MXPA02003915A - Hair coloring compositions and methods. - Google Patents

Abstract

A hair bleaching and coloring composition comprising: (a) an oxidising agent; and (b) an oxidative and or non oxidative hair coloring agent; and (c) ammonium carbonate and or carbamate; wherein the pH of the composition lies in the range of from about 7 to about 9. The products can provide excellent hair coloring, a wide variety of shades, good grey coverage, reduced skin irritation and hair damage and reduced odor.

Description

COMPOSITIONS AND METHODS TO DYE HAIR TECHNICAL FIELD This invention relates to compositions and processes for dyeing hair, and more especially to dyeing hair compositions that provide both discoloration and dyeing of hair from a simple composition.

BACKGROUND OF THE INVENTION The desire to alter the color of human hair is not an aspect of modern times. Since the days of the Roman Empire, the color of human hair has been routinely altered to adapt to changes and style of "fashion." However, the achievement of precise initial colors that are retained by the hair during a desirable period has been a more elusive objective.The difficulties in the development of compositions for dyeing the hair which can provide more lasting precise colors are partly due to the inherent structure of the hair itself and partly due to the necessary conditions of the effective processes for coloring of hair, the difficulties common with compositions Conventional dyes for hair dyeing include color fading, wash fading, uneven dye absorption, hair damage and brittleness, skin irritation, odor and skin staining. Over the years significant efforts have been directed towards the elimination of many of the problems associated with the dyeing of human hair. Various proposals have been developed for hair dyeing, these include direct-acting dyes, natural dyes, metallic dyes and oxidative dyes. To color human or animal hair using oxidative dye technology, hair is generally treated with a mixture of oxidative agents to dye hair and an oxidizing agent. Hydrogen peroxide is the most commonly used oxidizing agent. Oxidative agents for hair dyeing and peroxygen oxidizing agents can be used to supply a variety of hair colors. However, a substantial improvement is necessary to provide increased flexibility in the variety of hair shades that can be obtained. In general, oxidative compositions have been used for dyeing ii. i.jm.is .. hair to color / darken hair, and bleaching compositions have been used to discolor / lighten hair. In order to increase the variety of colors beyond that which is available for bleaching and staining compositions separately, in the past it has been necessary to carry out a two-step process whereby the hair undergoes a discoloration step with a decolorizing composition containing persulfate, followed by a coloring step with a separate coloring composition. However, a two-step process can be inconvenient and time-consuming. It has not been possible to include persulfate in a composition together with oxidative coloring agents due to the incompatibility of the persulfate and the oxidative dye components. It is also possible to provide some limited decolorization / clearance from a coloring composition by using ammonia or peroxide. However, this composition can be affected by undesirable odor and insufficient bleaching capacity. Therefore, it would be convenient to provide both a decolorization and an efficient dyeing from a composition implemented. -.a-at-t. U? T ^? ^? * Typically, hair dyeing compositions containing oxidative agents for dyeing hair are formulated at a high pH (between about pH 9 and pH 12) and usually contain, in addition to the agents oxidants for dyeing the hair and an inorganic peroxygen oxidizing agent, peroxide activating agents and an additional cosmetic variety, coloring agent and stabilizing agents for the peroxygen oxidizing agent. It is also known that the improved oxidation of the oxidative agent to dye the hair can be achieved via the use of a hair bulking agent (HSA). These HSA intensify the oxidation and coloring process by imparting volume to the hair fibers to aid both the diffusion of the peroxygen oxidizing agent and the oxidative agents to dye the hair in the hair as well as the oxidation of the dye and hair coloration, more thoroughly, with faster rating. A common HAS is an aqueous (alkaline) solution containing a source of ammonia, such as, for example, ammonium hydroxide. However, ammonia can cause skin irritation and also has an undesirable odor and can cause tear-jerking effects.

In this way, it would be convenient to develop a bleaching composition and to dye the hair having desirable odor characteristics comprising oxidative agents for dyeing the hair that provide improved benefits for dyeing the hair and variety in the nuances of the hair without the need for an HSA. . There is also a need for a composition for dyeing and bleaching hair that reduces hair damage and reduces irritation to the wearer's skin. There is also a need for a composition for dyeing and bleaching hair that provides effective coverage of gray hair. It is known that compounds that produce ions HC03 ~ in solution in water are used in compositions for dyeing hair. EP-A-435,012 discloses several of the compounds that produce ions of HC03", namely Na2CO3, NaHCO3, K2CO3, KHC03, (NH) 2C03, NH4HC03, CaCO3 and Ca (HC03") 2. It has now been found that a combination of oxidizing agents with one or more oxidizing or non-oxidative agents for dyeing hair and ammonium carbonate and / or ammonium carbamate at a pH of between about 7 and 9, in the Hair dyeing compositions can provide excellent discoloration and dyeing for the initial hair in combination with improved flexibility and variety of shades, reduced odor, reduced skin irritation and hair damage, and effective coverage of the gray hair without the need for amounts Substances of buffering agents, pH modifiers or agents for bulking hair. All percentages are presented by weight of the final compositions in the form intended for use unless otherwise specified.

BRIEF DESCRIPTION OF THE INVENTION The object of the present invention is a composition for bleaching and dyeing hair, suitable for the treatment of human or animal hair. In accordance with one aspect of the present invention, there is provided a composition for bleaching and dyeing hair comprising: (a) an oxidizing agent; (b) an oxidative and / or non-oxidative agent for dyeing the hair; - "- • -" --- • - * * - - - - - - - - - - - - - - - - - - - - - - - - - - - -. wherein the pH of the composition is between about 7 and 9. It should be understood that the percentages by weight of the components of the composition herein are expressed in terms of the total composition, and include the composition in the form of the intended use In accordance with a further aspect of the present invention, there is provided a method for bleaching and dying the hair wherein a hair bleaching and dyeing composition is applied directly to the hair and wherein the hair bleaching and dyeing composition comprises: (a) an oxidizing agent, (b) an oxidative and / or non-oxidative agent for dyeing hair, (c) ammonium carbonate and / or ammonium carbamate, wherein the pH of the composition is between about 7 and 9. In accordance with yet another aspect of the present invention, there is provided a case comprising a first component and a second component, the first component comprises an oxidizing agent, and the second component comprises an oxidative and / or non-oxidative agent for dyeing hair in combination with ammonium carbonate and / or ammonium carbamate.

DETAILED DESCRIPTION OF THE INVENTION In the sense in which the term "hair" is used herein it may be "living" ie, in a living body or it may be "non-living" ie in a wig, piece of hair or other extension of non-living fibers, such as for example those used in textiles and fabrics. In mammals, human hair is preferably chosen. However, wool, hair and other fibers containing melanin are suitable substrates for the compositions according to the present invention. In the sense in which the term "hair bleaching and dyeing composition" is used herein, it is used in the broad sense in which it is intended to encompass compositions containing the combinations herein of an oxidizing agent, an oxidative agent and / or non-oxidative dye and ammonium carbonate and / or carbamate^? lik. ^^ att ^^^^ i., ammonium, wherein the composition has a pH of between about 7 and 9. In addition, it is also intended to include complex compositions containing other components that may or may not be active ingredients. In this way, the term "hair bleaching and dyeing composition" is intended to apply to compositions containing, in addition to a mixture of active oxidizing agents, coloring agents and ammonium carbonate and / or ammonium carbamate, such as example, oxidation aids, sequestrants, stabilizers, thickeners, buffers, carriers, surfactants, solvents, antioxidants, polymers and conditioners.

Oxidizing agents The compositions of the invention comprise as an essential characteristic at least one oxidizing agent, which may be an inorganic or organic oxidizing agent. The oxidizing agent is preferably present at a level between about 0.01% and 10%, preferably between about 0.01% and 6%, more preferably between about 1% and 4% by weight of the composition.

,. J ".- * - ^! ^ -. T.JÉÍ» É - ^^ Inorganic Oxidizing Agents A preferred oxidizing agent for use herein is an inorganic peroxygen oxidizing agent. The inorganic peroxygen oxidizing agent should be safe and effective for use in the compositions herein. Preferably, the inorganic peroxygen oxidizing agents suitable for use herein will be soluble in the compositions according to the present invention when they are in liquid form or in the form intended for use. Preferably, the inorganic peroxygen oxidizing agents suitable for use herein will be water soluble. Water-soluble oxidizing agents, as defined herein, mean agents having a solubility ranging from about 10Og to 10000ml of deionized water at 25 ° C ("Chemistry" CE Mortimer, Fifth ed. P277) . The inorganic peroxygen oxidizing agents useful herein are, in general, inorganic peroxygen materials capable of providing peroxide in an aqueous solution. Inorganic peroxygen oxidizing agents are well known in the art and include hydrogen peroxide, inorganic alkali metal peroxides such as for example sodium periodate, sodium perbromate and sodium peroxide, and inorganic oxidation compounds with perhydrated salt, such as for example alkali metal salts of perborates, percarbonates, perfosphates, persalicates, persulfates and the like. These inorganic perhydrate salts can be incorporated as monohydrates, tetrahydrates, etc. If desired, mixtures of two or more of these inorganic peroxygen oxidizing agents can be used. While the alkali metal bromates and iodates are suitable for use herein, bromates are preferred. Hydrogen peroxide is more preferred for use in the compositions according to the present invention. It has been found that by using the compositions of the present invention, it is possible to provide effective discoloration and dyeing of the hair without the need to use ammonia, whereby there is no negative ammonia-related odor or skin irritation associated with these compositions. In preferred compositions, according to the present invention, the inorganic peroxygen oxidizing agent is present at a level of between about 0.01% to less than about 6%, preferably between about 0.01% and 4%, more preferably between about 1% and 4%, more preferably between about 2% and 3% by weight of the composition.

Preformed Organic Peroxyacid The compositions, according to the present invention, may comprise in place of the inorganic peroxygen oxidizing agent (s) or in addition thereto, one or more preformed organic peroxyacid oxidizing agents. Organic peroxyacid oxidizing agents suitable for use in the dyeing compositions, according to the present invention, have the general formula: RC (O) OOH wherein R is selected from straight or branched chain alkyl, aryl or alkaryl groups, substituted or unsubstituted, saturated or unsaturated, with 1 to 14 carbon atoms. A class of organic peroxyacid compounds suitable for use herein are r -? t, -jf ... j¡.JfHfÍ *? l¿l -, ** j? * ~ i. , .. «. "_»,., »..., ^,« .. ^ i. ^^^^ Ai ^. i ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ -OOH wherein R 1 is a saturated or unsaturated alkyl or alkaryl group, or an aryl group, having 1 to 14 carbon atoms, R 2 is a saturated or unsaturated alkyl or alkaryl group, or an aryl group, having 1 or to 14 carbon atoms, and R 5 is H or a saturated or unsaturated alkyl or alkaryl group, or an aryl group, having 1 to 10 carbon atoms. Amide-substituted organic peroxyacid compounds of this type are described in EP-A-0, 170, 386. Other suitable organic peroxyacid oxidizing agents include peracetic acid, pernanoic, nonilamidoperoxycaproic (NAPCA), perbenzoic, m-chloroperbenzoic acid, di-peroxyisophthalic, mono-peroxyphthalic, peroxylauric, hexansulfonyl peroxy propionic, N, N-ft alloyloxy peroxycaproic, monoper succinic, nonanoyloxybenzoic, dodecanedioylmonoperoxybenzoic, peroxydapic nonyl amide, diacyl and tetraacyl peroxides, especially diperoxydecandioic acid, diperoxytedecadetic acid ...., -,. ^. j-tit-ai_m and diperoxyhexadecandioic acid and derivatives thereof. Also suitable for use in the present mono and diperazelaic acid, mono and diperbrasyl acid and N-phthaloylaminoperoxycaproic acid and derivatives thereof. The preformed organic peroxyacid oxidizing agents should be safe and effective for use in the compositions herein. Preferably, the preformed organic peroxyacid oxidizing agents suitable for use herein will be soluble in the compositions according to the present invention when they are in liquid form and in the form intended for use. Preferably, organic peroxyacid oxidizing agents suitable for use herein will be soluble in water. Water-soluble preformed organic peroxyacid oxidizing agents, as defined herein, means those agents having a solubility to the extent of about 10Og in 100OOm of deionized water at 25 ° C ("CE Mortimer CE" 5a) Ed. P277). Preferred peroxyacid materials suitable for use herein are tA? i¡i? .. ~ e? LyMi * aié *? A? T select from peracetic and pernanoic acids and mixtures thereof. The preformed organic peroxyacid oxidizing agent, when present, is preferably present at a level of between about 0.01% and 8%, more preferably between about 0.1% and 6%, most preferably between about 0.2% and 4%, and especially between about 0.3% and 3% by weight of the composition for dyeing the hair. When both an inorganic peroxygen oxidizing agent and a preformed organic peroxyacid are present in the compositions herein, the weight ratio of the inorganic peroxygen oxidizing agent to the preformed organic peroxyacid is preferably in the range of between about 0.0125: 1 and 500. : 1, more preferably between about 0.0125: 1 and 50: 1. In addition to the inorganic peroxygen oxidizing agents and the preformed organic peroxyacid oxidizing agents suitable for use herein, the compositions according to the present invention may optionally comprise additional organic peroxides such as example, urea peroxide, melamine peroxide and mixtures thereof. The level of organic peroxide, when present, is between about 0.01% and 3%, preferably between about 0.01% and 2%, more preferably between about 0.1% and 1.5% and most preferably between about 0.2. % and 1% by weight of the composition.

Hair Coloring Agents Hair dyeing compositions of the present invention include as an essential feature an oxidative or non-oxidative agent for dyeing hair. These hair dyeing agents are used in combination with the oxidizing agent and the ammonium carbonate and / or ammonium carbamate to prepare compositions for permanently dyeing the hair, demi-permanent, semi-permanent or temporary. The compositions for permanently dyeing the hair, in the sense defined herein, are compositions that once applied to the hair are practically resistant to washing. Demi-permanent hair dyeing compositions, in the sense defined in the ... ^ .. ^ a-. present, are compositions that are substantially removed from the hair after up to 24 washes. Semi-permanent hair dyeing compositions, as defined herein, are compositions that once applied to the hair are substantially removed from the hair after up to 10 washes. The compositions dyeing the hair temporarily, in the sense in which it is defined herein, are compositions that once applied to the hair are substantially removed from the hair after up to 2 washes. These different types of compositions for dyeing the hair can be prepared via the specific combination of the oxidant and / or dyes at different levels and proportions. Washing, in the sense in which it is defined in the present, is the process by which hair color is removed from the hair over time during a normal hair-cleaning regime. Firmness to washing, in the sense defined herein, means the resistance of hair dyed to washing.

Oxidative agents for dyeing hair A hair dyeing agent preferred herein is an oxidative agent for dyeing hair. The concentration of each oxidative agent for dyeing the hair in the dyeing compositions according to the present invention is preferably between about 0.001% and 3% by weight, more preferably between about 0.01% and 2% by weight. The total combined level of the oxidative agents for dyeing the hair in the compositions according to the present invention is between about 0.001% and 5%, preferably between about 0.01% and 4%, most preferably between about 0.1% and 3%, most preferably between about 0.1% and 1% by weight. Any oxidative agent for dyeing the hair can be used in the compositions according to the present invention. Typically, although without pretending to be limited due to that, the oxidative agents for dyeing hair, essentially consist of at least two components, which are collectively referred to as dyeing intermediates (or precursors). Intermediates for dye formation can react in the presence of a suitable oxidant to form a dye molecule.

Intermediates for dye formation used in oxidative dyes for hair include: aromatic diammas, aminophenols, various heterocycles, phenols, naphthols and their various derivatives. These intermediaries for dye formation can be broadly classified as primary intermediates and secondary intermediaries. Primary intermediates, which are also known as oxidative dye precursors, are chemical compounds that become active at the time of oxidation and can then react with each other and / or with couplers to form dye complexes. Secondary intermediates, also known as color modifiers or couplers, are generally colorless molecules that can form colors in the presence of activated primary precursors / intermediates, and are used with other intermediates to generate specific color effects or to stabilize the color. Suitable primary intermediates for use in the compositions and processes herein include: aromatic diamines, polyhydric phenols, amino phenols and derivatives of these aromatic compounds (for example, N-substituted derivatives of the amines, and ethers of the phenols). These primary intermediates in general are colorless molecules before oxidation. While not wishing to be bound by any theory, it is proposed here that the process by which color is generated from these primary intermediates and secondary couplers in general includes a stepwise sequence whereby the primary intermediary is it can be made active (by oxidation), and then imposed with a coupler to provide a conjugated, dimeric dye species, which in turn can be imposed with another "activated" primary intermediate to produce a trimeric conjugated dye molecule.

Oxidative dye precursors In general terms, the primary intermediates of oxidative dye include those monomeric materials which, in oxidation, form oligomers or polymers having conjugated electron systems extended in their molecular structure. Because of the new electronic structure, the resulting oligomers and polymers exhibit a change in their electronic spectra for the visible range and appear colored.

For example, oxidative primary intermediates capable of forming dye polymers include materials such as for example aniline, which has an individual functional group and which, in oxidation, forms a series of conjugated imines and quinoid dimers, trimers, etc. They vary in color from green to black. Compounds such as, for example, p-phenylenediamine, having two functional groups, are susceptible to oxidative polymerization to provide higher molecular weight coloring materials having extended conjugated electron systems. The oxidative dyes known in the art can be used in the compositions according to the present invention. A representative list of primary intermediates and secondary couplers suitable for use herein is found in Sagarin, "Cosmetic Science and Technology," Interscience, Special Ed. Vol. 2 pages 308-310. It should be understood that the primary intermediaries detailed below they are provided by way of example only and are not intended to limit the compositions and processes herein. Typical aromatic diamines, polyhydric phenols, amino phenols and derivatives thereof, described above as primary intermediates may also have substituents I l t l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l additional in the aromatic ring, for example halogen, aldehyde, carboxylic acid, nitro, sulfonic acid and substituted and unsubstituted hydrocarbon groups, as well as further substituents on the amino nitrogen and the phenolic oxygen atom, for example alkyl and aryl groups replaced and not replaced. Examples of suitable aromatic diamines, amino phenols, polyhydric phenols and derivatives thereof, respectively, are compounds having the following general formulas (I), (II) and I I I) «I ... iAa ariisi-Ms. *. r 'rfi ii-ÉÍ .f? wherein Y is hydrogen, halogen, (for example fluorine, chlorine, bromine or iodine), nitro, amino, hydroxyl, O II -CH -COOM or -S03M (wherein M is hydrogen or an alkali metal or alkaline earth metal, ammonium, or substituted ammonium wherein one or more hydrogen atoms in the ammonium ion is replaced with an alkyl or hydroxyalkyl radical of 1 to 3 carbon atoms carbon), wherein Ri, R2, R3 and R4 are the same or different from each other and are selected from the group consisting of hydrogen, alkyl or alkenyl of Ci to C4 and aryl, alkaryl or aralkyl of C? to C9, and R5 is unsubstituted or substituted C2 to C4 hydrogen, alkyl or alkenyl wherein the substituents are selected from those designated as Y, above, or unsubstituted aryl, alkaryl or aralkyl or substituted from Ce to C9 wherein the substituents are selected from those defined as Y, above. Because the precursors of formula (I) are amines, they can be used herein in the form of peroxide-compatible salts, as noted, wherein X represents peroxide-compatible anions of the type herein detailed above. . It should be understood that the general formula of the indicated salt encompasses those salts having mono-, di-, and t-negative anions. Specific examples of the compounds of the formula (I) are: o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2-chloro-p-phenylenediamine, 2-iodo-p-phenylenediamine, 4-nitro-o-phenylenediamine, 2 -nitro-p-phenylenediamine, 1, 3, 5-triaminobenzene, 2-hydroxy-p-phenylenediamine, 2,4-diaminobenzoic acid, sodium 2,4-diaminobenzoate, calcium di-2, 4-diaminobenzoate, 2,4-diaminobenzoate ammonium, trimethylammonium 2, 4-, diaminobenzoate, tri- (2-hydroxyethyl) ammonium 2,4-diaminobenzoate, 2,4-diaminobenzaldehyde carbonate, 2, 4-diaminobenzenesulfonic acid or, 2, 4-d? aminobenzenesulfonate potassium, N, N-diisopropyl-p-, phenylenediamine bicarbonate, N, N-dimethyl-p-phenylenediamine, N-ethyl-N1 - (2 -propenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, N-phenyl-N-benzyl-p-phenylenediamine, N-ethyl-N '- (3-ethylphenyl) -p-phenylenediamine, 2,4-toluenediamine , 2-ethyl-p-phenylenediamine, 2- (2-bromoet il) -p-phenylenediamine, laurate of 2-phenyl-1-p-phenylenediamine, 4- (2,5-diaminophen-1) benzaldehyde, 2-benzyl acetate -p-feni lendiamma, 2 - (4-n-t-robenc'1) -p-phenylenediamine, 2- (4-methylphenyl) -p-phenylenediamine, 2- (2,5-diaminophenyl) -5-methyl-ylbenzoic acid, methoxyparaphenylenediamine, dimethyl-p-phenylenediamine, 2,5-dimethylparaphenylenediamine, 2-methyl-5-methoxy-para-phenylenediamine, 2,6-methyl-5- methoxy-para-phenylenediamine, 3-methyl-4-amino-N, N-diethylaniline, N, N-bis (β-hydroxyethyl) -para-phenylenediamine, 3-met il-4-amino-N, N-bis (ß-hydroxyethyl) aniline, 3-chloro-4-amino-N, N-bis (ß-hydroxyethyl) aniline, 4-amino-N-ethyl-N- (carbamethyl) aniline, 3-met il-4-amino -N-et il-N- (carbamethyl) aniline, 4-amino-N-yl- (ß-piperidono-ethyl) aniline, 3-met i 1-4 -amino-N-ethyl- (ß-piperidono- ethyl) aniline, 4-amino-N-ethyl-N- (β-morpholinoethyl) -aniline, 3-met i 1-4 -amino-N-et i 1-N- (β-morpholinoethyl) -aniline, 4 - amino-N-yl-N- (β-acetylaminoet yl) aniline, 4-amino-N- (β-methoxyethyl) aniline, 3-methyl-4-amino-N-ethyl-N- (β-acetylaminoethyl) ) aniline, 4-amino-N-yl-N- (ß-mes and laminoethyl) aniline, 3-met il-4-amino-N-ethyl-N- (ß-me silaminoethyl) aniline, 4-amino- N-ethyl-N- (β-sulfoethyl) aniline, 3-methylamino-N-yl-N- (β-sulfoethyl) aniline, N- (4-aminophenyl) morpholine, N- (4-aminophenyl) ) piperidine, 2,3-dimethyl-p-phenylenediamine, isopropyl-p-phenylenediamine, its N, N-bis- (2-hydroxyethyl) -p-phenylenediamine phosphate.

The compounds having the general structure (II) are as follows: wherein X and Y are the same as in formula (I), Ri and R2 may be the same or different from each other and are the same as in formula (I), R5 is the same as in formula (I) and R6 is hydrogen or substituted or unsubstituted alkyl or alkenyl Ci to C4 wherein the substituents are selected from those defined as Y in the formula (I). Specific examples of the compounds of the formula (II) are: o-aminophenol, m-aminophenol, p-aminophenol, 2-iodo-p-aminophenol, 2-nitro-p-aminophenol, 3,4-dihydroxyaniline, 3, 4 -diaminophenol, chloroacetate, 2-hydroxy-aminobenzoic acid, 2-hydroxy-4-aminobenzaldehyde, 3-amino-4-hydroxy acid ti-mirrtT tftt? i¡i ^ - * - ^ »» ^ - »^^ * benzenesulfonic acid, N, N-diisopropyl-p-aminophenol, N-methyl-N- (1-propenyl) -p-aminophenol, N-phenyl-N-benzyl-p-aminophenol sulfate, N-methyl-N- (3-ethylphenyl) -p-aminophenol, 2-nitro-5-et i 1-p-aminophenol, 2-nitro-5- (2-bromoet il) -p-aminophenol, (2-hydroxy-5-aminophenyl) acetaldehyde, 2-met i 1-p-aminophenol, (2-hydroxy-5-aminophenyl) acetic acid, 3- (2-hydroxy) -5- aminophenyl) -1-propene, 3- (2-hydroxy-5-aminophenyl) -2-chloro-1-propene, 2-phenyl-p-aminophenol palmitate, 2- (4-nitrophenyl) -p- aminophenol, 2-benzyl-p-aminophenol, 2- (4-chlorobenzyl-p-aminophenol, 2- (4-methylphenyl) -p-aminophenol, 2- (2-amino-4-methylphenyl) -p-aminophenol perchlorate , p-methoxyaniline, 2-bromoethyl-4-aminophenyl ether phosphate, 2-nitroethyl-4-aminophenyl ether bromide, 2-aminoethyl-4-aminophenylether, 2-hydroxyethyl-4-aminophenyl ether, (4-aminophenoxy) -acetaldehyde, (4-aminophenoxy) acetic acid, (4-aminophenoxy) methanesulfonic acid, i 1-propeni 1-4-aminophenylether, (2-chloro) -l-propenyl-4-aminophenyl ether, (2-nitro) -l-propenyl-aminophenylether, (2-amino) -propenyl-4-aminophenylether, (2-hydroxy) -l-propenyl-4-aminophenyl ether, N-methyl-p-aminophenol, 3-methyl-4-aminophenol, 2-chloro-4-aminophenol, 3-chloro-4-aminophenol, 2,6 -dimet i 1-4 - aminophenol, 3, 5-dimet i 1- -aminophenol, 2, 3-dimet i 1-4 - aminophenol, 2,5-dimethyl-4-aminophenol, 2-hydroxymethyl-aminophenol, 3-hydroxymethyl-4-aminophenol, 2,6-dichloro-4-aminophenol, 2,6-dibromo-4-aminophenol and 2- romo-4-aminophenol.

Specific examples of the compounds of the formula (III) are: o-hydroxy phenol (catechol), m-hydroxyphenol (resorcinol), p-hydroxyphenol (hydroquinone), 4-methoxyphenol, 2-methoxyphenol, 4- (2-chloroethoxy) phenol, 4- (2-propenoxy) phenol, 4- (3-chloro-2-propenoxy) phenol, 2-chloro-4-hydroxyphenol (2-chlorohydroquinhano), 2-nitro-4-hydroxy phenol (2-nitrohydroquinone) , 2-amino-4-hydroxyphenol, 1,2,3-trihydroxybenzene (pyrogallol), 2,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzoic acid, 2,4-dihydroxybenzenesulfonic acid, 3-ethyl-4-hydroxyphenol, 3- (2-Nitroethyl) -4-hydroxy phenol, 3- (2-propeni 1) -4-hydroxyphenol, 3- (3-chloro-2-propeni 1) -4-hydroxyphenol, 2-phenyl-4-hydroxy phenol, 2- (4-chlorophenyl) -4-hydroxyphenol, 2-benzyl-4-hydroxyphenol, 2- (2-nitrophenyl) -4-hydroxyphenol, 2- (2-methylphenyl) -4-hydroxyphenol, 2- (2-methyl) -4-chlorophenyl) -4- É ^ ^ ja ^ - ^^ A-i i- ^ i-t - = * ^ * '- *' * ^^. .'- a - = & Matetet. hydroxyphenol, 3-methoxy-4-hydroxy-benzaldehyde, 2-methoxy-4- (1-propenyl) phenol, 4-hydroxy-3-methoxycinnamic acid, 2,5-d-methoxyanilin, 2-methylresorcinol, alpha-naphthol and salts of them. Secondary coupling compounds which are suitable for inclusion in the coloring compositions and processes of the present invention described above include certain aromatic amines and phenols and derivatives thereof which do not individually produce color, but which modify the color, hue or intensity of the colors developed by the primary intermediaries of oxidized dye. Certain aromatic amines and phenolic compounds, and derivatives thereof, including some aromatic diamines and polyhydric phenols of the types described by the formulas (I), (a), (Ib), (II) and (III) above, although they are well known in the art are not suitable primary intermediates, without suitable as couplers herein. Polyhydric alcohols are also suitable for use as couplers herein. The aromatic amines and phenols and derivatives described above as couplers may also have additional substituents on the aromatic ring, for example, halogen, aldehyde, carboxylic acid, nitro, sulfonyl and substituted and unsubstituted by hydrocarbon groups, as well as, further substituents in the amino nitrogen, or phenolic oxygen, for example, substituted and unsubstituted alkyl and aryl groups. Again, the peroxide-compatible salts thereof are suitable for use herein. Examples of aromatic amines, phenols and derivatives thereof are compounds of the following general formulas (IV) and (V): OR wherein Z is hydrogen, Ci and C3 alkyl, halogen (e.g., fluorine, chlorine, bromine or iodine) nitro, O II -CH -COOM or -S03M, (wherein M is hydrogen or an alkali metal or alkaline earth metal, ammonium, or substituted ammonium wherein one or more hydrogen atoms in the ammonium ion is replaced with an alkyl or hydroxyalkyl radical of 1 to 3 atoms carbon), wherein Ri and R2 are the same or different and are selected from the group consisting of hydrogen, alkyl or alkenyl of Ci to C4 and aryl, alkaryl or aralkyl of C6 to C9, and R7 is hydrogen, alkyl or alkenyl Substituting or substituted Ci to C4 wherein the substituents are selected from those designated as Z above, or unsubstituted aryl, alkaryl or aralkyl or substituted from C to C9 wherein the substituents are selected from those defined as Z above - and where X is as defined in formula (I). Specific examples of the compounds of the formula (IV) are: aniline, p-chloroaniline, p-fluoroaniline, p-nit roaniline, p-aminobenzaldehyde, p-aminobenzoic acid, sodium-p-aminobenzoate, lithium-p-aminobenzoate, calcium -di-p-aminobenzoate, ammonium-p-aminobenzoate, trimethylammonium-p-aminobenzoate, tri (2-hydroxyethyl-1) -p-aminobenzoate, p-aminobenzenesulfonic acid, p-aminobenzenesulfonate potassium, N-met ilamline, N-propyl 1-N-phenylane 1 ina, N-met lN-2- Jj * ¡- * jfa-ifa * «< rt m -rifjflm, ,,,. ,, t "^ M * > t>, M '* AJ * Mjli" ^ aa g g¡s ^; propeni lanilin, N-benzylaniline, N- (2-ethyl phenyl) aniline, 4-methylaniline, 4- (2-bromoethyl) aniline, 2- (2-nitroethyl) aniline, (4-aminophenyl) acetaldehyde, acid (4- aminophenyl) acetic acid, 4- (2-propenyl) aniline acetate, 4- (3-bromo-2-propenyl) aniline, 4-phenylalanine hydrochloride, 4- (3-chlorophenyl) aniline, 4-benzylaniline, 4- ( 4- iodobenzyl) aniline, 4- (3-ethylphenyl) aniline, 4- (2-chloro-4-ethyl phenyl) aniline. wherein Z and R7 are defined as in formula (IV) and Re is hydrogen or substituted or unsubstituted alkyl or alkenyl "from Ci to C4 wherein substituents are selected from those defined as Z in formula (IV). specific to the compounds of the formula (V) are: phenol, p-chlorophenol, p-nitrophenol, p-hydroxybenzaldehyde, p-hydroxybenzoic acid, p-hydroxybenzenesulfonic acid, and the phenyl ether, 2-chloroethyl phenyl ether, 2-nitroethyl phenyl ether, phenoxyacetaldehyde, phenoxyacetic acid, 3-phenoxy-1-propene, 3-phenoxy-2-nitro-1-propene, 3-phenoxy-2 bromo-1-propene, 4-propyl-l-phenol, 4- (3-bromopropyl) phenol, 2 - (2-n-t-yl-yl) -phenol, (4-hydroxyphenyl) -acetaldehyde, (4-hydroxyphenyl) -acetic acid, 4- (2-propenyl) phenol, 4-phenylphenol, 4-benzyl phenol, 4 - (3-f luoro-2-propenyl) phenol, 4 - (4-chlorobenzyl) phenol, 4- (3-ethylphenyl) phenol, - ( 2-chloro-3-ylphenyl) phenol, 2,5-xylenol, 2,5-diaminopyridine, 2-hydroxy-5-aminopyridine, 2-amino-3-hydroxy pyridine, tetraaminopyrimidine, 1,2,4-tr ihydroxybenzene , 1,2,4-trihydroxy-5- (C 1 -C 6 alkyl) benzene, 1,2,3-trihydroxybenzene, 4-aminoresorcinol, 1,2-dihydroxybenzene, 2-amino-1,4-dihydroxybenzene, 2 - amino-4-methoxy-phenol, 2,4-diaminophenol, 3-methoxy-l, 2-dihydroxy-benzene, 1-, 4-dihydroxy-2- (N, N-diethylamino) -benzene, 2, 5- diamino-4-methoxy-l-hydroxybenzene, 4,6-dimethoxy-3-amino-l-hydroxybenzene, 2,6-dimethyl-4 - [N- (p-hydroxyphenyl) amino] -1-hydroxybenzene, 1, 5-diamino-2-met il-4 - [N- (p-hydroxyphenyl) amino] benzene and salts thereof. Additional primary intermediates suitable for use herein include catechol species and in particular the "dopa" catechol species which includes dopa itself as well as homologs, analogs and DOPA derivatives.

Examples of suitable catechol species include cysteinyl dopa, alpha alkyl dopa having 1 to 4, preferably 1 to 2 carbon atoms in the alkyl group, epinephrine and dopa alkyl esters having 1 to 6, preferably 1 to 2 carbon atoms in the alkyl group. In general, suitable catechols are represented by the following formula (VI): wherein Ri, R2 and R3, which may be the same or different, are electron donor or acceptor substituents selected from H, lower alkyl (C? t C6), OH, OR, COOR, NHCOR, CN, COOH, halogen, N02 , CF3, S03H or NR4R5, with the proviso that only one of Ri, R2 or R3 may be CN, COOH, halogen, N02, CF3 or S03H: R and R5, which may be the same or different, are H, alkyl lower (C? -C6) or substituted lower alkyl (C? -C6) in which the substituent may be OH, OR, NHCOR6, NHCONH2, NHC02R6, NHCSNH2, CN, COOH, S03H, S02-NR6, S02R6 or C02R6; R6 is lower alkyl (C? -C6), hydroxyalkyl lower phenyl (C? -C6) linked to the nitrogen atom by a chain of U jtni-tf-. The alkylene, phenyl or phenyl substituted with the substituent defined as Ri, and R is C?-C6 alkyl or Ci-Cβ hydroxyalkyl. Oxidative agents for dyeing the hair of the formula are also included herein: wherein: Ri = substituted or unsubstituted benzene ring, tertiary butyl, etc .; R = substituted or unsubstituted benzene ring and the formula: wherein R = aminoalkyl, amidoalkyl, aminobenzene (substituted or unsubstituted), amidobenzene (substituted or unsubstituted), alkyl, substituted or unsubstituted benzene ring; Rx = substituted or unsubstituted benzene ring. The primary intermediates can be used here alone or in combination with other primary intermediates, and one or more can be used in combination with one or more couplers.

The choice of primary intermediaries and couplers Aiíi ^ d.m.ákS & ^? ^ will be determined by the color, shade and intensity of coloring desired. There are nineteen primary intermediates and preferred couplers that can be used herein, singly or in combination, to provide dyes having a variety of shades ranging from tan blond to black; these are: pyrogallol, resorcinol, p-toluenediamine, p-phenylenediamine, o-phenylenediamine, phenylenediamine, o-aminophenol, p-aminophenol, 4-amino-2-nitrophenol, nitro-p-phenylenediamine, N-phenyl-p- phenylenediamine, m-aminophenol, 2-amino-3-hydroxypyridine, 1-naphthol, N, N-bis (2-hydroxyethyl) p-phenylenediamine, 4-amino-2-hydroxytoluene, 1,5-dihydroxynaphthalene, 2-methyl resorcinol and 2,4-diaminoanisole. These can be used in the molecular form or in the form of salts compatible with peroxide, as detailed above. For example, low intensity colors such as for example nuances of natural blonde to light brown hair generally comprise between about 0.001% and 5%, preferably between about 0.1% and 2%, most preferably between about 0.2. % and 1% by weight of the coloring composition of the oxidative agents for total dyeing and can be achieved by the mtek ki &t * - "* '- •» ** - *. - combination of primary intermediates such as, for example, 1,4-diamino-benzene, 2,5-diamino toluene, 2,5-diamino-anisole, 4-aminophenol, 2,5-diamino-benzyl alcohol and 2 - (2 ', 5'-diamino) phenyl-ethanol with couplers such as, for example, resorcinol, 2-methyl resorcinol or 4-chloro resorcinol. , the combination of the above primary intermediates with couplers, such as, for example, derivatives of 5-amino-2-methyl phenol and 1,3-diamino-benzene such as, for example, 2, -diamino-anisole at levels between approximately 0. 5% and 1% of the total dyeing agents can lead to medium intensity red colors. High intensity colors such as, for example, shades of hair from blue to blue-violet can be produced by the combination of the above primary intermediates with couplers such as for example 1,3-diaminobenzene or its derivatives such as 2, 5-diamino-toluene at levels between about 1% and 6% by weight of the composition of total dyeing agents. The black hair colors can be obtained by combining the primary intermediates mentioned above with couplers such as, for example, 1,3-diaminobenzene or its derivatives. 1 + AAAÍML ???????????????????????????????????????????????? the hair or instead of it Non-oxidative and other optional dyes suitable for use in hair dyeing compositions and processes according to the present invention include both semi-permanent, temporary and other dyes. Non-oxidative dyes, in the sense defined herein, include so-called "direct-acting dyes", metallic dyes, metallic chelate dyes, reactive dyes in fibers and other synthetic and natural dyes. Various types of non-oxidative dyes are detailed in: "Chemical and Physical ß-ehavior of Human Hair" 3rd. Ed. By Clarence Robbins (pp250-259); "The Chemistry and Manufacture of Cosmetics". Volume IV. 2nd Ed. Maison G. De Navarre in chapter 45 of G.S. Kass (pp841-920); "Cosmetics: Science and Technology" 2nd. Ed., Vol. II Balsam Sagarin, Chapter 23 of F.E. Wall (pp 279-343); "The Science of Hair Care" ed. By C. Zvia, 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).

Direct-acting dyes that do not require an oxidative effect to develop color are also referred to as hair dyes and are well known in the art. They are usually applied to hair in a base matrix that includes surfactant material. Direct-acting dyes include nitro dyes such as, for example, the nitroamino benzene or nitroaminophenol derivatives; disperse dyes such as, for example, nitroaryl amines, aminoanthraquinones or azo dyes; anthraquinone dyes, naphthoquinone dyes; basic dyes such as, for example, Acridine Orange C.l. 46005. The nitrotintes are added to the dyeing compositions to intensify the color of the dye and add an appropriate aesthetic color to the dye mixture before application. Additional examples of direct-acting dyes include Arianor basic chestnut dyes 17, C.l. (color index) -no. 12.251; basic red 76, C.l. -12, 245; chestnut core 16, C.1.-12,250; basic yellow 57, C.l. -12, 719 and basic blue 99, C.l. -56, 059 and additional direct-acting dyes such as, for example, acid yellow 1, C.l. -10, 316 (D &C Yellow No. 7); acid yellow 9, C.l. -13, 015; basic violet C.l. -45, 170; scattered yellow 3, • ••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••• C.l. -11, 855; basic yellow 57, C.l. -12, 719; dispersed yellow 1, C.l. -10, 345; violet basic 1, C.l. -42, 535, basic violet 3, C.1.-42,555; greenish blue, C.l. -42090 (FD &C Blue No. 1); ro]? yellowish, C.l. -14700 (FD &C Network No. 4); yellow, C.l. 19140 (FD &C Yellow No. 5); yellowish orange, C.l. 15985 (FD &C Yellow No. 6); bluish green, C.l. 42053 (FD &C Green No. 3); yellowish red, C.l. 16035 (FD &C Network No. 40); bluish green, C.l. 61570 (D &C Green No. 3); orange, C.l. 45370 (D &C Orange No. 5); red, C.l. 15850 (D &C Network No. 6); bluish red, C.l. 15850 (D &C Network No. 7); reddish blue, C.l. 45380 (D &C Network No. 22); bluish red, C.l. 45410 (D &C Network No. 28); bluish red, C.l. 73360 (D &C Network No. 30); purple reddish, C.l. 17200 (D &C Network No. 33); turbid red blue, C.l. 15880 (D &C Network No. 34); light red yellow, C.l. 12085 (D &C Network No. 36); light orange, C.l. 15510 (D &C Orange No. 4); yellowish green, C.l. 47005 (D &C Yellow No. 10) bluish green, C.l. 59040 (D &C Green No. 8); violet blue, C.l. 60730 (Ext. D &C Violet No. 2); greenish yellow, C.l. 10316 (Ext. D &C Yellow No. 7). Reactive fiber dyes include Procion®, Drimarene®, Cibacron®, Levafix® and Remazol® of the dyes available from ICI, Sandoz, Ciba-Geigy, Bayer and Hoechst, respectively. Natural dyes and vegetable dyes in the sense defined herein include henna (La wson i a a lba), camomile (Ma t ri ca ri chamomi l a or An themi s n obi l i s), indigo, palo campeche dye and nut shell extract. Temporary hair dyes, or hair dyeing rinses, generally consist of dye molecules that are too large to diffuse into the hair strand and act on the outside of the hair. They are usually applied via a non-rinsing procedure in which the dye solution is allowed to dry on the hair surface. As such, these dyes are typically less resistant to the effects of washing and cleansing the hair with surfactants and are removed by washing the hair with relative ease. Any temporary dye for hair can be used appropriately in the compositions of the invention and examples of preferred temporary hair dyes are illustrated below.

... «Jh ^ -l ^» A --- A. la¿ - = ^ Yellow Blue-Violet Semi-permanent hair dyes are dyes that are generally smaller in size and effects for temporary hair rinses but are generally larger than permanent (oxidative) dyes. Typically, semi-permanent dyes act in a manner similar to oxidative dyes since they have the potential to diffuse into strand hair. However, the semi-permanent dyes are generally smaller in size than the conjugated oxidative dye molecules mentioned above and as such are predisposed to gradual diffusion out of the hair again. A simple action of washing and cleaning the hair will promote this process and in general semi-permanent dyes are removed by washing completely of the hair after between approximately 5 and 8 washes. Any semi-permanent dye system can be suitably used in the compositions of the present invention. Semi-permanent dyes suitable for use in the compositions of the present invention are HC Blue 2, HC Yellow 4, HC Red 3, Disperse Violet 4, Disperse Black 9, HC Blue 7, HC Yellow 2, Disperse Blue 3, Disperse Violet 1 and mixtures thereof. Following are examples of semi-permanent dyes: Yellow Yellow Red Red Typical semi-permanent dye systems incorporate mixtures of both large and small color molecules. Depending on the size of the hair is not uniform from the root to the tip, the small molecules will diffuse both at the root and at the tip, but will not be retained inside the tip, while the larger molecules will generally be the only ones capable of spread at the ends of the hair. This combination of dye molecule size is used to help provide consistent color results from the root to the tip of the hair both during the initial dyeing process and during the subsequent wash.

Carbonate and / or ammonium carbamate Another essential component of the compositions herein is ammonium carbonate and / or hL? ± * ^ * ****. - ^^ ^, ^ J .., i ^ itr ^ ^^. Kte-t ... ,, AA?., Ammonium carbamate, preferably at a level of between approximately 0.01% and 10%, most preferred between about 0.1% and 5%, and especially between about 2% and 5% by weight. The dyeing compositions of the present invention have a pH in the range of between about 7 and 9, preferably between about 8 and 9. The pH of the preferred dyeing compositions of the present invention is kept within the desired pH range via the action of the inorganic peroxygen oxidizing agent and the ammonium carbonate and / or ammonium carbamate. However, if desired, the compositions may contain one or more optional buffering agents and / or hair bulking agents (HSAs). Various different pH modifiers can be used to adjust the pH of the final composition or any constituent part thereof. However, the preferred compositions herein are practically free of additional cushioning agents and bulking agents, ie, they comprise less than about 1%, preferably less than about 0.5%, of greater preference less than about 0.1% by weight of these agents. This adjustment of the pH can be effected by using well-known acidifying agents in the field of the treatment of keratinous fibers, and in particular human hair, such as, for example, inorganic and organic acids such as hydrochloric acid, tartaric acid, citric acid, succinic acid, phosphoric acid and carboxylic or sulphonic acids such as, for example, ascorbic acid, acetic acid, lactic acid, sulfuric acid, formic acid, ammonium sulfate and sodium diacid phosphate / phosphoric acid, disodium hydrogen phosphate / phosphoric acid, potassium chloride / acid hydrochloric, diacid potassium phthalate / hydrochloric acid, sodium citrate / hydrochloric acid, diacid potassium citrate / hydrochloric acid, diacid potassium citrate / citric acid, sodium citrate / citric acid, sodium tartarate / tartaric acid, sodium lactate / lactic acid, sodium acetate / acetic acid, disodium acid phosphate / citric acid and sodium chloride / glycine / hydrochloric acid, succinic acid and mixtures thereof. Examples of alkaline buffering agents are ammonium hydroxide, ethylamine, dipropylamine, triethylamine and alkanediamines such as, for example, 1,3-diaminopropane, anhydrous alkali metal alkanolamines such as, for example, mono- or di-ethanolamine, preferably those which are completely substituted in the amine group such as for example dimethylaminoethanol, polyalkylene polyamines such as for example diethylenetriamine or a heterocyclic amine such as for example morpholine as well as the alkali metal hydroxides, such as sodium and potassium hydroxide, alkaline earth metal hydroxides, such as hydroxide of magnesium and calcium, basic amino acids such as L-argenine, lysine, alanine, leucine, iso-leucine, oxilisin and histidine and alkanolamines such as dimethylaminoethanol and aminoalkylpropanediol and mixtures thereof. Also suitable for use herein are compounds other than ammonium carbonate or ammonium carbamate forming "HC03" by dissociation in water (hereinafter referred to as "ion-forming compounds") Examples of suitable ion-forming compounds are Na2C03, NaHC03, K2C03, NH4HC03, CaC03 and Ca (HC03) and mixtures thereof The bleaching and dyeing compositions according to the present invention may, as L4- "f r-4: rti? # ?? l TJ Jass-ui will be described hereinafter, consisting of a final solution containing an oxidizing agent, an agent for dyeing the hair and ammonium carbonate and / or Ammonium carbamate that have been mixed before application to the hair or an individual component system. As such, the compositions according to the present invention may comprise kits for dyeing several components separately. In oxidation and dyeing cassettes comprising a portion of the inorganic peroxygen oxidizing agent, such as for example hydrogen peroxide, which may be present in any solid or liquid form, a solution of buffering agent may be used to stabilize the peroxide of hydrogen. Because the hydrogen peroxide is stable in the pH range of 2 to 4, it is preferred to use a buffering agent having a pH within this range. Diluted acids are suitable hydrogen peroxide buffering agents.

Catalyst The dyeing compositions herein may optionally contain a transition metal containing a catalyst for the inorganic peroxygen oxidizing agents and the optional preformed peroxy acid oxidizing agents. One suitable type of catalyst is a catalyst system comprising a heavy metal cation of defined decolorizing catalytic activity, such as, for example, copper, iron or manganese cations, an auxiliary metal cation having little or no catalytic decolorizing activity, such as for example zinc or aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, in particular ethanediindiamine ethanediamine acid, ethylenediaminetetra (methylene phosphonic acid) and water soluble salts thereof. These catalysts are disclosed in US-A-4, 430, 243. Other types of suitable catalysts include the manganese-based complexes set forth in US-A-5, 246, 621 and US-A-5,244,594. Preferred examples of these catalysts include MnIV2 (u-O) 3 (1, 4, 7-1 rimet il-l, 4,7-triazacyclononane) 2- (PF6) 2, Mn? P (u-0)? (u- OAc) 2 (1, 4, 7-trimethyl-1, 7-triazacyclononane) 2- (C104) 2, MnIV (u-0) 6 (1, 4,7-triazacyclononane) 4- (C104) 2, MnII3: MnIV4 (uO) i (u-OAc) 2- (1, 4, 7-trimethyl-1, 4,7-triazacyclononane) 2- (C104) 3, and mixtures thereof. Others are described in EP-A-0, 549, 272. Other ligands suitable for use herein include 1, 5, 9-trimethyl-1, 5, 9-t-riazacyclododecane, 2-methyl-1, 4, 7-triazacyclononane, 2-met i 1- 1, 4, 7-triazacyclononane, 1, 2,4,7-tetramethyl-l, 4,7-tiazacyclononane, and mixtures thereof. For examples of suitable catalysts see US-A-4, 246, 612 and US-A-5, 227, 084. See also US-A-5, 194, 416 which shows mononuclear manganese (IV) complexes as Mn (1, 4,7-trimethyl-1,4-, 7-triazacyclononane) (OCH 3) 3- (PF 6). Still another type of suitable catalyst, such as that set forth in US-A-5, 114, 606, is a complex of manganese (III) and / or (IV) soluble in. water, with a ligand that is a polyhydroxy compound without carboxylate having at least three consecutive C-OH groups. Other examples include binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including N MnSI1 (uO) 2MnIVN4) + and [BipysMn111 (uO) 2MnIvbipy2] - (C104) 3. Additional suitable catalysts are described, example, in EP-A-0, 408, 131 (complex cobalt catalysts), in EP-A-0,384,503, and EP-A-0, 306, 089 (catalysts of úifcii¡a ±? ^ * Hu ^ - ** + * i metallo-porphyrin), in US-A4, 728, 55 (manganese catalyst / indented ligand), in US-A-4,711,748 and EP-A- 0, 224, 952, (manganese absorbed in aluminosilicate catalyst), in US-A-4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), in US-A-4, 626, 373 (catalyst of manganese / ligand), in US-A-4,119,557 (ferric complex catalyst), in DE-A-2, 054, 019 (cobalt chelating catalyst), in CA-A-866,191 (salts containing metal of transition), in US-A-4, 430, 243 (chelants with manganese cations and non-catalytic metal cations) u in US-A-4,728, 455 (manganese gluconate catalysts).

Heavy Metal Ionic Sequestrant The dyeing compositions of the invention may contain as an optional component a heavy metal ion sequestrant. By "heavy metal ionic sequestrant" is meant herein components that act to sequester (chelate or purify) heavy metal ions. These components may also have chelation capacity with calcium and magnesium, but preferably show a selectivity for binding heavy metal ions such as for example iron, manganese and copper. These sequestering agents are valuable in the compositions for dyeing the hair as described herein, the delivery of a controlled oxidation action, as well as for the provision of good storage stability of the products for dyeing the hair. Ionic heavy metal sequestrants are generally present at a level between about 0.005% and 20%, preferably between about 0.01% and 10%, more preferably between about 0.05% and 2% by weight of the compositions. Various sequestering agents are known for use, including amino phosphonates, available as Dequest® from Monsanto, nitriloacetates, hydroxyethyl-ethylenetriamines and the like. Ionic heavy metal sequestrants suitable for use herein include organic phosphonates, such as for example the amino alkylene poly (alkylene phosphonates), ethan-1-hydroxyl? di s phosphates of alkali metal and nitrile trimethylene phosphonates.

Among the above species, diethylenetriamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxyethyl 1,1-diphosphonate are preferred. The preferred non-phosphorus heavy metal ionic sequestrants suitable for use herein include nitric acid and polyaminocarboxylic acids, such as, for example, ethylene diamine ethoxy acid, ethylene glyceryl pentaacetic acid, ethylene diamine disuccinic acid, ethylene diamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof. Especially preferred is ethylene diamine N, N'-disuccinic acid (EDDS), see US-A-4,704,233, or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof. . Other ionic heavy metal sequestrants suitable for use herein are iminodiacetic acid derivatives such as, for example, 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399 , 133. Sequestrants of N-2-hydroxypropyl sulfonic acid of iminodiacetic acid and N-carboxymethyl N-2-hydroxypropyl-3-sulphonic acid of aspartic acid described in EP-A-516 are also suitable here. , 102. The binders of β-alanine-N, N'-diacetic acid, N, N'-diacetic acid of aspartic acid, N-monoacetic acid of aspartic acid and iminodisuccinic acid described in EP-A-509 are also suitable. , 382. EP-A-476,257 describes suitable amino-based sequestrants. EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein. EP-A-528,859 discloses a suitable alkyl iminodiacetic acid sequestrant. Also suitable are dipyclic acid and 2-phosphonobutan-1,2,4-tricarboxylic acid. Also suitable are glycinamide-N, N'-disuccinic acid (GADS), ethylenediamine-N- '-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N' disuccinic acid (HPDDS). The heavy metal ionic sequestering agents of the present invention can be used in their alkali metal or alkaline earth metal salts.

Thickeners The dyeing compositions of the present invention may additionally include a thickener at a level between about 0.05% and 20%, preferably between about 0.1% and 10%, more preferably between about 0.5% and 5% by weight . Thickening agents suitable for use in the compositions herein are selected from oleic acid, cetyl alcohol, oleyl alcohol, sodium chloride, cetearyl alcohol, stearyl alcohol, synthetic thickeners such as for example Carbopol, Aculyn and Acrosyl and mixtures thereof . Preferred thickeners for use herein are Aculyn 22®, steareth-20 methacrylate copolymer; Aculyn 44®, polyurethane resin and Acusol 830®, acrylate copolymers that are available from Rohm and Haas, Philadelphia, PA, USA. Additional thickeners, suitable for use herein, include sodium alginate or gum arabic, or cellulose derivatives, such as, for example, methyl cellulose or the sodium salt of carboxymethylcellulose or acrylic polymers.

Diluent Water is the preferred diluent for the compositions according to the present invention. However, the compositions according to the present invention can include one or more solvents as additional diluent materials. In general, suitable solvents for use in the dyeing compositions of the present invention are selected to be water-miscible and skin-friendly. Suitable solvents for use as additional diluents herein include C?-C2o mono- or polyhydric alcohols and their ethers, glycerin, with monohydric and dihydric alcohols and their preferred ethers. In these compounds, alcohol residues containing from 2 to 10 carbon atoms are preferred. Thus, a preferred group includes ethanol, isopropanol, n-propanol, butanol, propylene glycol, ethylene glycol monoethyl ether and mixtures thereof. Water is the preferred principal diluent in the compositions according to the present invention. Main diluent, in the sense in which it is defined herein, means, that the present water level is greater than the total level of any other diluents.

The diluent is present at a level of preference of between about 5% and 99.98%, preferably between about 15% and 99.5%, more preferably at least between about 30% and 99%, and especially between about 50 % and 98% by weight of the compositions herein.

Enzyme An additional useful material in the compositions for dyeing the hair according to the present invention is one or more enzymes. Suitable enzyme materials include commercially available lipases, cutinases, amylases, neutral and alkaline proteases, esterases, cellulases, pectinases, lactases and peroxidases conventionally incorporated in detergent compositions. Suitable enzymes are shown in U.S. Patents 3,519,570 and 3,533,139. Peroxidases are specific heme proteins for peroxide, but they use a wide range of substances as donors. The catalase that decomposes peroxide is included here in view of the fact that it is generally similar in structure and properties and is capable of causing certain oxidations by means of H202. The decomposition of H202 can be considered u ¿2á? ¿m as the oxidation of one molecule by the other. It spreads in aerobic cells and may have some more important function. Coenzyme peroxidases are not haemoproteins and at least one is a flavoprotein. Other flavoproteins such as, for example, xanthine oxides will also use H202 among other acceptors, and the coenzyme peroxidases resemble these in place of the classical peroxidases in that they are not specific for H202. Peroxidases suitable for the compositions of the present invention include horseradish peroxidase, horseradish peroxidase, cow's milk peroxidase, rat liver peroxidase, linginase, and haloperoxidase such as, for example, chloro- and bromo-peroxidase. Optionally, enzymes are incorporated at levels sufficient to provide up to about 50 mg by weight, more typically between about 0.01 mg and 10 mg of the active enzyme per gram of the hair treatment composition of the invention. In other words, the peroxidase enzyme can be incorporated in the compositions according to the invention at a level between approximately 0.0001% and 5%, preferably between approximately 0.001% and 1%, more preferably between approximately 0.01. % and 1% by weight of active enzyme of the composition. Commercially available protease enzymes include those sold under the trade names Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A / S (Denmark), those sold under the trade name Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the brand name Opticlean and Optimase by Solvay Enzymes. The protease enzyme can be incorporated in the compositions according to the invention at a level of between 0.0001% up to 4% by weight of active enzyme of the composition. Amylases include, for example, α-amylases obtained from a special strain of B l i ch in i forms, described in more detail in GB-1,269,839 (Novo). Preferred commercially available amylases include, for example, those sold under the tradename Rapidasa by Gist-Brocades, and those sold under the trade name Termamyl and BAN by Novo Industries A / S. The amylase enzyme can be incorporated into the composition according to the invention at a level of between 0.0001% up to 2% by weight of active enzyme of the composition. The lipolytic enzyme may be present at active lipolytic enzyme levels of between 0.0001% up to 2% by weight, preferably 0.001% up to 1% by weight, most preferably between 0.001% up to 0. 5% by weight of the compositions. The lipase can be obtained from fungal or bacterial origin, for example, from a strain for the production of lipase from Humicola sp., Thermomyces sp. or Pseudomonas sp. among which include Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains is also useful herein. A preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is described in European patent granted, EP-B-0218272. Another preferred lipase herein is that obtained by cloning the Humicola lanuginosa gene and expressing the gene in Aspergillus oryza, as a host, as described in the European patent application, EP-A-0258 068, which is available commercially from Novo Industri A / S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in the patent of the United States 4,810,414, Huge-Jensen et al, granted on March 7, 1989.

SURFACTANT MATERIALS The compositions of the present invention may additionally contain a surfactant system. Suitable surfactants for inclusion in the compositions of the invention generally have a lipophilic chain length of between about 8 and 22 carbon atoms and can be selected from anionic, cationic, nonionic, amphoteric, zwitterionic surfactants and mixtures thereof. (i) Anionic Surfactants Suitable anionic surfactants for inclusion in the compositions of the invention include alkyl sulfates, ethoxylated alkyl sulfates, alkyl glyceryl ether sulphonates, methyl acyl taurates, fatty acyl glycinates, N-acyl glutamates, acyl isethionates, alkyl sulfosuccinates, alkyl ethoxy sulphosuccinates. , alpha-sulfonated fatty acids, their salts and / or esters, alkyl ethoxy carboxylates, alkyl phosphate esters, alkyl phosphate ethoxylated esters, alkyl sulphates, acyl sarcosinates and fatty acid / protein condensates, and mixtures thereof. The alkyl and / or acyl chain lengths for these surfactants are C? 2-C22, preferably C? 2-C? B, more preferably C? 2-C? . (ii) Nonionic Surfactants The compositions of the invention may also comprise water-soluble nonionic surfactants. Surfactants of this class include mono and fatty acid diethanolamides of C? 2-C? , sucrose polyester surfactants and amide polyhydroxy fatty acid surfactants having the following general formula. 0 Rq Go I * RQ-C-N-Z2 The amide surfactants of N-alkyl, N-alkoxy or N-aryloxy polyhydroxy fatty acid surfactants, preferred according to the above formula are those in which Ra is C5-C3 hydrocarbyl, preferably C6-C hydrocarbyl? , which include straight-chain and branched-chain alkyl and alkenyl, or mixtures thereof, and R9 is typically hydrogen, alkyl or hydroxyalkyl of C? -C8, preferably methyl, or a group of the formula -R1- 0-R2, wherein R1 is C2-C8 hydrocarbyl including straight chain alkyl, cyclic branched chain and is preferably C2-C4 alkylene, R is straight chain, branched chain and cyclic hydrocarbyl including aryl and oxyhydrocarbyl, and preferably is C 1 -C 4 alkyl, especially methyl, or phenyl. Z2 is a polyhydroxyhydrocarbyl entity having a linear hydrocarbyl chain with at least 2 (in the case of glyceraldehyde) or at least 3 hydroxyl (in the case of another reducing sugar) directly connected to the chain, or an alkoxylated derivative (preferably , ethoxylated or propoxylated) thereof. Z2 will preferably be derived from a reducing sugar in a reductive amination reaction, most preferably Z-2 is a glycityl entity. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose, as well as glyceraldehyde. As raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup may be used, as well as the individual sugars listed above. These corn syrups can provide a mixture of sugar components for Z2. It should be understood that this is not intended to exclude other suitable raw materials. Preferably, Z2 will be selected from the group consisting of -CH2- (CHOH) n-CH2OH, -CH (CH2OH) - (CHOH) n -! - CH2H, CH2 (CHOH) 2 (CHOR ') CHOH) -CH2OH, wherein n is an integer from 1 to 5, inclusive, and R' is H or a cyclic mono or polysaccharide, and the alkoxylated derivatives thereof. As noted, glycityls are preferred to a greater extent where n is 4, in part CH2- (CHOH) 4-CH2OH. The most preferred polyhydroxy fatty acid amide has the formula R8 (CO) N (CH3) CH2 (CHOH) 4CH2OH, wherein R8 is a straight chain alkyl or alkenyl group of C6 ~ C? 9. In the compounds of the above formula, R8-CO-N < it can be, for example, cocoamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmiamide, seboamide, etc. The nonionic surfactants derived from oil suitable for use herein include emollients derived from vegetable and water soluble animals such as for example triglycerides with an inserted polyethylene glycol chain; mono and di-glycerides ethoxylates, polyethoxylated lanolins or ethoxylated butter derivatives. A preferred class of nonionic surfactants derived from oil for use herein has the following general formula: Mgkfa &? What is the difference between i and tk? y * J RCOCH2CH (OH) CH2 (OCH2CH2) nOH where n is between about 5 and 200, preferably between about 20 and 100, more preferably between about 30 and 85, and wherein R comprises an aliphatic radical having an average of between about 5 and 20 carbon atoms, preferably between about 7 and 18 carbon atoms. Suitable ethoxylated oils and fats of this class include glyceryl cocoate glyceryl polyethylene glycol derivatives, glyceryl caproate, glyceryl caprylate, glyceryl sebacate, glyceryl palmate, glyceryl stearate, laurate. glyceryl, glyceryl oleate, glyceryl ricinoleate and glyceryl fatty esters derived from triglycerides, such as, for example, palm oil, almond oil and corn oil, preferably glyceryl sebacate and glyceryl cocoate. Polyethylene glycol-based polyethylene glycol non-ionic C9-C? Fatty alcohol surfactants containing an average of between about 5 and 50 ethyleneoxy entities per mole of surfactant are preferred for use herein.

C9-C5 polyethoxylated fatty alcohols based on polyethylene glycol suitable for use herein include Pareth-3 C9-Cu, Pareth-4 of C9-Cn, Pareth-5 of C9-Cn, Pareth-6 of C9- Cu, Pareth-7 from C9-Cn, Pareth-8 from C9-Cn, Pareth-3 from C11-C15, Pareth-4 from Cn-C15, Pareth-5 from C11-C15, Pareth-6 from C11-C15, Pareth-7 from C11-C15, Pareth-8 from C11-C15, Pareth-9 from Cn-Ci5, Pareth-10 from Cn-C? 5, Pareth-11 from Cn-C? 5, Pareth-12 from Cp- C? 5, Pareth-13 of C11-C15 and Pareth-14 of C11-C15. PEG 40 hydrogenated castor oil is commercially available under the tradename Cremophor® from BASF. Glyceryl cocoate PEG 7 and glyceryl laurate PEG 20 are commercially available from Henkel under the tradenames Cetiol® HE and Lamacit® GML 20 respectively. Pareg-8 of Cg-Cn is commercially available from Shell Ltd under the tradename Dobanol® 91-8. Particularly preferred for use herein are polyethylene glycol ethers of certiary alcohol such as, for example, Ceteareth 25 which is available from BASF under the tradename Cremaphor A25. Also suitable for use herein are nonionic surfactants derived from mixed vegetable fats extracted from the fruit of the .-A - ^. ^ .. ^ iat? T. JAA jt ..

Shea Tree (Butyrospermum Karkii Kotschy) and derivatives thereof. Similarly, the ethoxylated derivatives of Mango, Cocoa butter and Illipe can be used in the compositions according to the invention. Although these are classified as non-ionic ethoxylated surfactants it should be understood that a certain proportion can remain as a non-ethoxylated vegetable oil or fat. Other nonionic surfactants derived from Suitable oils include ethoxylated derivatives of almond oil, peanut oil, rice bran oil, wheat germ oil, linseed oil, jojoba oil, apricot kernel oil, walnut nuts, palm nuts, walnuts 15 pistachio, sesame seeds, rape seed, juniper oil, corn oil, peach kernel oil, poppy seed oil, pine oil, castor oil, soybean oil, avocado oil, oil safflower, coconut oil, oil 20 of hazelnuts, olive oil, grape seed oil and sunflower seed oil. (i) Amphoteric Surfactants Amphoteric surfactants suitable for use in the compositions of the invention include: (a) imidazolinium surfactants of the formula (VII) wherein Ri is C7-C22 alkyl or alkenyl, R2 is hydrogen or CH2Z, each Z is independently C02M or CH2-C02M, and M is H, alkali metal, alkaline earth metal, ammonium or alkanolammonium; and / or ammonium derivatives of the formula (VIII) C2H4OH R1CONH (CH2) 2N + CH2Z wherein Rx, R2 and Z are as defined above; (b) aminoalkanoates of the formula (IX) R? NH (CH2) nC02M iminodialkanoates of the formula (X) R? N [(CH2) raC02M] 2 . & - & - .-- > * »_« & i.it? ¡Á and iminopolialcanoatos of the formula (XI) R1- [N (CH2) p] qN [CH2C02] 2 I CH2C02M wherein n, m, p, and q are numbers from 1 to 4, and Ri and M are independently selected from the groups specified above; and (c) mixtures thereof. Suitable amphoteric surfactants of type (a) are marketed under the tradename Miranol and Empigen and are understood to comprise a complex mixture of species. Traditionally, miranoles have been described to have the general formula (VII), although the CTFA Cosmetic Ingredient Dictionary, 3rd. Edition indicates the structure (VIII) non-cyclical while the 4th. Edition indicates yet another structural isomer in which R2 is bound to O instead of being bound to N. In practice, it is likely that there is a complex mixture of cyclical and non-cyclic species and both definitions are provided here in order to complete . However, non-cyclic species are preferred for use herein.

Examples of suitable amphoteric surfactants of type (a) include the compounds of the formula XII and / or XIII in which Ri is C8H? 7 (especially iso-capryl), C9Hi9 alkyl and CnH23. Especially preferred are compounds in which Ri is C9H? 9, Z is C02M and R2 is H; the compounds in which Ri is CnH23, Z is C02M and R2 is CH2C02M; and the compounds in which Rx is CnH23, Z is C02M and R2 is H. In the CTFA nomenclature, materials suitable for use in the present invention include cocoanfocarboxipropionate, cocoanfo-carboxy propionic acid, and especially cocoanfoacetate and cocoamphodiacetate (other way called cocoanfocarboxiglycinate). Specific commercial products include those sold under the tradenames Ampholak 7TX (carboxy methyl tallow polypropyl amine sodium), Empigen CDL60 and CDR 60 (Albright &Wilson), Miranol H2M Conc. Miranol C2M Conc. NP, Miranol C2M Conc. OP, Miranol C2M SF, Miranol CM Special (Rhone Poulenc); Alkateric 2CIB (Alkaril Chemicals); Amphoterge W-2 (Lonza, Inc.); Monateric CDX-38, Monateric CSH-32 (Mona Industries); Rewoteric AM-2C (Rewo Chemical Group); and Schercotic MS-2 (Scher Chemicals). Additional examples of amphoteric surfactants suitable for use in JLMÍl? Yt t? Li * eJ e. .Y .. . . the present include Octoxynol-1®, polyoxethylene octyl 1-phenylether (1); Nonoxynol-4®, polyoxyethylene nonylphenyl ether (4) and Nonoxynol-9, noni 1 phenolite full polyoxyeth (9). It will be understood that several of the commercially available amphoteric surfactants of this type are manufactured and sold in the form of electroneut complexes with, for example, hydroxide or anionic sulfate counterions or sulfonate surfactants., especially those of the sulphonated C8-Ciß alcohol, C8-C? 8 ethoxylated alcohol or C8-C? 8 acyl glyceride types. Note also that the concentrations and proportions by weight of the amphoteric surfactants are based herein on the uncomplicated forms of the surfactants, any anionic surfactant counterions that are considered as part of the content of the total anionic surfactant component. Examples of preferred amphoteric surfactants of type (b) include poly-carboxymethylamines of N-alkyl polytrimethene sold under the tradenames Ampholak X07 and Ampholak 7CX by Berol Nobel and also the salts, especially the triethanolammonium salts and the salts of the acid N-lauryl 1-beta-amino propionic acid and N-acid yHy ¡i * i.yyy y. l-t-É-Ü • •? í Jíftiir ffftlHÉ-Éif-lauryl-imino-dipropionic. These materials are sold under the trade name Deriphat by Henkel and Mirataine by Rhóne-Poulenc. (iv) Zwitterionic Surfactants The water-soluble auxiliary zwitterionic surfactants suitable for inclusion in the compositions of the present invention include alkyl betaines of the formula R5R6R7N + (CH2) nC02M and amido betaines of the following formula (XII): R5CON (CH2) m (CH2) nC02M wherein R5 is Cn-C22 alkyl or alkenyl, R6 and 7 are independently C1-C3 alkyl, M is H, alkali metal, alkaline earth metal, ammonium or alkanolammonium, and n, m are each numbers from 1 to 4. Preferred betaines include cocoamidopropyl-dimet and Icarboxymethyl betaine, laurylamidopropyl-dimethylcarboxymethyl betaine and Tego betaine®. The water-soluble auxiliary sultaine surfactants suitable for inclusion in the compositions of the present invention include alkyl sultaines of the following formula (XIII): lMuA. *! ..

R R1CON (CH2) mN + (CH2) nCH (OH) CH2S? 3'lv1 + wherein Ri is C to C22 alkyl or alkenyl, R2 and R3 are independently Ci to C3 alkyl, M is H, alkali metal, alkaline earth metal, ammonium or alkanolammonium and m and n are numbers from 1 to 4. It is preferred to be used in the present the coco amido propylhydroxy sultaine. The water-soluble auxiliary amine oxide surfactants, suitable for inclusion in the compositions of the present invention, include alkylamine oxide R5R6R7NO and amido amine oxides of the following formula (XIV): H.H R5CON (CH2) mN wherein R5 is C22 to C22 alkyl or alkenyl, Re and R are independently Ci to C3 alkyl, M is H, alkali metal, alkaline earth metal, ammonium or alkanolamome and m is a number from 1 to 4. Preferred amine oxides include cocoamidopropylamine oxide, lauryl dimethyl amine oxide and myristyl dimethyl amine oxide.

Optional materials Several of the optional additional materials can be added to the dyeing compositions herein described at a level of between about 0.001% and 5%, preferably between about 0.01% and 3%, most preferably between about 0.05% and 2% by weight of the composition. These materials include proteins and polypeptides and derivatives thereof; water-soluble or solubilizable preservatives such as, for example, DMDM Hydantoin, Germall 115, methyl, ethyl, propyl and butyl esters of hydroxybenzoic acid, EDTA, Euxilo® K400, natural preservatives such as, for example, benzyl alcohol, potassium sorbate and bisabalol , benzoic acid, sodium benzoate and 2-phenoxyethanol; antioxidants such as, for example, sodium sulfite, hydroquinone, sodium bisulfite, sodium metabisulfite and thioglycolic acid, sodium dithionite, erythrobic acid and other mercaptans; dye solvents such as, for example, oxalic acid, sulfated castor oil, salicylic acid and sodium thiosulfate; H202 stabilizers such as, for example, tin compounds such as sodium stannate, stannic hydroxide and stannous octoate, acetanilide, colloidal phenacetin silica such as, for example, magnesium silicate, oxyquinoline sulfate, sodium phosphate and tetrasodium pyrophosphate; and p-hydroxybenzoates; wetting agents such as, for example, hyaluronic acid, chitin, and sodium polyacrylates grafted with starch such as Sanwet® IM-1000, IM-1500 and IM-2500 available from Celanese Superabsorbent Materials, Portsmith, VA, USA and described in US Pat. A4, 076, 663 as well as, methylcellulose, starch, higher fatty alcohols, paraffin oils, fatty acids and the like; solvents; anti-bacterial agents such as, for example, Oxeco (phenoxy isopropanol); low temperature phase modifiers as ionic ammonium sources (for example NH4C1); agents for controlling viscosity such as, for example, magnesium sulfonate and other electrolytes; quaternary amine compounds such as distearyl-, dilauryl-, di-hydrogenated tallow, dimethylammonium chloride, dicetyldiethalammonium ethiisulfate, disodbodimethylammonium methylisulfate, disodium dimethylammonium chloride and dicoco dimethylammonium chloride; agents hair conditioners such as, for example, silicones, higher alcohols, cationic polymers and the like; enzymatic stabilizers as calcium sources soluble in water or borate species; coloring agents; Ti02 and mica coated with Ti02; perfumes and perfume solubilizers; and zeolites such as, for example, Valfour BV400 and derivatives thereof, and Ca2 + / Mg2 + sequestrants such as polycarboxylates, amino polycarboxylates, polyphosphonates, amino polyphosphonates etc. and water softening agents such as, for example, sodium citrate. The present invention is represented by the following non-limiting examples. In the examples, all concentrations are presented on a 100% active basis and all percentages are presented by weight unless otherwise stated and the abbreviations have the following designations: Oxidizing agent hydrogen peroxide Oxidative stain 1 para-phenylene diamine Oxidative stain 2 2,5-diaminotoluene sulfate Oxidative stain 3 para-aminophenol Oxidative stain 4 resorcinol Oxidative stain 5 m-aminophenol Oxidative stain 6 m-phenylenediamine Oxidative stain 7 2-amino -3-hydroxypyridine Oxidative Dye 8 1-naphthol Oxidative Dye 9-amino-2-hydroxytoluene Chelating Agent tetrasodium EDTA Surfactant 1 Ceteareth-25 Thickener 1 Cetyl alcohol Thickener 2 Stearyl alcohol Alkali 1 Ammonium carbonate Solvent Dipropylene glycol EXAMPLES I -XV The following are compositions for hair treatment in the form of hair dyeing compositions which are representative of the present invention.

Ingredient I II III IV V VI VII VIII Oxidizing Agent 3 3 3 3 3 4.5 3 4.5 Oxidative Dye 1 0., 85 0 0 0.37 0 0 0.75 0 Oxidative Dye 2 0 0.43 0. 5 0 0 0.1 0 0.09 Oxidative Dye 3 0 0.16 0 0.25 0.4 0.1 0 0.02 Oxidative Stain 4 0. 21 0.05 0 0.2 0 0.8 0.27 0.04 Oxidative Stain 5 0. 21 0.05 0 0.9 0 0.005 0.15 0.008 Oxidative Stain 6 0. 05 0 0 0 0 0 0.01 0.001 Oxidative Stain 7 0 0 0 0 0 0 0 0 ». ^ - ^? B ^ - ^^ '? ^ Ii ^ s ^' tM m ^^ '^^' '* Oxidative Stain 8 0 0 0 0 0.11 0 0 0 Oxidative Stain 9 0 0.25 0.25 0.7 0.16 0.0025 0 0 0 Chelating Agent 0.2 0.2 0.2 0.2 0.2 0.2 0. .2 0. .2 Antioxidant 1 0.2 0.2 0.2 0.2 0.2 0.1 0. .2 0. .2 Antioxidant 2 0.5 0.5 0.25 0.25 0.5 0.1 0. .5 0. .5 Surfactant 1 1.5 1.5 1.5 2.1 1.5 1.5 2. .1 1. .5 Thickener 1 2.25 2.25 2.25 3.12 2.25 2.25 3. 12 2. 25 Thickener 2 2.25 2.25 2.25 3.12 2.25 2.25 3. 12 2. 25 Alcali 1 3 3 3 3 3 4 3 4 Solvent 0 3 3 0 3 0 0 0 Water p / 100 p / 100 p / 100 p / 100 p / 100 p / 100 p / 100 p / 100 pH 8.9 8.8 8.9 8.9 8.9 8.9 8.9 8.9 Ingredient IX X XI XII XIII XIV XV Oxidizing Agent 3 3 3 3 3 4.5 4.5 Oxidative stain 1 0 0. .3 0.55 0 0.16 0 0 Oxidative stain 2 0.3 0 0 0.26 0 0.03 0.1 Oxidative Dye 3 0.3 0. .05 0 0.19 0.12 0.16 0.05 Oxidative Dye 4 0.05 0. .14 0.05 0.16 0.15 0.05 0.05 Oxidative stain 5 0 0., 025 0.09 0.01 0.02 0 0.005 Oxidative stain 6 0 0 0.13 0 0 0 0 Oxidative stain 7 0 0 0.1 0 0 0 0 Oxidative Dye 8 0.13 0 0.04 0 0 0.015 Oxidative Dye 9 0.16 0 0 0.013 0.025 0.06 0.001 Chelating Agent 0.2 0. 2 0.2 0.2 0.2 0.2 0.2 Antioxidant 1 0.2 0. 2 0.2 0.2 0.2 0.2 0.2 . ..-. iaéi ".aA.n? t¡ imf tnkm '* 1 nm (-1 &,? * < * á ÍJLM Antioxidant 2 0.5 0.5 0.5 0.5 0.5 0.2 0.2 Surfactant: e 1 1.5 1.5 2.1 1.5 1.5 1.5 1.5 Thickener 1 2.25 2.25 3.12 2.25 2.25 2.25 2.25 Thickener 2 2.25 2.25 3.12 2.25 2.25 2.25 2.25 Alkali 1 3 3 3 3 3 4 4 Solvent 3 0 1 1 1 1.5 1 Water p / 100 p / 100 p / 100 p / 100 p / 100 p / 100 p / 100 pH 8.9 8.9 8.9 8.8 8.9 8.9 8.8 In the previous examples, water is used as the diluent. However, in variations thereof the water may be replaced, in part, by between about 0.5% and 50% by weight of the total water content of the examples by diluents such as for example, lower alcohols, eg, ethylene glycol, ethylene glycol monoethylether, diethylene glycol, monoethylether of 10 diethylene glycol, propylene glycol, 1,3-propanediol, ethanol, isopropyl alcohol, glycerin, butoxyethanol, ethoxydiglycol, hexylene glycol, polyglyceryl-2-olelether and mixtures thereof. Examples I-XV provide a range 15 full of colors, that is, from blond to black, while reducing skin irritation, hair damage and odor. The compositions of the Examples also provide excellent gray coverage.

Method of use It is important that the compositions for dyeing are in a form that is easy and convenient to prepare and use by the consumer, since the oxidizing agent must remain in contact with the hair for a certain period of time and not run or dripping of the hair, possibly causing irritation of the eyes or skin. To face the above, the dyeing compositions of the present invention can be provided in either an individual package or in a pack form as the components are packaged separately to maintain stability, and, if desired, either mixed by the user just before application to the hair, or mixed and stored for future use, or mixed and partially used and the rest stored for future use. As described above, the compositions according to the present invention can be used by the consumer as a single component package. This individual package could comprise a single solution at a pH of 7 to 9 containing the oxidizing agent, the agent for dyeing the hair and the ammonium carbonate and / or ammonium carbamate. The solution could be applied directly to the hair by the consumer without the need for any pret or mixed treatments thereby providing a system for dyeing the hair "without problems", simple, fast, easy to use. An additional advantage of this individual component system is that it could be stored and reused; that is, an individual container could contain enough coloring composition for several applications over time. Thus, according to a further aspect of the present invention, there is provided a method for bleaching and dyeing the hair, wherein a composition for bleaching and dyeing the hair is applied directly to the hair and wherein the composition for bleaching and dyeing the hair comprises: (a) an oxidizing agent; (b) an oxidative or non-oxidative agent for dyeing the hair; and (c) ammonium carbonate and / or ammonium carbamate; wherein the composition has a pH of between about 7 and 9. The dyeing compositions herein are applied to the hair for periods of between 1 minute and 60 minutes depending on the degree of coloring required. A preferred time is between 5 minutes and 30 minutes. The dyeing compositions according to the present invention can be applied to both wet and dry hair. In accordance with yet a further aspect of the present invention, there is provided a method for bleaching and dyeing the hair comprising the steps of applying to the hair a first component comprising an oxidizing agent followed by the application to the hair of a second component comprising an oxidative and / or non-oxidative agent for dyeing the hair in combination with ammonium carbonate and / or ammonium carbamate. In addition, the present invention provides a method for bleaching and dyeing hair comprising the steps of applying to the hair a first component comprising an oxidative and / or non-oxidative agent for dyeing the hair in combination with ammonium carbonate and / or carbamate. ammonium followed by the application to The hair of a second component comprising an oxidizing agent.

Cases In accordance with the present invention, a case for dyeing is also provided. hair where the case consists of two or more components separately. In preferred embodiments the components of the kit are combined to form a composition for dyeing before application to the hair. In alternative embodiments, the individual components can be applied separately to the hair in a sequential manner. A preferred case of the present invention comprises at least two components, a first component comprising a combination of an oxidative and / or non-oxidative agent for dyeing hair and ammonium carbonate and / or ammonium carbamate and a second component comprising an oxidizing agent. The components can be mixed by the user just before application to the hair or can be applied separately. The components can also be mixed and the resulting composition can be stored for a future use or part of the resulting composition can be used and the rest of the composition is stored for future use. In one embodiment of the present invention, the oxidizing component comprises a stabilized aqueous solution of an inorganic peroxygen oxidizing agent, more generally hydrogen peroxide in an amount such that the final concentration of the dyeing composition for use in the hair is between about 0.05% and 6% by weight and the additional agents described above.

Examples of these kits are as follows: I. A hair dyeing kit comprising a single package including therein is assembled: (1) a 50 ml bottle of hydrogen peroxide (6 wt.% H202), and optionally buffering and / or stabilizing agents; and (2) a 50 ml bottle containing one or more oxidative agents for dyeing hair, ammonium carbonate and / or ammonium carbamate and, optionally, additional agents such as surfactants, stabilizers, buffering agents, antioxidants, thickeners, The component containing the oxidative agents for dyeing the hair and carbonate and / or ammonium carbamate can be combined with the hydrogen peroxide to form the dyeing system of the present invention and the resulting solution can be either apply to the hair to dye it or it can be stored for future use, or the stable components packed separately can be stored and mixed when required. II. A kit for dyeing the hair as described in I above, wherein the component containing hydrogen peroxide is applied to the hair prior to the application of the oxidative agents to dye the hair, ammonium carbonate and / or ammonium carbamate and the additional materials to the hair. III. A kit for dyeing the hair as described in I above, wherein the component containing hydrogen peroxide is applied to the hair after the application of the oxidative agents to dye the hair, the ammonium carbonate and / or the ammonium carbamate and the additional materials to the hair. IV Additional examples of the kit components for the hair dyeing compositions, according to the present invention, include the separately packaged oxidizing component and a component of the oxidative agent for dyeing the separately packaged hair, comprising the dyeing agent hair and ammonium carbonate and / or ammonium carbamate wherein either or both components are present in particular form.

Claims (14)

1. CLAIMS 1. A composition for bleaching and dyeing hair comprising: (a) an oxidizing agent; (b) an oxidative or non-oxidative agent for dyeing the hair; and (c) ammonium carbonate and / or ammonium carbamate; wherein the pH of the composition is between about 7 and 9.
2. 2. The composition according to claim 1, wherein the pH of the composition is in the range between about 7.25 and 9.0, preferably between about 7.75 and 9.0, more preferably between about 8 and 9, most preferably between approximately 8.25 and 9.
3. 3. The composition according to claim 1 or 2, wherein the oxidizing agent is an inorganic peroxygen oxidizing agent.
4. 4. The composition according to any of claims 1 to 3, wherein the oxidizing agent 7 of inorganic peroxygen is present at a level of 0.01% less than between about 6%, preferably between about 0.01% and 4%, more preferably between about 1% and 4%, most preferably between about 2 % and 3% by weight of the composition.
5. 5. The composition according to any of claims 1 to 4, wherein the oxidizing agent is hydrogen peroxide.
6. 6. The composition according to any of claims 1 to 5, wherein the coloring agent is an oxidative coloring agent.
7. 7. The composition according to claim 6, wherein the total level of the oxidative agent for dyeing hair is between about 0.001% and 5%, preferably between about 0.01% and 4%, more preferably between about 0.1% and 3% , most preferably between about 0.1% and 1% by weight.
8. 8. The composition according to rei indication 6 or 7, wherein each oxidative agent to dye the Hair is present at a level between about 0.001% and 3%, preferably between about 0.01% and 2% by weight.
9. 9. The composition according to any of claims 1 to 8 which is practically free of additional buffering agents and pH modifiers.
10. 10. The use of the composition according to any of claims 1 to 9 for decolorizing and dyeing human or animal hair.
11. 11. A method to decolor and stain the 15 human or animal hair comprising applying to the hair a composition for decolorizing and dyeing the hair according to any of claims 1 to 9.
12. 12. A kit for bleaching and dyeing the hair comprising at least two components, a first component comprising an oxidizing agent and a second component comprising a combination of a hair coloring agent and a carbonate 25 ammonium and / or ammonium carbamate.
13. -Na i £ Y $ .J 13. A method for decolorizing and dyeing human or animal hair comprising the steps of applying to the hair a first component followed by the application to the hair of a second component, wherein the first component comprises an oxidizing agent and wherein the second component comprises a combination of an agent for dyeing the hair and carbonate and / or ammonium carbamate.
14. 14. A method for decolorizing and dyeing human or animal hair comprising the steps of applying a first component to the hair followed by the application of a second component, the first component comprising a combination of a hair coloring agent and carbonate and / or carbamate of ammonium and the second component comprises an oxidizing agent.