WO2003089330A1

WO2003089330A1 - Hair dye compositions

Info

Publication number: WO2003089330A1
Application number: PCT/EP2003/003242
Authority: WO
Inventors: David Howard Birtwistle; Mark Graham Branch; Terence Davies; Janice Wu
Original assignee: Unilever N.V.; Unilever Plc; Hindustan Lever Limited
Priority date: 2002-04-22
Filing date: 2003-03-27
Publication date: 2003-10-30
Also published as: AU2003216897A1; AR044187A1

Abstract

A permanent hair dye composition together with a two compartment flexible walled container.The hair dye composition being such that it gradually dyes hair treated therewith on successive applications and; the container comprising three layers (11, 12, 13) of material which are completely peripherally sealed along the same peripheral seal thereby forming the two compartments (14, 15), the middle layer (12) having substantially uniform strength on those parts of its' surfaces which have contact with the two compartments (14, 15).

Description

Hair Dye Compositions

This invention relates to a permanent hair dye composition contained within a flexible walled container.

Background of the invention

Hair dyes are commonly sold as semi-permanent hair colours or permanent hair colours. Permanent hair colours normally have two main components; a dye component and a developer component which are kept apart prior to use. Just prior to use, the dye component is mixed with the developer component to activate it. These activated dyestuffs are difficult to handle or store for long periods of time even under carefully controlled conditions, since they rapidly loose activity. Once the developer activates the dye component, thereafter for a short period of time the dyestuff is capable of dyeing hair.

We have realised that many people do not want a product that colours their hair intensely in one dramatic step, nor do they want to commit to a product that promises to colour their hair gradually but only if they purchase a large volume of product that will achieve that change.

WO 01/76546 describes a method for gradually colouring the hair by multiple application of a hair dye. This application teaches that a kit is bought that dispenses a determined level of product but fails to teach the need for selling a product that can be purchased in a progressive manner. Description of the Invention

The present invention relates to a permanent hair dye composition contained within a two compartment flexible walled container; the hair dye composition being such that it gradually dyes hair treated therewith on successive applications and; the container comprising three layers of material which are completely peripherally sealed along the same peripheral seal thereby forming the two compartments, the middle layer having substantially uniform strength on those parts of its' surfaces which have contact with the two compartments.

The invention also relates to a method of treating the hair by applying a permanent hair dye composition from a two compartment flexible walled container as described above, the method comprising the following steps: a) tearing open both compartments of the container; b) emptying the contents of both compartments onto a hand; c) optionally mixing the contents; d) applying the contents to wet hair; e) leaving the contents on the hair for two to ten minutes and; f) rinsing the hair with water.

By the term "gradually dyes" it is meant that a single application of dye does not give the hair the required colour parameter.

The present invention solves the problem of how to achieve a gradual colour change, as opposed to colouring the hair in one intensive treatment. By buying as many gradual hair colouring treatments as they require the consumer has a cost effective method obtaining their desired shade of colour.

Detailed Description

The Composition

The composition of the invention is hair dye composition that gradually dyes hair treated therewith on successive applications.

In particular the present invention relates to specific compositions which are a mixture as described just below:

Part i) a dye intermediates preferably with a conditioner at an alkaline pH

Part ii) an oxidising compound, preferably hydrogen peroxide in a conditioner at an acidic pH.

Parts i) and ii) are held separately within the claimed container.

Unless indicated otherwise, all percentages used herein are percentages by weight of active material based on the weight of the respective composition.

More preferably, in the case of compositions in a conditioner base, part i) can comprise from a) about 1 to about 5 % of a conditioning agent; b) about 0.1 to about 0.5 % of dye; c) about 0.1 to about 1% coupling compound,

For compositions in a conditioner base, Part ii) comprises from: a) about 1 to about 5 % of a conditioning agent; and b) about 1 to about 5 % of an oxidizing compound.

Specific preferred conditioner bases of the invention, part i) , comprise about 0.5 to about 5% of a quaternary nitrogen- containing conditioning agent having two long aliphatic chains each of which contains about 12 to about 18 carbons and two short chain alkyl groups having one or two carbon atoms each bonded to quaternary nitrogen, 10% higher molecular weight fatty alcohols such as cetyl alcohol and stearyl alcohol; and about 1% to about 4% of a volatile silicone such as dimethicone and the dyestuff.

Conditioning compositions of the present invention comprise a mixture of part i) and part ii) wherein:

Part i) comprises: a) about 0.1% to about 99.9% of a conditioning base, which comprises about 0.05% to about 10% of a conditioning agent based upon the total composition; b) about 0.1% to about 1% of a dye; and c) a volatile silicone;

Part ii) comprises: a) about 1 to about 5% of a conditioning base; b) about 1 to about 5% of an oxidative compound.

Hair dyes

The part i) compositions of the present invention include one or more permanent hair colouring agents. Permanent hair dye compositions as defined herein are compositions, which once applied to the hair, are substantially resistant to washout.

The majority of permanent dye systems are based on oxidative dyes. The dye forming intermediates used in oxidative dyes are essentially aromatic diamines, aminophenols and their derivatives.

The oxidation dye intermediates, which are suitable for use in the compositions and processes herein include aromatic diamines, polyhydric phenols, aminophenols and derivatives of these aromatic compounds (e.g., N-substituted derivatives of the amines, and ethers of the phenols) . Primary oxidation dye intermediates are generally colourless molecules prior to oxidation. The oxidation dye colour is generated when the primary intermediate is activated" and subsequently enjoined with a secondary intermediate

(coupling agent) , which is also generally colourless, to form a coloured, conjugated molecule.

Colour modifiers (couplers), such as those detailed hereinafter, are preferably used in conjunction with the oxidation dye precursors herein and are thought to interpose themselves in the coloured polymers during their formation and to cause shifts in the electronic spectra thereof, thereby resulting in slight colour changes. A representative list of oxidation dye precursors suitable for use herein is found in Sagarin, "Cosmetic Science and

Technology"," Interscience, Special Edition, Volume 2, pages 308 to 310.

The typical aromatic diamines, polyhydric phenols, aminophenols, and derivatives thereof, described above as primary dye precursors can also have additional substituents on the aromatic ring, e.g. halogen, aldehyde, carboxylic additional substituents on the amino nitrogen and on the phenolic oxygen, e.g. substituted and unsubstituted alkyl and aryl groups.

The hair colouring compositions of the present invention may, in addition to the essential oxidative hair-colouring agents, optionally include non-oxidative and other dye materials. Optional non-oxidative and other dyes suitable for use in the hair colouring compositions and processes according to the present invention include semi-permanent, temporary and other dyes. Non-oxidative dyes as defined herein include the so-called "direct action dyes", metallic dyes, metal chelate dyes, fibre reactive dyes and other synthetic and natural dyes. Various types of non-oxidative dyes are detailed in: Chemical and Physical Behaviour of Human Hair" 3rd Edn. by Clarence Robbins (pp 250-259); "The Chemistry and Manufacture of Cosmetics". Volume IV. 2nd Edn. Maison G. De " Navarre at chapter 45 by G. S. Kass (pp 841- 920); "cosmetics: Science and Technology" 2nd Edn, Vol II Balsam Sagarin, Chapter 23 by F. E. Wall (pp 279-343); "The Science of Hair Care" edited by C. Zviak, Chapter 7 (pp 235- 261) and "Hair Dyes", J. C. Johnson, Noyes Data Corp., Park Ridge, U. S.A. (1973), (pp 3-91 and 113-139).

Specific hair dyes which may be included in the compositions of the invention include m-aminophenol, p-phenylene diamine, p-toluenediamine; p-phenylenediamine; 2-chloro-p- phenylenediamine; N-phenyl-p-phenylenediamine; N-2- methoxyethyl-p- phenylenediamine; N, N-bis- (hydroxyethyl) -p- phenylenediamine; 2-hydroxymethyl-p-phenylenediamine; 2- hydroxyethyl-p-phenylenediamine; 4, 4 ' -diaminodiphenylamine; 2, 6-dimethyl-p-phenylenediamine; 2-isopropyl-p- phenylenediamine; N- (2-hydroxypropyl) -p-phenylenediamine; 2- propyl-p- phenylenediamine; 1,3-N, N-bis- (2-hydroxyethyl) -N, N-bis (4-aminophenyl) - 2-propanol; 2-methyl-4- dimethylaminoaniline; p-aminophenol; p- methylaminophenol; 3-methyl-p-aminophenol;2-hydroxymethyl-p-aminophenol; 2- methyl-p-aminophenol; 2- (2-hydroxyethylaminomethyl) -p- aminophenol; 2-methoxymethyl-p-aminophenol; and 5- aminosalicylic acid; catechol; pyrogallol; o-aminophenol; 2, 4-diaminophenol; 2,4, 5-trihydroxytoluene; 1,2,4- trihydroxybenzene; 2- ethylamino-p-cresol; 2,3- dihydroxynaphthalene; 5-methyl-o-aminophenol; 6-methyl-o- aminophenol; and 2-amino-5-acetaminophenol; 2-methyl-l- naphthol; l-acetoxy-2-methylnaphthalene; 1 , 7- dihydroxynaphthalene; resorcinol; 4-chlororesorcinol; 1- naphthol; 1, 5-dihydroxynaphthalene; 2,7- dihydroxynaphthalene; 2-methylresorcinol; l-hydroxy-6- aminonaphthalene- 3-sulfonic acid; thymol (2-isopropyl-5- methylphenol) ; 1, 5-dihydroxy-l, 2, 3, 4-tetrahydronaphthalene; 2-chlororesorcinol; 2, 3-dihydroxy-l, 4- naphthoquinone; and l-naphthol-4-sulfonic acid; m-phenylenediamine; 2- (2, 4- diaminophenoxy) ethanol;N, N-bis (hydroxyethyl) -m- phenylenediamine; 2,6- diaminotoluene; N,N- bis (hydroxyethyl) -2, 4-diaminophenetole;bis (2, 4- diaminophenoxy) -1, 3-propane; l-hydroxyethyl-2, 4- diaminobenzene; 2-amino- 4 hydroxyethylaminoanisole; aminoethoxy-2, 4-diaminobenzene; 2,4- diaminophenoxyacetic acid; 4, 6-bis (hydroxyethoxy) -m-phenylenediamine; 2,4- diamino-5-methylphenetole; 2, 4-diamino-5- hydroxyethoxytoluene; 2,4- dimethoxy 1, 3-diaminobenzene; and2, 6-bis (hydroxyethylamino) toluene; m-aminophenol; 2- hydroxy-4- carbamoylmethylaminotoluene;m- carbamoylmethylaminophenol; 6- hydroxybenzomorpholine; 2- hydroxy-4-aminotoluene; 2-hydroxy-4- hydroxyethylaminotoluene; 4, 6-dichloro-m-aminophenol; 2- methyl-m- aminophenol; 2-chloro-6-methyl-m-aminophenol; 2- hydroxyethoxy-5- aminophenol; 2-chloro-5- trifluoroethylaminophenol; 4-chloro-6-methyl-m- aminophenol; N-cyclopentyl-3-aminophenol; N-hydroxyethyl-4-methoxy-2- methyl-m-aminophenol and 5-amino-4-methoxy-2-methylphenol; 2-dimethylamino-5-aminopyridine; 2,4,5, 6-tetra- aminopyrimidine;4, 5-diamino-l-methylpyrazole; l-phenyl-3- methyl-5-pyrazolone; 6-methoxy-8-aminoquinoline; 2,6- dihydroxy-4-methylpyridine; 5-hydroxy-l, 4-benzodioxane; 3,4- methylenedioxyphenol; 4-hydroxyethylamino-l, 2- methylenedioxybenzene; 2, 6-dihydroxy-3, 4- dimethylpyridine; 5-chloro-2, 3-dihydroxypyridine; 3, 5- diamino-2, 6- dimethoxypyridine; 2-hydroxyethylamino-6- methoxy-3-aminopyridine; 3,4- methylenedioxyaniline;2, 6-bis- hydroxyethoxy-3, 5-diaminopyridine; 4- hydroxyindole; 3- amino-5-hydroxy-2, 6-dimethoxypyridine; 5, β-dihydroxyindole; 7-hydroxyindole; 5-hydroxyindole; 2-bromo-4,5- methylenedioxyphenol; 6-hydroxyindole; 3-amino-2-methylamino- 6- methoxypyridine; 2-amino-3-hydroxypyridine; 2,6- diaminopyridine; 5- (3, 5-diamino-2-pyridyloxy) -1, 3- dihydroxypentane; 3- (3, 5-diamino-2-pyridyloxy) - 2- hydroxypropanol and 4-hydroxy-2, 5, 6-triaminopyrimidine, or combinations thereof.

Buffering agents

The colouring compositions of the present invention which are a mixture of Part i) and Part ii) have a preferred pH in the range of from about 7.5 to about 12, more preferably from about 8 to about 10.

Buffering agents may be present in part i) compositions of the present invention which have a conditioner base, and compositions of the present invention which have a shampoo base. Coloring compositions of the present invention may contain one or more hair swelling agents (HSAs) such as urea, to adjust the pH to the desired level. Several different pH modifiers can be used to adjust the pH of the final composition or any constituent part thereof.

As herein before described certain alkaline buffering agents such as ammonium hydroxide and monoethylamine (MEA) can also act as hair swelling agents (HSA's) such as urea and the like. Preferred for use as a buffering agent for the colouring compositions according to the present invention is ammonium hydroxide and/or sodium hydroxide.

In part ii) a buffering agent solution is required; especially to stabilise hydrogen in the pH range from 2 to 4. Dilute acids are suitable hydrogen peroxide buffering agents. Phosphoric acid is a preferred agent for buffering hydrogen peroxide solutions.

SOLVENTS

Water is the preferred principal diluent for the compositions according to the present invention. However the compositions according to the present invention may include one or more additional solvents. Additional solvent are selected to be miscible with water and innocuous to the skin, a particularly preferred group includes ethanol, isopropanol, n-propanol, butanol, propylene glycol, ethylene glycol monoethyl ether, and mixtures thereof.

Surfactants

The compositions of the present invention can additionally contain a surfactant system. Suitable surfactants for inclusion in the compositions of the invention generally have a lipophilic chain length of from about 8 to about 22 carbon atoms. Surfactants which are either amphoteric or anionic or zwitterionic are included in compositions of the present invention which have a shampoo base. In addition, there may be included in shampoo compositions of the present invention, cationic, nonionic or zwitterionic surfactants. Compositions of the invention having a conditioner base can include cationic, nonionic or zwitterionic surfactants. Surfactants may be present in part A and part B compositions of the invention.

Amphoteric Surfactants

Amphoteric surfactants suitable for use in the compositions of the invention include: alkyl betaines, alkyl sultaines, alkyl amphoacetates, alkyl amphodiacetates, alkyl amphopropionates, and alkyl amphodipropionates.

Zwitterionic Surfactants

Water-soluble auxiliary zwitterionic surfactants suitable for inclusion in the compositions of the present invention include alkyl betaines.

Water-soluble auxiliary sultaine surfactants suitable for inclusion in the compositions of the present invention include alkyl sultaines. Preferred for use herein is coco amido propylhydroxy sultaine.

Water-soluble auxiliary amine oxide surfactants suitable for inclusion in the compositions of the present invention include alkyl amine oxide corresponding to the general formula RιR₂R₃NO, wherein Ri contains an alkyl, alkenyl or monohydroxyl alkyl radical of from about 8 to about 18 carbon atoms, from 0 to about 10 ethylene oxide moieties, and from 0 to about 1 glyceryl moiety, and R₂ and R₃ contain from about 1 to about 3 carbon atoms and from 0 to about 1 hydroxy group, e.g., methyl, ethyl, propyl, hydroxyethyl, or hydroxypropyl 'radicals.. Preferred amine oxides include cocoamidopropylamine oxide, lauryl dimethyl amine oxide and myristyl dimethyl amine oxide.

Cationic Surfactants

Cationic surfactants include polyethylene condensates of alkyl phenols, condensation products of ethylene oxide, propylene oxide, and ethylene oxide, propylene oxide, and ethylene diamine, long chain tertiary amine oxides, long chain tertiary phosphine oxides, and the like.

Conditioners

The conditioning compositions of this invention also contain at least a water-soluble or water-dispersible quaternary nitrogen-containing conditioning agent that is also sometimes referred to herein as a cationic compound. A long chain fatty alcohol is also present in more preferred compositions, and a tertiary amidoamine is additionally present in particularly preferred compositions.

The quaternary nitrogen-containing conditioning agents are preferably present at from about 0.5 to about 5 percent by weight of the composition as an active ingredient. More preferably, the quaternary nitrogen-containing conditioning agent is present at from about 2 to about 3 weight percent, as an active ingredient. The class of quaternary nitrogen-containing conditioning agents useful herein contain one quaternary nitrogen atom having (a) two long aliphatic chains and (b) two identical or different short chain alkyl groups having one or two carbon atoms, each bonded to the quaternary nitrogen atom. The two long chains each contain about 12 to about 18 carbon atoms.

Illustrative conditioning agents include distearyldimethylammonium chloride and dilauryldimethylammonium chloride. These compounds are named Quaternium-5 and Quaternium-47, respectively, in the CTFA Cosmetic Ingredient Dictionary, 2nd ed., 1977, published by the Cosmetic, Toiletry and Fragrance Association, Inc., hereinafter referred to as the CTFA Dictionary.

It is noted that the long aliphatic chain of the before- mentioned conditioning agents need not be solely or primarily of one chain length, i.e., the long chain need not be cetyl, myristyl, lauryl or stearyl. Rather, conditioning agents whose long aliphatic chain contains a mixture of lengths can be used. Such conditioning agents are conveniently prepared from naturally occurring materials, such as tallow, coconut oil, soya oil and the like, or from synthetically produced mixtures. Examples of useful conditioning agents having mixed aliphatic chain lengths include dimethyldi- (hydrogenated tallow) ammonium chloride and dialkyldimethylammonium chloride wherein each alkyl group is a saturated group consisting primarily of 16 carbon atoms. These quaternary nitrogen-containing conditioning agents are named Quaternium- 18 and Quaternium-31, respectively, in the CTFA Dictionary.

The compositions of this invention can also be in the form of emulsions that contain additional amounts of hydrophilic and/or hydrophobic ingredients. Emulsions containing additional hydrophobic materials are particularly preferred. It is preferred that those emulsions be stable to phase separation at a temperature of about 25 degree C for a period of about 24 hours after their preparation. The emulsions are more preferably stable to phase separation at temperatures normally found in commercial product storage and shipping for periods of one year or more.

Thickeners

Thickeners may be included in compositions of the invention. It is preferred if the thickener is a long chain fatty alcohols having from about 11 to about 18 carbon atoms, especially preferred are cetyl alcohol and stearyl alcohol.

Preferably the thickener is present at from about 0.5 to about 10 weight percent of the composition, and more preferably at from about 2 to about 5 weight percent. Fatty alcohols of the above discussed carbon chain lengths which are ethoxylated to contain an average of one or two moles of ethylene oxide per mole of fatty alcohol can be used in place of the fatty alcohols themselves. Examples of such useful ethoxylated fatty acids include ethylene glycol cetyl ether, polyoxyethylene (2) stearyl ether, and the like; the exemplary compounds having CTFA Dictionary names of Ceteth-1 and Steareth-2, respectively.

Additional thickening agents suitable for use herein include sodium alginate or gum arabic, or cellulose derivatives, such as methyl cellulose or the sodium salt of carboxymethylcellulose or acrylic polymers.

Optional Ingredients

The compositions of the present invention can comprise a wide range of optional ingredients. Examples of these functional classes include: anticaking agents, antioxidants, binders, biological additives, bulking agents, chelating agents, chemical additives, colorants, cosmetic astringents, cosmetic biocides, denaturants, drug astringents, emulsifiers, film formers, fragrance components, humectants, opacifying agents, plasticizers, preservatives, propellants, reducing agents, solvents, foam boosters, hydrotropes, solubilizing agents, suspending agents (nonsurfactant) , sunscreen agents, ultraviolet light absorbers, and viscosity increasing agents (aqueous and nonaqueous) . Examples of other functional classes of materials useful herein that are well known to one of ordinary skill in the art include solubilizing agents, sequestrants, and the like.

Other optional ingredients include organic acids. A non- exclusive list of examples of organic acids which can be used as the proton donating agent are adipic acid, tartaric acid, citric acid, maleic acid, malic acid, succinic acid, glycolic acid, glutaric acid, benzoic acid, malonic acid, salicylic acid, gluconic acid, polyacrylic acid, their salts, and mixtures thereof. Non-exclusive lists of examples of mineral acid for use herein are hydrochloric, phosphoric, sulfuric and mixtures thereof.

It is preferable if the composition has a viscosity from 2000 to 9000 cps (spindle 4 speed, 30rpm 25°C) , preferably 3000 to 8000 cps (spindle 4 speed, 30rpm 25°C) .

The Container

It is an advantage of the present invention to be able to address some of the problems associated with prior two component systems, and their packaging.

In a first aspect, there is provided a two compartment flexible walled container such as a sachet, the container comprising three layers of material which are completely peripherally sealed along the same peripheral seal thereby forming the two compartments, the middle layer having substantially uniform strength on those parts of its surfaces which contact the two compartments.

In this embodiment, the flexible walled container may have the appearance of two individual containers or sachets linked "back to back", with a single wall (i.e. the middle layer of material) between the compartments providing the contained volumes of the two sachets. The middle layer preferably has uniform rupture strength of those parts of it's surfaces which contact the two compartments; that is it does not have any weaknesses on these parts of the surface which may facilitate failure and mixing of the contents of the two compartments before the container itself is opened. However in certain embodiments this may not exclude the provision of line of weakness on the peripheral seals of the container, which would primarily be on the outer layers of the container but may extended also to the middle layer on the peripheral seal, to facilitate the tearing open of the container.

Such a container has the advantage in that it may readily be made from known materials and using known manufacturing equipment, by modifying equipment used to produce conventional sachets having two layers and produced from continuous rolls of plastic film, for example on a vertical or horizontal form filling machine.

Such a container is also beneficial in that it provides for the rapid and accurate dispensing of two components from the container, in particular if the container is small enough to be readily held by an end in one hand, and have the contents dispensed by drawing the fingers, or fingers and thumb optionally of one hand along both sides of the container towards an opposite open end. Such dispensing and subsequent mixing provides visual reassurance to the user that the two components are properly mixed prior to use. In an envisaged embodiment, the central layer of material in the three layer material may be relatively rigid, compared to the two outer layers which are preferably flexible. However, in a preferred embodiment, all three layers of material of the container are flexible; ideally all three layers will have substantially the same flexibility. The desired degree of flexibility may be that which facilitates easy and simultaneous dispensing of the two components as mentioned above.

Conveniently, all three layers of material are made from plastics materials; any or all three of the layers may be plastics laminate materials. Conveniently all three layers are plastics laminate materials. The plastics materials, and in particular any laminate materials, may contain one or more layers of thermoplastic materials. Preferable, all three layers of material are such that they are readily tearable, so that in use, one end or part of one end of the container may readily be torn off, and both compositions may be dispensed.

Preferably, the container will be generally rectangular in shape, though other shapes may be contemplated.

The container of the invention is suitable for use with any two component compositions which requires the two components of the composition to be kept separate until just prior to use. This may because the two components react with each other to form a reactive mixture which may subsequently loose activity. Alternatively (though in some instances less preferably) it may simply be desired to may the composition in a two part from which the user has to mix and prepare prior to use. Hence, according to a further aspect of the invention, there is provided a two component cosmetic composition for topical application comprising the two components of the composition packaged in the two compartment flexible walled container as described herein, one composition in each compartment.

Containers and packaged products according to the invention are typically not resealable.

With regard to the plastics materials used to form the walls of the containers, which may conveniently be film or sheet materials, one or all of the plastics materials may be an oxygen barrier, or contain a material which provides it with oxygen barrier properties. Particularly preferably, the central wall of the container will be or contain an oxygen barrier, as preferably will any outer layer of material which bounds a compartment containing an oxygen sensitive component .

Where one of the components in a compartment of the container is a dyestuff, it is also important that the central wall of the container and the outer wall of the dyestuff containing compartment contains a suitable barrier to dyestuff migration, which barrier may also be a barrier to both water migration and hydrogen peroxide migration. When a dyestuff is contained in the container, both the central wall and also the outer wall of the dyestuff material containing compartment should contain both an oxygen barrier material, and a material which acts as a barrier to dyestuff migration (which materials may be the same material) . Conveniently, a suitable oxygen barrier, which also serves as a barrier to dyestuff migration is a layer of aluminium foil, which aluminium foil preferably has a thickness of at least 12 μm. Preferably, the aluminium foil is located as a layer within a laminate material which is coated with at least one plastics layers on its outer layers to prevent reaction of the aluminium with other possibly reactive components of the composition. The aluminium layer may also be coated with a layer of primer.

Alternatively, a suitable oxygen barrier layer for use in one or more layers of the plastics materials which make the container of the invention is one comprising (individually) ethylene vinyl alcohol, a polyamide (including for example, amorphous polyamide) , polyacrylonitrite, aliphatic polyketones, PVDC (commercially available as Saran) or polyester, such as e.g. polyethylene terephthalate, including metallised polyethylene terephthalate. This oxygen barrier layer may preferably be incorporated in a sufficient thickness to act as an oxygen barrier.

In particular where one of the compartments of the container contains a dyestuff, it is important that this is protected from exposure to oxygen, which decomposes the dyestuff.

Hence, in a topical product containing a dyestuff, at least the walls of the container in contact with the contained dyestuff (i.e. the central wall and the outer wall of the dyestuff containing compartment) should be made of a material containing an oxygen barrier. These walls should also contain a material, which is a sufficient barrier to the dyestuff, which material may be the same as or separate to the oxygen barrier.

It is preferable that the peripheral seals of the container be heat-sealed. To this end, when the container is made from laminate materials, one or preferably both of the outer surface of the central layer material and the outer surface of the outer layer material adjacent the central material sheet should heat sealable. However, other methods of sealing include ultrasonic sealing and high frequency sealing, which methods are known to those skilled in the art .

Suitable heat sealable layers comprise non-polar thermoplastic resins, preferably polyolefin resins, for example polymers derived from one or more aliphatic or aromatic alkylenes, such as polymers containing units derived from at least one of ethylene, propylene, butylene, styrene, bexene and octane. The non-polar resin may also comprise a compound of one or more polymers, including polyolefinic resins such as polyethylene, polypropylene, ethylene/propylene copolymers, ethylene/propylene/ butylene terpolymers and PET. Polyethylenes are preferred; the polyethylene can be low density polyethylene (having a density of for example 0.910 to 0.925 g/cm³), linear low density polyethylene, medium density polyethylene, linear medium density polyethylene, or high density polyethylenes (having for example a density of 0.950 to 0.980 g/cm³). Linear low density polyethylenes are particularly preferred. The width of the seal between the layers is preferably 3mm to 10 mm, more preferably 5 mm to 9 mm. It has been found that this seal width prevents air ingress gel is still easy for a consumer to open.

In addition, it is highly preferred for ease of manufacture that the outer surfaces of the outer layer materials not in contact with the central layer material are not heat sealable. Again, such materials are well known in the art, and the outer layer of the outer sheet material may comprise for example, a layer of polyester, polyethylene terephthalate or orientated polypropylene.

Particularly preferred materials for manufacturing containers according to the invention are;

1. For manufacturing the outer layers of the container, a laminate of (working from the outer surface towards that contacting the central layer) : a 12 micron layer of PET, a layer of dry lamination adhesive (e.g. a polyurethane), a 12 micron layer of aluminium foil, a layer of dry lamination adhesive, and a 30 micron layer of LLDPE comprised of three separate 10 micron LLDPE layers.

2. For manufacturing a central layer, a 30 micron LLDPE layer comprised of three separate 10 micron LLDPE layers, a layer of dry lamination adhesive, a 12 micron layer of PET, a layer of dry lamination adhesive, a 12 micron layer of aluminium foil, a layer of dry lamination adhesive, and a 30 micron LLDPE layer comprised of three separate 10 micron LLDPE layers. Both of these laminates provide adequate oxygen, dyestuff and moisture barrier properties.

Conveniently, containers produced according to the invention will have dimensions of 20mm to 100mm wide, more preferably 40mm to 80mm wide, even more preferably 50mm to 70mm wide. Conveniently, the containers will have a length of 40mm to 160mm, more preferably 70mm to 80mm. Conveniently, the containers will have a volume in each compartment of 3ml to 40ml, more preferably 5ml to 30ml.

The invention will now be described by way of example only with reference to the accompanying figures, in which;

- Figure 1 shows a longitudinal cross section of a package according to the invention; and

- Figure 2 shows a schematic cross section of a package.

As shown in Figure 1, the package typically comprises three layers, two outer layers 11 and 13, and a middle layer 12, together producing compartments 14 and 15. The respective layers have the compositions detailed above as being particularly preferred. The layers are peripherally heat sealed in the vicinity of arrows 16 and 17, which provide the peripheral seals of the package.

Figure 2 shows a peripherally sealed package of the invention. Internal compartment 14 has the shape shown in Figure 2; the package generally has a closed end 21 and a dispensing end 22. Dispensing end 22 generally has a narrowed neck portion 23 which is narrower than the longitudinal parallel side walls of compartment 14, which is joined to the longitudinal parallel side walls by sloping portions 24a, 24b. The package may also have a product level line 25 generally indicated on the outside of the package, which may serve to indicate the level of the product in the package when the package is filled. The product level line may also serve to give the user an indication of where the package should be torn or cut in use.

Other shapes of container other than rectangular are specifically contemplated, including shaped curved sachets with longitudinal sides of the container or compartments which are not parallel, which shapes will be known to the skilled person.

Method for using the Compositions of the Invention

Shampoo the hair as usual. Tear open the sachet and apply the composition into the palm and optionally mix. Apply product to the hair like a regular conditioner. Rinse the hands. Leave product in the hair for about 2 minutes for colour maintenance to about 5 minutes for colour change. Rinse the hair thoroughly.

In general the method for permanently dyeing hair comprises subjecting said hair to a number of treatments, having a set time interval between each two consecutive such treatments, wherein each treatment comprises steps a.) and b. ) below: a.) contacting said hair, for a period of about 5 seconds to about 5 minutes with a recently made mixture of: i.) an alkaline composition comprising a dye intermediate in a shampoo base or in a conditioner base; and ii.) an acidic composition comprising an oxidizing compound in a shampoo base or in a conditioner base; b. ) rinsing said mixture from said hair with water;

with the proviso that when a conditioner base is present in a.) i.) above, an independently selected conditioner base is also present in a.) ii.) above; and when a shampoo base is present in a.) i.) above, an independently selected shampoo base is also present in a.) ii.) above.

The number of treatments is between about 2 to about 30; and wherein said set time interval between each two consecutive treatments is between about 8 hours and 30 days.

The following examples, which were made, are shown as illustrations only and are not intended to limit the scope of the invention.

Unless indicated otherwise, all parts and percentages used in the examples are parts and percentages by weight of active material based on the weight of the respective composition. EXAMPLE # 1

Dark Brown Colour conditioner: Part i)

1. DI Water 70. (

2. Stearamidopropyl dimethylamine 0.1

3. Dicetyldimonium chloride/PG, 68%/27% active 2 . ^'. 4. Stearyl alcohol and Ceteareth-20, 70% active l.(

5. Cetyl alcohol 3.(

6. DI water 3. (

7. Disodium EDTA 0.:

8. Dimethicone 100% l.( 9. DC silicone fluid 245 l.{

10. Preservatives 0.:

11. DMDM Hydantoin 55% active 0.:

12. Fragrance 0..

13. Sodium metabisulfite 0.^' 14. DI water 15.:

15. m- Aminophenol 0.(

16. N,N Bis (2-hydroxyethyl) -p-phenylenediamine sulfate 0.

17. p-Phenylenediamine 0.^

18. o-Aminophenol 0.( 19. Resorcinol 0..

20. Sodium hydroxide 50% solution 0.^

PH= 8 to 9 Peroxide conditioner: Part ii

I. D.I. Water 74.00 2. Liquid Citric acid, 50% 0.20

3. Stearamidopropyl dimethylamine 0.50

4. Dicetyldimonium chloride/PG, 68%/27% 2.10

5. Stearyl alcohol and Ceteareth-20, 70% 1.00

6. Cetyl alcohol 3.80 7. DI water 5.00

8. Disodium EDTA 0.10

9. Dimethicone 100% 1.00

10. DC silicone fluid 245 1.80

II. Hydrogen Peroxide (35%) 10.00 12. DMDM Hydantoin 55% 0.10

13. Fragrance A42867H/7454965 0.20

14. Phosphoric acid, 85% 0.09

PH=2.5 to 3.5

The two part sachets were flushed with nitrogen each compartment was respectively filled with part i) and ii) .

The outer layer of the sachet was composed of a laminate of PET/A1/LLDPE, the middle layer was composed of LLDPE/AL/LLDPE

Claims

1. A permanent hair dye composition contained within a two compartment flexible walled container; the hair dye composition being such that it gradually dyes hair treated therewith on successive applications and; the container comprising three layers of material which are completely peripherally sealed along the same peripheral seal thereby forming the two compartments, the middle layer having substantially uniform strength on those parts of its' surfaces which have contact with the two compartments .

2. A permanent hair dye composition according to claim 1 comprising two parts i) and ii) : in which part i) comprises a dye intermediate and part ii) comprises an oxidising compound and in which parts i) and ii) are separately contained within the two compartments of the container.

3. A permanent hair dye composition according to claim 2 in which the dye intermediate comprises an aromatic diamine, aminophenol or mixture thereof.

4. A permanent hair dye composition according to claim 2 or claim 3 in which part i) further comprises a cationic conditioning compound.

5. A hair dye composition according to any one of claims 2 to 4 in which the oxidising part ii) further comprises a cationic conditioning compound.

6. A permanent hair dye composition contained within a two compartment flexible walled container according to any preceding claim wherein the contents of the two compartments of the container are dispatched simultaneously during use.

7. A container according to any preceding claim, wherein the peripheral seal is a heat-seal.

8. A container according to any preceding claim wherein any or all of the three layers are plastics laminate materials.

9. A container according to any preceding claim wherein any of the layers is or contains an oxygen or dyestuff barrier.

10. A container according to Claim 9 wherein a central wall of the container is or contains an oxygen or dyestuff barrier.

11. A container according to Claims 9 or 10 wherein the oxygen or dyestuff barrier comprises aluminium foil.

12. A container according to Claim 11 wherein the aluminium foil is at least 12μ thick.

13. A container according to Claims 9 or 10 wherein the oxygen or dyestuff barrier comprises a nylon, an ethylene vinyl alcohol, a polyamide, a polyacrylonitrite, an aliphatic ketone, a polyethylene terephthalate or a metallised polyethylene terephthalate.

14. A container according to any preceding claim wherein at least one of the layers comprises a non-polar thermoplastics resin.

15. A container according to Claim 14 wherein the non-polar thermoplastics resin comprises a polyolefin resin.

16. A container according to Claims 14 or 15 wherein the non-polar thermoplastics resin is a polyethylene resin.

17. A container according to any of the preceding claims wherein an outer surface of the outer layer materials not in contact with the central sheet material are not heat sealable.

18. A container according to Claim 17 wherein the non-heat sealable material is polyester, polyethylene terephthalate or orientated polypropylene.

19. A container according to any of the preceding claims wherein the container has a width of 20mm to 100mm.

20.A container according to any of the preceding claims wherein the container has a length of 40mm to 160mm.

21. A container according to any of the preceding claims wherein the volume of each compartment in the container is 3ml to 30ml.

22. A container according to any preceding claim that has a seal width from 5mm to 9 mm.

23. A container according to any one of claim 2 to 22 wherein the central wall and the outer wall of the compartment containing the dyestuff part i) comprise both an oxygen and a dyestuff barrier material.

24.A method of treating the hair by applying a permanent hair dye composition from a two compartment flexible walled container as claimed in any preceding claim, the method comprising the following steps: a) tearing open both compartments of the container; b) emptying the contents of both compartments onto a hand; c) optionally mixing the contents; d) applying the contents to wet hair; e) leaving the contents on the hair for two to ten minutes and; f) rinsing the hair with water.