FORM 2
THE PATENTS ACT 1970
(39 of 1970)
AND
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See section 10 and rulel3)
1. Title of the invention:
"POWDER HAIR DYE COMPOSITION USING CHLORITES"

2. Applicant (s):
(a) Name: Godrej Consumer Products Limited
(b) Nationality: Indian company incorporated under the Indian Companies
Act, 1956
(c) Address: Pirojshanagar, Eastern Express Highway, Vikroli, Mumbai -
400079, Maharashtra State, India.
3. Preamble to the description:
The following specification particularly describes the invention and the manner in which it is to be performed.

Field of invention:
The present invention generally relates to hair colour imposition, and particularly to powder hair colour composition and more particularly to a novel powder hair colour composition using alkali or alkaline earth metal chlorite salts as oxidants capable of colouring hair at neutral or near neutral pH.
Background and Prior art:
The most commonly used method of dyeing hair, hair particularly human hair is oxidative dying, also referred to as permanent dyeing, in which are of aromatic compounds, generally of the benzenoid series containing a plurality of nuclear amino and hydroxy functions, and which are themselves colorless converted by coupling reactions well known to those skilled in the art, to a ble of colored compounds within the hair fibers by oxidative processes. The colourless ar0matic compounds, in a suitable base formulation are normally mixed with hydrogen peroxide or other strong oxidizing agent shortly before use. The colored compounds or dyes tvpically formed by oxidative coupling between primary intermediates (usuajiy diamino benzenes or amino phenols) and couplers, which are phenols or related cyclic compounds. Various shades are developed by using a mixture containing more than one off both the intermediate and the coupler. The intermediates and couplers, because of there low molecular weights and water solubility diffuse easily into the hair, where the coupling reaction takes place. The colored products developed by oxidation, however, remain trapped in the hair by virtue of their higher molecular weights, relative insolubility in water and absorptive affinity to the internal hair surface. This is the basis for permanent tint toners which, ideally, last for the life of the hair and are relatively unaffected b;, shampooing and perspiration. Additive materials including thickeners, fillers and performes are sometimes included in the hair dye system.
The two parts of the system are packaged separately. They are combined in one container just prior to their use and mixed well to activate the product. The mixture is applied on hair and usually left on the hair for about 15 to 30 minuteS depending upon the shade and color depth desired. Finally, the dye solution is shampoo out of the hair and the hair is dried.
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One of the chief disadvantages of conventional oxidative dyeing is that the oxidant most often used is hydrogen peroxide. Although this chemical has the advantage of being harmless to the skin and inexpensive, it has the severe disadvantage of destructively oxidizing the hair keratin, causing oxidative and bleaching damage to the hair.
Moreover, hydrogen peroxide is normally used under alkaline conditions using ammonia or an amine as the alkaline reagent. These bases impart strong odors to the hair dyeing compositions to which many users strongly object.
Other oxidants have been suggested in attempts to avoid the problems of using hydrogen peroxide.
For example United States Patent No. 2,944,869 teaches the use of orthophenols with alkali metal iodates, periodates and persulfates to form color in hair.
United States Patent No. 3,698,852 suggests that combinations of DOPA derivatives and arylamine derivatives in mixture v/ith alkaline H2O2, dye hair permanently. The patent also teaches that chlorate (CIO3') salts can be employed with or without peroxide. It is required that the couplers be catechols.
United States Patent No. 3,838,966 teaches that periodate and permanganate are useful for oxidizing lower valency metal ions to their oxides. The process may be carried out in the hair to color the hair permanently. No organic dyes are used; rather the hair dyeing is by the colored metal oxides.
United States Patent Nos. 3,948,596 and 3,961,879 teach the oxidation of novel aminophenols with peroxide, persulfate or perborate to color hair.
United States Patent No. 3,986,825 teaches that persulfates or percarbonates may be used in a permanent waving neutralizer, which also contains oxidative dyes in the setting solution. This gives concurrent permanent waving and coloring.
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United States Patent No. 4,104,021 claims various compositions using perborate, periodate or percarbonate in oxidation dye mixtures incorporating a polymer/conditioner.
United States Patent No. 5,413,612 describes aqueous dye compositions containing sodium chlorite together with 5.6-dihydroxyindoline or 5,6-dihydroxyindole, its analogs, homologs or derivatives, methods of using the compositions to color hair and packages containing such compositions.
United States Patent 5,032,138 by Wolfram, et al. describes the use of chlorites as oxidants in hair colouring. The invention provides compositions and methods for oxidative hair dyeing, utilizing a chlorite salt as the oxidizing agent. A package essentially containing two separate compositions, the first comprising an aqueous solution containing an alkali or alkaline earth metal chlorite salt, preferably Sodium Chlorite, the other containing in an aqueous composition an amount of an oxidative primary intermediate and a coupler, which will react to form a tinctorially effective amount of hair dye composition. The patent also teaches us that the use of chlorite induces lesser oxidative damage as compared to lhat of peroxide, which is used at higher pH values. However the use of chlorite is restricted to aqueous preparations.
In the Asian region and particularly in the Indian subcontinent the preferred format used for hair colouring is powder hair colour or dye. Two types of powder hair dyes are generally known. The first being a one component type, that is a mixture of a powdered oxidation dye and a powdered oxidizing agent packaged together. The powder dye is mixed with water and applied to head to colour the hair and the mixture is kept on hair for 30 to 45 minutes to get the desired colour. The second is the two component type, wherein powdered oxidation dye and a powdered oxidizing agent are packaged separately. The two component mixture is mixed just prior to their use to prepare a colouring mixture. Both types of dyes can be stored without deterioration until being prepared as the tinting mixture. Method of preparation plays an important role in stability of the product.
There is ample literature available on synthetic dyes, precursors to dyes, coupling agents, oxidizing agents etc. in powder form.
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United States Patent No 5,769,901 describes a powdered hair dye composition comprising an oxidative dye component in powdered form, in an amount effective for coloring hair; an oxidizing component in powdered form in an amount effective to activate the oxidative dye component; an effective amount of a thickening component in powdered form; and sucrose in powdered form, wherein the sucrose is present in the hair dye composition in an amount of approximately 30-65 weight percent, based on the total weight of the powdered hair dye composition, wherein said powdered hair dye composition is mixed with water before application to the hair.
European Patent EP1733761 describes an oxidative hair colouring composition comprising yogurt powder for improving combability of hair and further relates to process of coloring hair, using said composition in combination with an oxidizing agent, preferably hydrogen peroxide.
US Patent 4,808,189 discloses a powdered hair dye comprising an admixture of an oxidative dye component and an amount of a powdered oxidizing agent, effective to react with said dye component, wherein said dye component is present in the form of a cyclodextrin inclusion complex, which will give high stability for longer shelf life, color-fastness and deeper color.
United States Patent No. 6,488,918 describes methods of making the powdery cosmetic composition using cross-linked silicone elastomer to improve the storage stability.
US Patent 6,613313 describe an oxidation hair dye composition containing aniline compound which exhibits excellent spreadability, applicability, level-dyeing property and shampoo resistance and a method of dyeing hair with the hair dye composition.
Such a conventional system has a variety of shortcomings, including: (1) problems in mixing the components together; (2) the harshness of the systems to the hair due to oxidative damage coupled with high pH of the mixtures (3) the additional processing steps, packaging, shipping expenses, and waste generated due to multiple containers.
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In view of the above, there is need to develop a formulation in powder format by using an alternate oxidant to peroxides and precursors to peroxides; like alkali or alkaline earth metal chlorites, which are capable of delivering long lasting colour in various shades without the harshness associated with the former.
Objects and Advantages:
It is an object of the present invention to provide an oxidative hair colouring product that is able to provide colour at a neutral or near neutral pH as against the conventional peroxide or peroxide precursor systems that are used at an alkaline pH.
Another object of the present invention is to make the colouring process more pleasant for the user, as the composition does not contain ammonia or amines added to it.
Yet another object of the present invention is to reduce oxidative damage to the hair that is caused by use of conventional oxidizing systems that use peroxides or its precursors at an alkaline pH, by use of alkali or alkaline earth metal chlorites as the oxidant.
Yet another objective of the present invention is to maintain the original colour of the hair by avoiding the bleaching effect inflicted by peroxides and its precursors used in conventional dyeing systems.
A further objective of the present invention is to reduce the confusion at the user's end of mixing adequate quantities of colourant and oxidant in the correct proportion by combining the primary intermediates, couplers and oxidant in one stable formulation.
Another object of the present invention is to provide a composition with better colour retention properties as compared to the conventional oxidative dye systems.
Oxidative hair dyeing compositions and methods for their use as a one component type powder hair dye format have now been discovered, which avoid the disadvantages of damaging the hair. These novel compositions are characterized by the use of chlorite salts as the oxidizing agent in lieu of hydrogen peroxide and its precursors.
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There are many advantages to the compositions and methods of the invention. These
include:
The actual coloring of the hair is performed at a pH which is at, or close to, neutrality
rather than under the strongly basic condition associated with the use of hydrogen
peroxide-ammonia or amine combinations.
There is no issue of unwanted odours, since there is no use of ammonia or amines in the composition.
Chlorite salts do not bleach or cause other oxidative damage to human hair as does hydrogen peroxide.
There is no issue of mixing ratios of the colourant and the oxidant as the primary dye intermediates, couplers and the oxidant are premixed into a single stable formulation.
The presence of the alkali metal chlorite in the compositions permits utilization of
primary intermediates which could not be usefully employed with hydrogen peroxide,
thus raising the possibility of new and heretofore unavailable tints and hues in the treated
hair.
The wear quality of the colors produced in the dyed hair is appreciably enhanced.
Although this invention is generally applicable to chlorites, particularly metal chlorites such as alkali and alkaline earth metal chlorites, it will be principally described as it applies to the use of sodium chlorite. This reagent is by far the most preferred, because it is very effective, soluble in water and aqueous alkanols, easily available in a purified state and relatively inexpensive. It has a much lower electrochemical half-wave oxidation potential as compared to the other commonly used oxidants in the art, thereby reducing the likelihood of oxidative hair damage. Yet it is able to impart the desired colour on hair tresses at lower concentrations than those required in the conventionally used oxidants in the art. Additionally, it is substantially non-toxic; the LD50 in rats is 140 mg/kg.
Because it does not degrade the dyes formed by the coupling reaction, the color produced in its presence has outstanding wear qualities.
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Further objects and advantages of the invention will become apparent from the consideration of the ensuing description.
Summary of the invention:
In accordance with the above objectives, the present invention discloses an oxidative powdery hair colour or dye composition for colouring hair fibres comprising from about 0.5% to 25% by weight of an alkali or alkaline earth metal chlorite salt together with an amount of oxidative primary intermediates and couplers, which will react to form a tinctorially effective amount of a hair dye; an oxidative hair dye composition further comprising at least one of the following: surface active agents in an amount up to about 15% by weight, thickening agents in an amount up to about 20% by weight, and antioxidant up to about 1% by weight, pH modifying agents in an amount up to 15 % by weight, silica in an amount up to 25%) by weight and the remaining weight being made up by an inorganic salt, which is essentially inert to the other ingredients of the composition; an oxidative hair dye composition, which may further contain at least one of the following: up to 10 % direct dyes, up to 1% fragrance, up to 5% hair conditioning agents, up to 2% hair nourishing agents.
In another aspect, the process for preparation of the powder hair colour composition, wherein the primary intermediates, couplers and the oxidant are present in a single package is described.
Detailed description of the invention:
The invention will now be described in detail in connection with certain preferred and optional embodiments, so that various aspects thereof may be more fully understood and appreciated.
Accordingly, the present invention describes a novel cosmetic composition for dyeing human hair, as well as process for preparation of the said composition.
In a preferred embodiment of the present invention, the powder hair colour compositions as applied to the human hair, either living or in a wig or other artificial device with
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implanted human hair, will comprise selected primary intermediate and coupler, or a plurality of each, (hereinafter sometimes identified as the reactants) together with from about 0.5 to 25%, preferably 5 to 20%, more preferably 5 to 15% by weight of chlorite salt. All percent by weights defined in this disclosure and claims are percents by weight based on the total weight of the composition.
The amount of dye(s) or couplers) employed will be about the same as utilized in conventional powder oxidant compositions. The amounts which will be tinctorially effective will vary with the selected reactants as is well known in the art. Since the amounts will not vary appreciably from those employed with ordinary oxidant compositions containing hydrogen peroxide, the skilled artisan will have no difficulty in selecting the reactants and the amounts to be employed. Generally each reactant will be present in an amount of from about 0.1% to 25% The said composition needs to be suitably mixed with a vehicle, preferably water to achieve the desired thickness and reactant concentration before applying to hair. Those skilled in the art will have no difficulty in deciding and recommending the amount of said vehicle that needs to be added to the composition prior to application.
The term "package" is used in the widest possible sense. It includes retail packages, such as might be sold to an individual consumer or compositions in large amounts, such as might be sold to a beauty salon. The package must be constructed in a manner such that it protects the contents from moisture throughout the shelf life of the composition.
Any of the conventional dyes and coupling agents used with ordinary oxidant compositions for hair coloring can be employed in the compositions of this invention to achieve a wide variety of tints and hues. Typically useful primary intermediates and couplers are mentioned, for example in U.S. Pat. Nos. 3,536,436; 4,092,102; 3,884,627: 3,981,677; 5,032,138 and British Patent 2,205,329, incorporated by reference herein.
A wide variety of primary intermediates can be employed in this invention including, for example, para-phenylenediamines, corresponding to the formula:
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Formula I

in which: R1 and R2, which may be identical or different, can denote hydrogen, a C| -C$ lower alkyl group, a C1-C6 alkyl radical substituted with one or more hydroxy group(s) or with a methoxy, methylsulphonylamino or aminocarbonyl group, a furfuryl group, or a phenyl radical optionally substituted with an amino group; R3 and R6 can denote, independently of one another, hydrogen, a C1-C6 lower alkoxy group, a halogen atom such as a chlorine atom, a CI -C6 lower alkyl group, or a CI -C6 lower alkyl group substituted with one or more hydroxy group(s): and R4 and R5 denote, independently of one another, hydrogen, a CI -C6 lower alkoxy group, a CI -C6 lower alkyl group, or a halogen atom such as chlorine, as well as their salts with inorganic or organic acids; N.N'-diphenylalkylenediamines in which the phenyl groups are substituted at the para position with an OH or amino group optionally substituted with a C1-C6 alkyl group, it being possible for the amino groups joined by the alkylene group to be substituted with C1-C6 alkyl, C1-C6 hydroxyalkyl or C1-C6 aminoalkyl; para-aminophenols; ortho-aminophenols; orthophenylenediamines and heterocyclic oxidation bases.
Among the useful compounds of formula (1), there may be mentioned p-
phenylenediamine, 2-methyl-para-phenylenediamine, 2-methoxy-para-phenylenediamine,
2-chloro-N-methyl-paraphenylenediamine, N-furfuryl-para-phenylenediamine? 3-
methoxy-N1 -methyl-paraphenylenediamine, 2-chloro-para-phenylenediamine, N-methyl-
para-phenylenedi amine, 2,3-dimethyl-paraphenylenediamine, 5-chloro-N'-methyl-p-
phenylenediamine, 5-methyl-N \N-dimethy]-p-phenylenediamine, 5-methyl-N1 -ethyl-
N'aminocarbonyl-methyO-p-phenylenediamine, 5-methyl-N l-ethyl-N'-(methyl-
sulphony!aminoethyl)-p-phenylenediamine, N-(2-methoxy-ethyl)-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, N,N-bis(2-hydroxyethyl)-p-phenylenediamine. The N'-diphenylalkylenediamines include, for example N,N1-bis-(2-hydroxyethyl)-N,Nl-bis(p-aminophenyl)ethylenediamine. Their salts with acids such as the monohydrochlorides dihydrochlorides or sulphates are also suitable.
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Among p-aminophenols, which are more especially usable according to the invention. there may be mentioned p-aminophenol, 2-methyl-p-aminophenol, 2,3-dimethyl-p-aminophenol, 2,6-dimethyl-p-aminophenol, 3-methoxy-p-aminophenoi 2-chIoro-p-aminophenol, N-methyl-p-amino-phenol and 3-(methylthio)-p-aminophenol, of which p-aminophenol is preferred.
Among ortho bases, ortho-aminophenol, 5-chloro-orthoaminophenol and ortho-phenylenediamine are chosen more especially according to the invention.
Among heterocyclic bases, it is preferable, according to the invention, to use 2,3-diamino-
6-methoxy-pyridine and 2-(2-hydroxyethyl)amino-5-aminopyridine and their salts, and
still more especially 3,6-diarninopyridine, 2,6-dimethoxy-3-aminopyridine, 2-
methylamino-3-amino-6-methoxypyridine, 2,5-diaminopyridine, 2-(N-
hydroxyethyl)amino-5-amino pyridine, and 2-(N,N-bishydroxyethyl)amino-5-aminopyridine.
More especially preferred oxidation bases are p-phenylenediamine 2-methyl-p-phenyIenediamine,N-(2-methoxyethyl)-p-pheny]enediamine, N,N-bis(2-hydroxyethy])-p-phenylene-diamine and p-aminophenol, mono- or polyhydroxylated derivatives of naphthalene and of aminonaphthalene, pyrazolones and benzomorpholines. Among couplers or colour modifiers, there may be mentioned, in particular, the compounds corresponding to the formula:

in which: Rl denotes hydroxy or an amino group which can be substituted with one or more C1 -C6 hydroxyalkyl groups; R3 and R5, independently of one another, can denote hydrogen, a hydroxy group, an amino group optionally substituted with a C1 -C6 lower hydroxyalkyl group or a C1 -C6 lower alkyl group; and R2, R4 and R6 can denote a
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hydrogen atom or a C1 -C6 alkoxy group, a hydroxyalkoxy group or a C1 -C6 lower alkyl group; it also being possible for R3 and R4 together to form a methylenedioxy group.
Among the suitable couplers, there may be mentioned 2-methoxy-5-aminophenol. 2-
methoxy-5-[N-(2-hydroxyethyl)amino]phenyl, l,3-diamino-2,6-dimethoxybenzene, 2-
methoxy-I-(N-methylamino)-4-(2-hydroxyethoxy)-3-amino-benzene, l,3-diamino-6-
methoxybenzene, l,3-diamino-4;6-dimethoxybenzene, 4,6-dimethoxy-l,3-bis[N-(2-
hydroxyethyl)-amino]benzene, 2,6-dimethoxy-3-[N-(2-hydroxyethyl)amino]-l-
aminobenzene, 2,4-dimethoxy-3-|lJ-(2hydroxyethyl)amino]-l-aminobenzene, 2-methyl-
5-[N-(2hydroxyethyl)amino]phenol, l,3-bis[N-(2-hydroxyethy!)amino]-
4methoxybenzene, 3-amino-4-methoxyphenol, 3,4-methylenedioxy-l-aminobenzene, 2,6-dimethyl 3-[N-(2-hydroxyethyl)amino]phenol, 2,6-dimethyl-3-aminophenol, 4-ethoxy-l-amino-3-[N,N-bis(2-hydroxyethyl)amino]benzene, (2,4-diaminophenoxy)ethanol, (2-amino-N-methyl-4-aminophenoxy)ethanol, l-methoxy-2-[N-(2hydroxyethyl)amino]-4-aminobenzene, 3,4-methylenedioxy-6-methoxyphenol, 3-amino-6-methylphenol, 3,4-methylenedioxy-6-methoxyaminobenzene, 3-aminophenoI, l,3-dihydroxybehzene-4-(hydroxyethoxy)-l,3-phenylenediarnine, 4,6-(dihydroxyethoxy)-l,3-phenylenediamine, and 1,3-phenylenediamine.
Other suitable couplers are 6-aminobenzomorpholine, l-amino-7-naphthol, 6-hydroxybenzomorpholine, 1-naphthol, 1,3-dihydroxynaphthalene and 1,2-dihydroxy-benzene. Among heterocyclic couplers there may be mentioned 2,6-dihydroxypyridine, 2,6-diaminopyridine, 2-amino-4hydroxypyridine, 2~hydroxy-4-amino-pyridine, 2-hydroxy-5-aminopyridine, 2-amino-6-hydroxypyridine and the like. Included also are further derivatives of 2,6-diamino alkyl pyridines, where the amino nitrogen of one or both amino groups is mono- or disubstituted with a CI to C6 alkyl group such as the methyl, propyl, isopropyl; butyl, iso- or sec-butyl, pentyl, sec-pentyl, neopoentyl, t-butyl hexyl, 3-methyl pentyl or 4-methylpentyl groups. The amino groups of either the amino-4-hydroxy- or 2-hydroxy-4-amino-pyridines may also have mono- or di- CI-C6 alkylation on the nitrogen atoms.
The 2,6-amino-, or 4-amino-2-hydroxy- or 2-amino-4-hydroxy pyridine nitrogens may also either singularly or doubly be derivatized with alkoxy substituents of carbon lengths
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of 1 to 6 with specific mention of 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl, 2-hydroxypropyl, 2-hydroxybutyl, 2-hydroxypentyl, 2-hydroxyhexyl, 3-hydroxybutyl, 3-hydroxypentyl, and 4-hydroxypentyl groups.
Among trihydroxylated derivatives of benzene, there may be mentioned 1.2,4-trihydroxybenzene, l,2,4-trihydroxy-5-alkylbenzenes in which the alkyl group is a Cl -C6 lower alkyl group and 1,2,3-trihydroxybenzene, and their salts.
Among diaminohydroxybenzenes, there may be mentioned 2,4-diaminophenol and 2,5-diamino-4-methoxy-l-hydroxybenzene, and their salts.
Among aminodihydroxybenzenes, there may be mentioned 2-amino-1,4-dihydroxybenzene, l,4-dihydroxy-2-diethylaminobenzene and 4-aminoresorcinol, and their salts.
Among substituted 1,2-dihydroxybenzenes, 4-methyl-l,2-dihydroxybenzene and 3-methoxy-l,2-dihydroxybenzene are especially preferred.
The aminohydroxybenzenes are chosen, in particular, from 2-amino-4-methoxyphenol, 2-aminophenol, 4,6-dimethoxy-3-a.mino-l-hydroxybenzene and 2,6-dimethyl-4-[N-(p-hydroxphenyI)amino]-I-hydroxybenzene, and their salts.
By way of a triaminobenzene, there may be mentioned 1.5-diamino-2-methy!-4-[N-(p-hydroxyphenyl)amino]-benzene and its salts.
The essential components of the present composition comprise at least one primary dye intermediate and coupler or only primary intermediates, in an amount between 0.1 % to 30 % by weight relative to the total weight of the said composition.
Representative primary dye intermediates include, for instance, p-phenylene diamine, p-toluene diamine, o-phenylene diamine, methoxy paraphenylene diamine, ortho aminophenoi, para aminophenol, of a salt of said compound for example a mono, di or tri hydrochloride or hydro bromide or even sulphate thereof. The composition of the invention may comprise mixture of the above.
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The composition of the invention comprises up to 15% weight of a surface active agent. Surface active agent employed in the dyeing compositions of this invention can be anionic, nonionic or cationic. By way of examples of the various types of surface active agents, there can be mentioned: higher aikylbenzene sulfonates: alkylnaphthalenesulfonates; sulfonated esters of alcohols and polybasic acids: taurates; fatty alcohol sulfates; sulfates of branched chain or secondary alcohols; al kyldi methyl-benzylammonium chlorides, salts of fatty acids or fatty acid mixtures; N-oxyalkylated fatty acid alkanolamides, and the like. Illustrative of Specific surfactants there can be mentioned: sodium lauryl sulfate; polyoxyethylene lauryl ester myristyl sulfate; glyceryl monostearate; triethanolamine oleate, sodium salt of palmitic methyl taurine; cetyl pyridinium chloride; lauryl sulfonate; myristyl sulfonate; lauric diethanolamide; polyoxyethylene stearate; ethoxylated oleoyl diethanolarnide; polyethylene glycol amides of hydrogenated tallow; stearyldimethyl benzyl ammonium chloride; dodecylbenzene sodium sulfonate; 2-amino-2-methy| propanol; triethano|amine salt of p-dodecylbenzene sulfonate; triethanolamine salt of p-dodecylbenzene sulfonate; nonylnaphthalene sodium sulfonate; dioctyl sodium sulfosuccinate; cetrimmoniurri chloride; cetrimide; sodium N-methyl-N-oleoyl taurate; oleic acid ester of sodium isothionate; sodium dodecyl sulfate; sodium salt of 3-diethyl tridecanoI-6-sulfate and the like. Preferred surfactants in the present invention are sodium lauryl sulfate, ammoniui-n lauryl sulphate, or potassium lauryl sulphate. A combination of different surfactants can be used to impart particular viscosity, spreadability and foaming properties. The quantity of surface active agent can vary over a wide range, such as from about 1% to 15% and preferably from about 5 to 10% by weight of the composition.
A thickening agent may also be incorporated in the dyeing composition of this invention, which may be one or several of those commonly used in hair dyeing. These are exemplified by sodium alginate or gum arabic, or cellulose derivatives, such as methylcellulose, e.g., Methocel 60HG, or the sodium salt of carboxymethylcellulose, or hydroxyethylcellulose, e.g., Cellosize QP-40 or hydtoxypropylmethylcellulose, e.g., Methocel 1000M, guar gum and derivatives thereof, carboxy vinyl polymers, hydroxylpropylcellulose, xanthan gum, gum carrageenah, alginic acid salts, pectin, gum Arabic, Karaya gum, Tragacanth gum, agar powder, 0r acrylic polymers, such as
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polyacrylic acid sodium salt, or inorganic thickeners such as bentonite. Among them carboxymethyl cellulose, sodium salt of carboxymethylcellulose, hydroxyl ethyl cellulose and xanthan gum are preferred. The quantity of this thickening agent can also vary over a wide range, even as high as 20%. Ordinarily it will range from about 5 to 20%, preferably between 5-15% by weight of the composition.
It may also be useful to incorporate an antioxidant in the present dye compositions. A variety of antioxidants are known in the prior art, which would be useful for this purpose. Among these, mention may be made of the inorganic sulfites, e.g., sodium sulfite, thioglycollic acid and other mercaptans, butylated hydroxytoluene, sodium dithionite, various forms of ascorbic acid and its derivatives, e.g., sodium ascorbate, erythorbic acid, ascorbyl palmitate, ascorbyl laurate, etc. The quantity of antioxidant when in use can vary quite a bit. However, this will, in general, be up to about 1%, typically 0.01 to 1% by weight.
The composition of the invention comprises 0.10 to 15 percent weight of pH modifying agents. These agents are selected from the group of lactic acid, citric acid, succinic acid, tartaric acid, malic acid, or their corresponding sodium and potassium or ammonium salts. Preferably citric acid or tartaric acid may be employed in an amount of from 2 to ] 0 weight percent to modify the pH of the composition.
Silica is used in the composition as an anti-caking agent and a desiccant agent. The silica component can be used up to about 25% w/w of the oxidative powder hair dye composition of the present invention.
The above composition, which may also include a sufficient amount of inorganic salts selected from salts of sodium, potassium, magnesium or calcium, so as to make the weight of the composition to hundred by weight. Preferred salts are the sulphates of sodium, potassium, magnesium or calcium.
The composition of the present invention comprises a hair conditioning agent in an amount of up to 5% by weight. A variety of hair conditioning agents are known in the prior art, which would be useful for this purpose. Examples from United States Patent
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7303592 are included by reference. Mention may be made of cationic polymers; silicones and silicone derivatives; hydrocarbon oils; monomeric quaternary compounds, and quatemized polymers; silicone conditioners. The term "cationic polymer" means a polymer having a cationic group or a group, which can be ionized into a cationic group. Examples of the cationic polymer include polymers, having on the side chain of its polymer chain, an amino or ammonium group, or a diallyl quaternay ammonium salt as a constituent such as cationic cellulose derivatives, cationic starches, cationic guar gum derivatives, polymers or copolymers of a diallyl quaternary ammonium salt, and quatemized polyvinylpyrrolidone derivatives. Monomeric quaternary compounds are typically cationic compounds, but may also include betaines and other amphoteric and zwitterionic materials that provide a conditioning effect. Suitable monomeric quaternary compounds include behentrialkonium chloride, behentrimonium chloride, benzalkonium bromide or chloride, benzyl triethyl ammonium chloride, bis-hydroxyethyl tallowmonium chloride, Cn-is dialkyldimonium chloride, cetalkonium chloride, ceteartrimonium bromide and chloride, cetrimonium bromide, chloride and methosulfate, cetylpyridonium chloride, cocamidoproypl ethyldimonium ethosulfate, cocamidopropyl ethosulfate. cocoethyldimonium ethosulfate, cocotrimonium chloride and ethosulfate, dibehenyl dimonium chloride, dicetyldimonium chloride, dicocodimonium chloride, dilauryl dimonium chloride, disoydimonium chloride, ditallowdimonium chloride, hydrogenated tallow trimonium chloride, hydroxyethyl cetyl dimonium chloride, myristalkonium chloride, olealkonium chloride, soyethomonium ethosulfate, soytrimonium chloride, stearalkonium chloride, and many other compounds. Quatemized polymers are typically cationic polymers, but may also include amphoteric and,zwitterionic polymers. Useful polymers are exemplified by polyquatemium-4, polyquaternium-6, polyquaternium-7, poIyquaternium-8, polyquatemium-9, polyquaternium-10, polyquaternium-22, polyquatemium-32, polyquaternium-39, polyquaternium-44 and poIyquaternium-47. Silicones suitable to condition hair are dimethicone, amodimethicone, dimethicone copolyol and dimethiconol. Suitable hydrocarbon oils would include mineral oil. Conditioners are usually present in the hair dye composition in an amount of from about 0.01 to about 5% by weight of the composition. Two or more of these conditioning agents may be used in combination. Their content in the whole composition is preferably from 0.01 to 5 wt. %, more preferably from 1 to 5 % by weight.
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The hair dyeing compositions according to the invention can also comprise compatible direct dyes including Disperse Black 9, HC Yellow 2, HC Yellow 4, HC Yellow 15, 2-nitro-p-phenylenediamime, 4-nitro-o-phenylenediamine, 2-amino-6-chloro-4-nitrophenol, HC Red 3, Disperse Violet 1, HC Blue 2, Disperse Blue 3, Basic Red 51 and Disperse Blue 377. These direct dyes can be contained in the hair coloring compositions of the invention in an amount of from about 0.01 to 10.0 % by weight preferably 0.05 to 5.0% by weight.
The hair dyeing compositions according to the invention further comprise nourishing ingredients: For example, proteins and protein derivatives, vitamins, and plant materials such as aloe, chamomile, indigo, hibiscus, amla, bhringaraj, brahmi, shikakai, and henna powders or extracts. The above nourishing ingredients present in the inventive composition in an amount of 0.5 to 2%w/w of the total composition.
The composition of the present invention may also comprise of 0.01 to 1 % by weight of fragrance.
A typical composition according to the present invention comprises: from about 0.5% to 25% by weight of an alkali or alkaline earth metal chlorite salt together with I to 30 % w/w primary intermediates and couplers; 1 to 15% weight of a surface active agent; 5 to 20% thickening agent; 0.01 to 1% antioxidant; 0.01 to 15% pH modifying agent: up to 25% by weight silica; 0.01 to 5% hair conditioning agent; up to 2% hair nourishing agents; optionally 0.01 to 10% direct dyes and fragrance 001% to 1% by weight; and inorganic salts to make the weight of the composition to hundred by weight.
In another preferred embodiment, the invention describes a process of preparing the composition, wherein said process comprises:
1. drying of surfactant, thickener, silica, pH modifying material and inorganic salts to reduce the moisture levels to below 5%;
2. mixing 5 to 25 % by weight of an alkali or alkaline earth metal chlorite salts and up to 25% by weight silica in a ribbon blender for up to 20 minutes at temperature below 40°C and keeping the mixture aside;
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3. adding up to 15% by weight powder surfactant up to 20% by weight thickening
agent, up to 15 % by weight of pH modifying materials, up to 1 % by weight of
antioxidant and inorganic salt one by one into the ribbon blender;
4. blending the mixture for up to 20 minutes at temperature below 40°C and adding
primary intermediates and couplers into said mixture;
5. blending the mixture for up to 20 minutes at temperature below 40°C and adding up to 10 % direct dyes, up to 1% fragrance and up to 5% hair conditioning agents and mixing for a period of up to 20 min; and
6. blending the whole mixture with the blend obtained in step 2), in the ribbon blender at temperature below 40°C for 30 to 60 minutes, preferably 40-50 minutes to obtain powder hair colour composition.
The performance of the composition improves significantly when mixed with water. The oxidative hair dye composition of the present invention as a single product can be packed in a manner that protects the composition from moisture
A suitable container that protects the composition from ingress of moisture may be constructed from glass in the form of a bottle with a suitable closure mechanism which may comprise a combination of rubber plug enclosed with a metallic seal; the metal may be aluminium. It may alternately have a plastic plug with a screw on cap made of metal or plastic. The container may alternately be packaged in a container constructed from organic polymeric material of thickness such that it provides a moisture barrier, comprising two layers wherein the contact layer has added to it a desiccant material that offers product protection against moisture. It may also be packaged for single use in glass ampoules. The composition may also be packed in pouches or sachets such as formed by sealing a durable laminated packaging material from all four sides under appropriate sealing conditions sufficient to produce a good seal and not damage package contents. The durable laminated packaging material includes a contact layer that enables a good seal when the pouches are being formed. This may usually comprise of low density polyethylene. Further the durable laminated packaging material includes a moisture barrier layer comprising a metal foil which may be Aluminium. The outer layer generally comprises an organic polymer which may be polyethylene terephthalate. The Jayers may have an adhesive disposed between the layers. Alternately the durable laminated packaging material may comprise an additional layer placed between the contact layer
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and the metal foil which may comprise of an organic polymer which may be polyethylene terephthalate in order to further enhance the barrier properties. The durable laminated packaging material must be evaluated for any separation of one or more laminate layers by observing the laminate appearance for delamination, perforations, wrinkles, discolouration, and other laminate defects over time when brought into contact with such a composition that has been revealed in this invention. Several such pouches may be packaged into a secondary container to provide for multiple uses.
The following examples, which include preferred embodiments, will serve to illustrate the practice of this invention, it being understood that the particulars shown are by way of example and for purpose of illustrative discussion of preferred embodiments of the invention and in no way limit the scope of the invention.
EXAMPLES: Example 1
Powder hair dye is prepared with the composition in Table 1. Table 1

Ingredients %
p-phenylenediamine IS
Tartaric acid 4
Sodium lauryl sulphate 5
Sodium Carboxymethylcellulose 12
Magnesium sulphate 38
Centella extract 0.5
Aloe Vera Extract 0.5
Protein hydrolysate 0.5
Fragrance 0.5
Sodium Chlorite 7
Silica 14
L* a* b*
7.308 ! 0.419 -1.369
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One part the powder was mixed with 9 parts of water to obtain a uniform paste. It was applied to 3 tresses weighing 800-1100 mg of virgin white human hair and left to develop for 30 min; the tresses were washed and dried. It was observed that the tresses had developed a natural black colour. The colour intensity obtained on the tresses was measured with TECHKON Spectro Dense A802030 on the CIELAB L*a*b scale. The average readings were as listed in Table I. The readings so obtained were compared with tresses, similarly dyed using a conventional powder composition with 25 % p-phenylenediamine and 30% sodium perborate. The L*a*b values were measured in a similar manner. These are shown in Table 2.
Table 2

Name L* a* b*
Conventional Powder Hair Dye Natural Black 7.561 0.972 -2.405
It can be seen that there is no significant difference between the L*a*b values though the quantity of p-phenylenediamine and the oxidant is significantly reduced in the composition that is revealed in this invention.
Example 2
Powder hair dye is prepared with the composition in Table 3.
Table 3

Ingredients %
p-phenylenediamine 5.5
p-aminophenol 0.5
p-amino-o-cresol 6
Sodium lauryl sulphate 5
Sodium chlorite 10
Sodium Carboxymethylcellulose 12
Calcium sulphate 40
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Silica 20
Centella extract 0.5
Aloe Vera Extract 0.5
Polyquaternium 22 0.5
Fragrance 0.5
Citric acid 1
L a b
31.065 5.95 -0.196
Nine parts of water were added to one part of the powder and mixed to obtain a uniform paste. It was applied to 3 tresses of virgin white human hair and left to develop for 30 min: the tresses were washed and dried. It was observed that the tresses had developed a reddish violet colour and had good shine and gloss. The colour intensity obtained on the tresses was measured with TECHKON Spectro Dense A802030 on the CIELAB L*a*b scale. The average readings were as listed in Table 3.
Example 3
Powder hair dye is prepared with the composition in Table 4 Table 4

Ingredients %
p-phenylenediamine 1.0
p-amino-o-cresol 4.0
a- Naphthol 1.0
Nitro PPD 2.0
Sodium lauryl sulphate 5.0
Sodium chlorite 10.0
Sodium Carboxymethylcellulose 10.0
Magnesium sulphate 48.5
Hibiscus extract 0.5
Aloe Vera Extract 0.5
Mineral oil 2.0
Fragrance 0.5
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Silica 20.0
Tartaric acid 0.5
L* a* b*
29.339 20.313 13.804
Nine parts of water were added to one part of the powder and mixed to obtain a uniform paste. It was applied to 3 tresses of virgin white human hair and left to develop for 30 min; the tresses were washed and dried. It was observed that the tresses had developed a red colour and had good shine and gloss. The colour intensity obtained on the tresses was measured with TECHKON Spectro Dense A802030 on the CIELAB L*a*b scale. The average readings were as listed in Table 4.
Example 4
Powder hair dye is prepared with the composition in Table 5. Table 5

Ingredients %
p-phenylenediamine 5
p-aminophenol 4
m-aminophenol 5
p-amino-o-cresol 3
Sodium lauryl sulphate 5
Sodium chlorite 15
Sodium Carboxymethylcellulose 10
Calcium sulphate 32
Emblica officinalis extract 0.5
Aloe Vera Extract 0.5
Polyquaternium 22 0.5
Fragrance 0.5
Silica 20
Tartaric acid 1
L* a* b*
15.14 2.4 1.1
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Nine parts of water were added to one part of the powder and mixed to obtain a uniform paste. It was applied to 3 tresses of virgin white human hair and left to develop for 30 min; the tresses were washed and dried. It was observed that the tresses had developed a brown colour and had good shine and gloss. The colour intensity obtained on the tresses was measured with TECHKON Spectro Dense A802030 on the CIELAB L*a*b scale. The average readings were as listed in Table 5.
Advantages of the invention:
There are many advantages to the compositions and process of the invention. The actual coloring of the hair is performed at a pH which is at, or close to, neutrality; there is no issue of unwanted odours, since there is no use of ammonia or amines in the composition: chlorite salts do not bleach or cause other oxidative damage to human hair; there is no issue of mixing ratios of the colourant and the oxidant, as the primary dye intermediates, couplers and the oxidant are preniixed into a single stable formulation and the wear quality of the colors produced in the dyed hair is appreciably enhanced.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative examples and that the present invention may be embodied in other specific forms without departing from the essential attributes thereof, and it is therefore desired that the present embodiments and examples be considered in all respects as illustrative and not restrictive, reference being made to the appended claims, rather than to the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
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We Claim,
1. A stable oxidative powder hair dye composition comprising from about 0.5% to 25% by weight of an alkali or alkaline earth metal chlorite salt and silica together with an amount of oxidative primary intermediates and couplers, which will react to form a tinctorially effective amount of a hair dye.
2. The oxidative powder hair dye composition of claim 1. wherein the chlorite salt is sodium chlorite.
3. The oxidative powder hair dye composition of claim 2, wherein the amount of sodium chlorite is 5% to 25% by weight.
4. The oxidative powder hair dye composition of claim 3, wherein the amount of sodium chlorite is 5% to 15% by weight.
5. The oxidative powder hair dye composition of claims 1 to 4 further comprising at least one of the following: surface active agents in an amount up to about 15% by weight, thickening agents in an amount up to about 20% by weight, antioxidant up to about 1% by weight, pH modifying agents in an amount 15% by weight, silica in an amount up to 25% by weight; and the remaining weight being made up by an inorganic salt which is essentially inert to the other ingredients of the composition.
6. The oxidative powder hair dye composition of any of the preceding claim further comprises at least one of the following: up to 10 % direct dyes, up to 1% fragrance, up to 5% hair conditioning agents, up to 2% hair nourishing agents.
7. The oxidative powder hair dye composition of any of the preceding claim
comprises: from about 0.5% to 25% by weight of an alkali or alkaline earth metal
chlorite salt together with 1 to 30 % w/w primary intermediates and couplers; 1
to 15% weight of a surface active agent; 5 to 20% thickening agent; 0.01 to 1%
antioxidant; 0.01 to 15% pH modifying agent; up to 25% by weight silica; 0.01 to
5% hair conditioning agent; up to 2% hair nourishing agents; optionally 0.01 to
10% direct dyes and fragrance 0.01% to 1% by weight; and inorganic salts to
make the weight of the composition to hundred by weight.
8. A process of preparing the oxidative powder hair colour or dye composition of
claims 1 to 7, wherein said process comprises
a. drying of surfactant, thickener, silica, pH modifying material and inorganic salts to reduce the moisture levels to below 5%;
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b. mixing 0.5 to 25 % by weight of an alkali or alkaline earth metal
chlorite salt and up to 25% by weight silica in a ribbon blender for up
to 20 minutes at temperature below 40°C and keeping the mixture
aside;
c. adding up to 15% by weight powder surfactant, up to 20% by weight
thickening agent, up to 15 % by weight of pH modifying materials, up
to 1 % by weight of antioxidant and inorganic salt one by one into the
ribbon blender;
d. blending the mixture for up to 20 minutes at temperature below 40°C
and adding primary intermediates and couplers into said mixture;
e. blending the whole mixture with blend obtained in step b). in the
ribbon blender at temperature below 40°C for 30 to 60 minutes,
preferably 40-50 minutes to obtain powder hair colour composition.
9. A package containing the oxidative hair dye composition of claims 1 to 6 as a single product packed in a manner that protects the composition from moisture.
10. An oxidative hair dye composition of claims 1 to 6, wherein the primary intermediate is selected from the group consisting of ortho- and para-phenylenediamines; heterocyclic bases, and ortho- and para-aminophenols selected from the group consisting of o-aminophenol, 5-chloro-o-aminophenol, p-aminophenol, 2-methyl-p-aminophenol, 2,3-dimethyl-p-am inophenol, 2,6-dimethyl-p-aminophenoi, 3-methoxy-p-aminophenol, 2-chloro-p-aminophenol, N-methyl-p-aminophenol and 3-(methylthio)-p-aminophenol.
11. The package of claim 9, wherein the contents need to be mixed with water prior to application to hair, where the mixing ratio of the said composition to water is 1:5 to 1:12 by weight.