (C 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 imgf000018_0001

in which R 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 cha

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,

stearamidoethyldimethylamine, palmitamidopropyldimethylamine,

palmitamidopropyl-diethylamine, palmitamidoethyldiethylamine,

palmitamidoethyldimethylamine, behenamidopropyldimethyl-amine,

behenamidopropyldiethylmine, behenamidoethyldiethyl-amine,

behenamidoethyldimethylamine, arachidamidopropyl-dimethylamine,

arachidamidopropyldiethylamine, arachid-amidoethyldiethylamine,

arachidamidoethyldimethylamine, 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.

Further Conditioning Agents

Compositions of the invention may comprise further conditioning agents to optimise wet and dry conditioning benefits.

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 a 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.

Other Optional Ingredients

A composition of the invention may contain other ingredients for enhancing performance and/or consumer acceptability. Such ingredients include fragrance, dyes and pigments, pH adjusting agents, pearlescers or opacifiers, viscosity modifiers, preservatives, and natural hair nutrients such as botanicals, fruit extracts, sugar derivatives and amino acids.

Method of use

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

(i) a first aqueous composition comprising

a) at least 0.01 wt% of a metal ion in the form of a salt and/or complex in which the metal is selected from the group consisting of iron, copper, zinc, aluminium, manganese and mixtures thereof; and

b) a suspending agent comprising at least 0.1 wt%, of the total

composition citrus fibre that has been mechanically pulped and swollen in water. (ii) a second aqueous second composition, which comprises at least 0.01 wt% of a polyphenol

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.

A method preferably comprises the step of rinsing hair between application of the shampoo composition (i) and the second composition (ii). It is highly preferred if the hair is rinsed after application of both compositions of the invention.

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 preferably 10 to 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 of the invention are illustrated by a number comparative examples are illustrated by a letter Examples

Shampoo

Figure imgf000026_0001
Figure imgf000027_0001

Quality Standard (q.s.) pH 5 - 7; Viscosity 5000-9000cPs Conditioner

Figure imgf000027_0002

Figure imgf000028_0001

Water Aqua water I Local ! to 100

The conditioner has a creamy / pink appearance. Product pH specification: 4.0-5.0

Shampoo stability Assessment

Example 1 - The freshly made formulation has a green appearance. It has no phase separation after 12 hrs at 45 deg C storage nor at 12 weeks storage at 45 deg C. Example A - The freshly made formulation has a green appearance. It phase separated after 12 hrs at 45 deg C storage; a dark green layer appears at the top. After 1 week at 45 Deg C the formulation has separated into a dark green layer and a solid sediment at the bottom of the jar.

Claims

C LAI MS
1 . A kit for colouring hair, comprising:
(i) a first aqueous composition comprising
a) at least 0.01 wt% of a metal ion in the form of a salt and/or
complex in which the metal is selected from the group consisting of iron, copper, zinc, aluminium, manganese and mixtures thereof; and
b) a suspending agent comprising at least 0.1 wt%, of the total
composition citrus fibre that has been mechanically pulped and swollen in water.
(ii) a second aqueous second composition, which comprises at least 0.01 wt% of a polyphenol selected from the group consisting of gallic acid, methyl gallate, ethyl gallate, propyl gallate and mixtures thereof.
2. A kit as claimed in claim 1 in which the metal is in the form of a metal
complex.
3. A kit as claimed in any preceding claim in which the metal ion is selected from the group consisting of Fe(ll), Fe(lll), Cu(ll) and mixtures thereof.
4. A kit as claimed in claim 3 in which the metal ion is Fe (II).
5. A kit as claimed in any preceding claim in which complex comprises a ligand of gluconate, lactate or ascorbate.
6. A kit as claimed in any preceding claim in which the metal salt and/or
complex is iron (II) gluconate.
7. A kit according to any preceding claim in which the level of metal ion is from 0.01 wt% to 5 wt% of the first composition.
8. A kit according to any preceding claim in which the level of polyphenol is from 0.1 wt% to 5 wt% of the total second composition of a polyphenol.
9. A kit according to any preceding claim in which the iron containing
composition further comprises an anionic cleansing surfactant.
10. A kit according to any preceding claim in which the polyphenol is present in a conditioning composition.
1 1 . A kit according to any preceding claim in which the level of citrus fibre is at least 0.15wt% of the first composition..
12. A kit according to any preceding claim in which the pulped citrus fibre is derived from lemons or limes.
13. A kit according to any preceding claim in which the first composition further comprising at least 0.1 wt% of the total composition of a cationic deposition polymer.
14. A method of colouring hair comprising the steps of applying to hair
sequentially in any order: the compositions described in the claims above.
15. A method according to claim 16 which further comprises the step of rinsing the hair between application of the compositions.
PCT/EP2013/050748 2012-01-18 2013-01-16 Hair care composition WO2013107771A1 (en)

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