GB2361247A - Aqueous oxidative hair dye compositions characterised by particular hydrophilic-lipophilic balance, primary intermediates and coupler - Google Patents

Abstract

An aqueous oxidative hair dye composition comprising a coupler, at least one primary intermediate, an oxidizer, water and one or more surfactants is disclosed wherein the hair dye composition has a Cumulative HLB Index below about 2.5, and either (i) one primary intermediate is a compound of formula I,<BR> wherein R<SB>1</SB> is a C<SB>2</SB>-C<SB>6</SB> alkyl group or a C<SB>2</SB>-C<SB>6</SB> alkyl group in which one or more of the hydrogen atoms is replaced by a hydroxyl and X and Y are independently hydroxyl or amino groups, provided that, if one of X and Y is hydroxyl the other is amino, or (ii) a primary intermediate is a compound of formula II,<BR> wherein R<SB>2</SB> is a C<SB>1</SB>-C<SB>6</SB> alkyl or C<SB>1</SB>-C<SB>6</SB> hydroxyalkyl group and R<SB>3</SB>, R<SB>4</SB>, R<SB>5</SB> and R<SB>6</SB> are independently hydrogen, C<SB>1</SB>-C<SB>6</SB> alkyl or C<SB>1</SB>-C<SB>6</SB> hydroxyalkyl, with the proviso that at least one of R<SB>3</SB> and R<SB>5</SB> is hydrogen and the coupler is a compound of formula III,<BR> where R<SB>7</SB> and R<SB>8</SB> are independently hydrogen, C<SB>1</SB>-C<SB>6</SB> alkyl or C<SB>1</SB>-C<SB>6</SB> hydroxyalkyl, provided that one of R<SB>7</SB> and R<SB>8</SB> must be other than hydrogen limited class of coupler/primary intermediate combinations, in aqueous oxidative dye compositions having a cumulative HLB Index (as defined herein) below about 2.5, can be employed to dye hair and impart highly desirable colours which manifest unexpectedly improved wash fastness and resistance to light fading compared to hair coloration achievable with conventional oxidative hair coloring compositions and permit more intense vivid dyeouts to be obtained.

Description

2361247

RELATED APPLICATIONS

This is a continuation in part of copending application Serial No. 081972, 979 filed November 19, 1997.

FIELD OF INVENTION

This invention relates to aqueous oxidative, hair coloring compositions, which produce a vivid, intense dyeout having superior wash fastness and high resistance to light fading.

AL, It" BACKGROUND OF INVENTION is Modem hair dyeing methodology has developed from its initiation in the 1950's to the point where, folloWing shampoos and conditioners, today it is the third largest product type in the hair care category.

The most commonly used method of dyeing hair, particularly human hair, is oxi dative dyeing in which a mixture of essentially colorless; aromatic compounds, generally diaminobenzenes, dihydroxy benzenes and aminophenols, are converted by chemical reactions, that are well known to those skilled in the art, to a blend of colored com pounds within the hair fibers. Shortly before use, the colorless; aromatic compounds, in a suitable base formulation, are normally mixed with hydrogen peroxide or other strong oxidizing agents. The colored compounds or dyes are typically formed by oxidative cou pling between primary intermediates (usually p-phenylenediamines or p- aminophenols) and couplers which are phenols, resorcinols,. m-aminophenols or related cyclic com pounds. Various shades are developed by using mixtures containing more than one of both the intermediate and the coupler.

1 Because of their low molecular weights and water solubility the primary interme- diates and couplers diguse easily into the hair where the coupling reaction takes place.

The col&ed products developed by oxidation remain trapped in the hair because of their higher molecular weights, relative insolubility in-water and absorptive affinity to the in s ternal hair surface. This is the basis for permanent tints and toners which ideally last for the life of the hair and are relatively unaffected by light shampooing and'perspiration.

The practice of oxidative hair coloring is well known. Typically, it involves the use of a two-part system. One part the dye component contains at least one primary in io termediate and at least one coupler. Before use, the dye component is mixed with a second part, which is a developer formulation containing an oxidizing agent. The devel oper oxidizes the primary intermediate to a quinone imine. This, in tum, reacts with a coupler to form a colored compound.

There are a number of primary intermediates and couplers that are used in the practice of oyidative dyeing of hair. Based on their frequency of use, the most useful primary intermediates, are the following: p-phenylenediamine, p- toluenedlamine, P" amino-phenol, 2-chicro-p-phenylenediamine and 2-methoxy-"henylens-diamine. The most useful couplers, based on their frequency of use, are the following: resorcinol, 1 - napthol, 2-methyl-resordn61, m-aminophenol, 2.4-diaminophenolethanol, 5- methyl-3 aminophenol, 4-methyi-3-aminophenot and m-phanylenediarnine. Many combinations of prim" intermediates and couplers are known and described. The following United States patents contain some representative examples:

5,032,138; 5.393.305; 5.344,463; 5,609,651; 5,393,305;' and 5,843,193; Although hydrogen peroxide is the most widely employed oxidant other oxidizing agents are known and sometimes used. These include alkali and alkaline earth metal chlontes, which are described in U.S. Patent 5,032,138. Other oxidizing agents em ployed in oxidative hair coloring include urea peroxide, melamine peroxide and perbo- 2 rates and percarbonates such as sodium perborate and sodium percarbonate.

All of the above-identified patents are incorporated herein by reference in their entirety.

To be useful for coloring hair, oxidative dye formulations should meet at least the following conditions:

1. They must provide a range of color shades that are acceptable to practitioners io of hair coloring.

2. The couplers and primary intermediates must be properly dispersed to ensure that they rapidly penetrate into the hair.

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3. The dye component should have the necessary properties so that when it is mixed with the developer, the resulting mixture has the desired rheological properties. The mixture preferably is thin enough to be able to spread onto the hair, but thick enough to stay in place during the color development period. If thickened, the mixture should also be readily rinsable from the hair with water.

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4. The formulations should not be irritating to the scalp.

In order to meet conditions 2 and 3 above, mixtures of surfactants, organic solvents and thickeners, are included in all commercial hair dye preparations. Typical sur- factants that are used in hair color formulations are nonoxynol-2, nonoxynol-4, nonoxynol-9, octoxynol-1, laureth-4, laureth-23, oleth-4, oleth-21, sodium lauryl sulfate, sodium lauryl ether sulfate, sodium dodecyl benzene suffonate, sodium cocamido propylbetaine, soyatrimmonium chloride, cetyl trimmonium chloride and behenyitdmmonium chloride.

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Typical organic solvents used in hair color formulations include ethyl alcohol, isopropyl alcohol, carbitol, propylene glycol and hexylene glycol.

Typical thickeners used in hair color formulations include the surfactants de- scribed above, lauric acid diethanolamide, cocamide DEA and polyacrylic acid derivatives.

DETAILED DESCRIPTION OF THE INVENTION

This invention relates to the use of certain combinations of dye intermediates to gether with certain dyeing vehicles. Some of the dye intermediates are known. They have been described as providing superior brightness and wear-4astriess. The present inventors have discovered that, suprisingly, these dye intermediates can only be used effectively in certain dyeing vehicles. These vehicles can be distinguished by a measis ured quantity, the Cumulative HLB Index, which will be defined hereinafter. In order to practice the current invention the Cumulative HLB Index of the vehicle must be below a value of about 2.5.

For example, in U.S. Patent 5,344,463, the combination of 3-methyl-paminophenol and 2-methyl-naphthol was disclosed as giving intense vibrant red shades with superior wash-fastness. All of the examples given in U.S. Patent 5,344,463 consist of dye formulations in a dyeing vehicle that consists of water, ethanol and ammonia. The patent does state that solvents and surfactants may be added to the formulation up to 50% and 20% respectively. Normally, solvents and surfactants are required for good performance of a hair dye, in order to provide suitable rheology, to help wet the hair and to help remove the formulation from the hair after the dyeing is finished. Although U.S. Patent 5,344,463 does teach that surfactants and solvents can be added to its compositions, it does not teach or appreciate that the nature and amount of surfactant is critical. For example, when the composition of Example 5 in U.S. 5344463 is formulated to contain 15% of Oleth-2 (an ethoxylated alcohol with a low HLB value), the color produced on hair is drastically reduced from bright red to a dull light orange color. By com- 4 panson when these dyes are formulated, in accordance with the present invention, in a composition such that the Cumulative HLB Index is 2.5, vivid and fade-resistant colors are enabled.

.aim T is In U. S. Patent 4,507,280, the patentees disclose that solvents and surfactants interfere with the dyeing of oxidation dyes, and that dyeing can be effected with lower levels of dye in a highly aqueous base with low concentrations of solvent and surfactant. HoWever, U. S. Patent 4,507, 280 does not disclose or suggest that there are differences between surfactants and that some surfactants have a lesser effect on dyeing than others. Also, U. S. Patent 4,507,280 does not teach or suggest that some dye intermediates are more affected than others by the nature and concentration of the surfactants in the dyeing vehicle. Although the dyes specified in U.S. Patent 4,507,280 are more efficient at dyeing in a highly aqueous base, they can be used in other vehicles to provide a full range of shades. This includes vehicles typical of those used in commercial hair color products that generally contain quantities of low HLB surfactants.

The dyes disclosed in U.S. 5,344,463, which are shown in Formulas 1 and 11 as well as the primary intermediates shown in Formula [if, are greatly affected by surfactants. They give very weak colors when used in vehicles containing quantities of low 20 HLB surfactants.

The present inventors have found that, suprisingly, in order to make optimal use of the oxidation dyes summarized by Formulas 1, 11 and Ill, the dyeing vehicle must have certain properties. The characteristics of the vehicle that are essential to securing the benefits of the present invention include the amount of water, organic solvents and the nature of the surfactants in the composition. We will define a quantity that we call the 'Cumulative HLB Indwe of the final composition as it is applied to the hair. The usefulness of a vehicle for dyeing with the intermediates of U.S. 5,344,463 can be determined from the 'Cumulative HLB Index' of the final dye formulation.

The 'Cumulative HLB Index' is defined as the sum of the HLB Indexes of each ingredient in the formulation. HLB is a concept well known and understood by the swilled artisan. It is an expression of the relative simultaneous attraction of a material, particularly a surfactant, for water and oil. A surfactant having a high HLB is considered hy5 drophilic. A surfactant having a low HLB is considered lipophilic.

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The HLB of a surfactant can be calculated in several different ways, but for the purlioses of this invention, the HLB index of the ingredients of a composition is calculated from the Hildebrand Solubility Parameters (, alMpa'r2) according to the following io equation, as outlined in the CRC Handbook of Solubility Parameters and Other Cohesion Parameters, Barton, Allan F. M., CRC Press (1983):

H -16.8) L3 = (D1AIpaII2 x54 alA_IpaII2 -12.3 Atk IT is The values for the Hildebrand Solubility Parameters were taken from Barton. The HLB values that are calculated from this equation do not always agree with values calculated by other methods, but the present inventors found that they work particularly well for the purpose of predicting whether a particular dye vehicle is suitable for the practice of the present invention.

HLB Index' of an ingredient is calculated by dividing its formula weight percent by its HLB. Thus, the Cumulative HLB Index would be equal.to WM of ingredient 1 /HLB value of ingredient 1 + WM of ingredient 211-11-13 value of ingredient 2+ WM of ingredient 311-11-13 value of ingredient 3, etc., etc., etc.

6 The following is an example of how the Cumulative HLB Index is calculated for a composition containing water, Surfactant A and Surfactant B. Inaredients Wt% HLB value of the ingredien Water 80 Surfactant A 15 Surfactant B 5 io 2.95.

is 47 20 10 Thus, the'Cumulative HLB Index'= 80147 + 15120 + 5110 = 1.7 + 0.75 + 0.5 All components in a formulation contribute to the Cumulative HLB Index, however, when there are many ingredients in a formula, it may be acceptable to exclude some ingredients that are at very low concentrations, as they will have a negligible effect on the calculated result For example, a preservative with an HLB of 1 at a concentration of 0.02% would increase the HLB index by only 0.02 units. Eliminating this calculation would save a great deal of time, since the HLB or the Hildebrand Solubility Parameter of the preservative might not be known.

Although the HLB values calculated using the above equation may be slightly different than the HLB values calculated by other means, the concept is the same, and is well known and understood by the skilled artisan.

With the novel compositions of this invention, the Cumulative HLB Index will be up to about 2.5, although useful results can be obtained with somewhat higher values. This can be seen in Figure 1, wherein CIE a value (in other words red intensity) is plotted against Cumulative HLB Index for a sedes of compositions using the dye intermediates of Examples 1. It should be noted that when the C 1E a value is higher than about 14, indicated by a dashed line in the figure, the hair appears to be an intense red shade. When the CIE a value is below about 13.5 the color of the hair is a reddish brown and the color does not appear to be very saturated. In Figure 1, it can be seen 7 c AA qc- that the red intensity decreases as the Cumulative HLB Index increases. The CIE a value decreases quite rapidly until the Cumulative HLB Index is about 2.8, by which point the CIE a value is well below 14. The Cumulative HLB Index must be below about 2.5 in order to obtain the benefits of the present invention.

is When the Cumulative HLB Index of the dyeing vehicle is significantly higher than 2.5, it may be possible to get some color from the dyes of the current invention, specifically those defined by Formulas 1, 11 and Ill below. However, the dyeing will be very weak and will not allow formulation of a range of shades.

The novel oxidation dye formulations that are the subject of this invention contain one or more of the following intermediates:

X 0Rl Y I OH R2 R4 1 R3)l R5 HN, R6 R ill OH R7 R8 in which Rl is a C2 C6 alkyl group Or a C2 - C6 alkyl group substituted with one or more hydroxyl groups, R2 denotes a C 1 -C6 alkyl group or a C 1 -C6 alkyl group substituted with at least one hydroxyl group, R3, R4, R5, R6, R7 and R8 are independently hydrogen, Cl -C6 alkyl or hydroxyalkyl provided that at least one of R3 and R5 must be hydrogen and X and Y are amino or hydroxyl groups with the further provision that, if one of X and Y is a hydroxyl group, the other is an amino group.

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We have suprisingly found that, when these intermediates are used with a dyeing medium having a Cumulative HLB Index lower than about 2.5, intense, wear-stable colors are obtained.

is As in the production of other oxidative dye compositions, other couplers or pri- mary intermediates may be added to after the improved color. These compounds, as the skilled artisan will recognize, may be selected from a wide variety of couplers and primary intermediates well known to those skilled in the art. As primary intermediates, there may be mentioned by way of example, p-phenylenediamine, p- toluenediamine, 2-chloro-p-phenylenediamine, 2-methoxy-p-phenylenediamine, p-aminophenol and N,N bis(2-hydroxy-ethyi)-p-phenylenediamine. Examples of couplers that may be added to the intermediates that are the subject of the current invention include m- phenylene diamine, m-aminophenol, 2-methyl-5-aminophenol, 'I -naphthol, resorcinol and 2-me thylresorcinol. The salts of the foregoing compounds, especially the acid salts such as the monohydrochlorides, the dihydrochlorides or the corresponding sulfuric acid salts, may also be employed.

Other conventional agents often employed in hair coloring compositions may be employed in the dye component or in the developer component. These include, for ex ample, fragrances, coloring agents and chelating agents.

Antioxidants, such as sodium suffite, erythorbic acid and ascorbic acid, may also be included to inhibit premature oxidation.

Although the dye composition of the invention has been described heretofore as containing the developer so that the oxidative hair dye is produced, the developer can, as is usually the case, be a separate composition, which is mixed with the dye precur sors just prior to use. When this is done, the amount of water in the developer compo sition and in the composition containing the dye precursors and the Cumulative HLB index of the final composition should be such that the final composition produced by mixing the developer composition and dye precursor composition meets the require- 9 -tlkd AR qT Y.:

merits set forth previously herein for the final dye composition so that the benefits of the invention are obtained.

The dye and developer components of the compositions of this invention may be prepared in any of the usual formats, such as liquids, lotions, g els and the like. It is of course important that the compositions applied to the hair have and maintain sufficient viscosity to stay on the hair during the coloring procedure.

It is desirable, but not essential, that the viscosities of the dye and developer io components be close to each other. If the difference in viscosities is too great they will be difficult to mix. On shaking, the thinner component will aggregate and the rate of blending will be retarded. Typically, the viscosities of the components and of the final compositions will be from about 1000 to 25,000 cps.

1 The essence of the present invention is the discovery of a limited cJass of cou pierlprimary intermediate combinations which in aqueous oxidative dye compositions having the essential characteristics described herein can be employed to dye hair and impart highly desirable colors which manifest unexpectedly improved wash fastness and resistance to light fading compared to hair coloration achievable with conventional oxi dative hair coloring compositions and/or permit more intense vivid dyeouts to be ob tained.

The total amount of coupler in the oxidative dye compositions of this invention is from about 0.01 % to 10%, preferably 0.05% to 5%. This is the same amount of coupler normally employed with conventional oxidative dye compositions. If an auxiliary coupler is employed, from about 0.01 % to 3%, preferably 0.01 % to 1.5%, Will be a coupler rep resented by formula lit.

The amount of primary intermediate in the final compositions will be the amount normally employed, i.e., from about 0.01% to 10%, preferably 0.1% to 5%. Ifanauxil iary primary intermediate is employed from about 0.01 % to 3%, preferably 0.01 % to 1.5%, will be a primary intermediate represented by formula 1 or formula 11.

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A wide variety of surfactants and surfactant mixtures may be employed in the practice of this invention. Several typically useful surfactants are set forth below. They may be used singly or in blends containing at least two of them. Useful surfactants include amphoteric surfactants such as betaines, sultaines, glycinates, proprionates; alkylpolyglycosides; fatty acid soaps such as alkanolamine, alkali metal or alkaline earth metal salts of a carboxylic acid containing from about 11 to 19 carbon atoms; higher alkylbenzene suifonates; alkyl-naphthalenesuifonates; sulfonated esters of alcohols and polybasic acids; taurates; fatty alcohol sulfates; sulfates of branched chain or secondary io atcohols; alkyidimethyibenzyiammonium chlorides, salts of fatty acids or fatty acid mixtures. Illustrative of specific surfactants that can be used are sodium lauryl sulfate; polyoxyethylene lauryl ether myristy) sulfate; glyceryl monostearate; triethanolamine oleate, sodium salt of palmitic methyl taurine; cetyl pyridinium chloride; lauryl sulfonate; myristyl suffonate; lauric diethanolamide; polyoxyethylene stearate; ethoxyiated ofeoyl is diethanolamide; stearyidimethyl benzyl ammonium chloride; dodecylbenzene sodium suffonate; triethanolamine salt of p-dodecylbenzene sulfonate; nonyinaphthalene sodium sulfonate; dioctyl sodium sulfosuccinate; sodium N-methyl-Woleoyl taurate; oleic acid ester of sodium isothionate; sodium dodecyl sulfate; the sodium salt of 3-diethyl tridecanol-6-sulfate and the like.

If a thickening agent is employed to control the viscosity of the composition, two classes of these products have been found to be useful. One is a modified polyurethane of which several are available. They are sold under the trade names Aculyn 440 and Aculyn 460 (Rohm & Haas) 46. These are also known as Cl 8 polycarbarnyl poly- glycol ester. The other type of thickener that has been found useful is a hydrophobically modified polyacrylic acid. Examples are steareth-10 alkyll etherlacrylate polymer (Aculyn 220 from Rohm & Haas), acrylates copolymer (Aculyn 330 from Rohm & Haas), steareth-1 0 ally] etherlacrylate copolymer (Salcare SC800 from Allied Colloids) and Acrylates/Ceteth-20 Itaconate Copolymer (Structure 30000 from National Starch) 11 nT Any of a wide variety of alkaline reagents may be employed with the modified polyacrylic acids. Because of its freedom from toxicity over a wide concentration range and its economy, ammonium hydroxide is an acceptable alkalizing agent. However, any other compatible ammonia derivative can be used in place of, or together with, ammonium hydroxide to effect the desired alkalinity. For example, an alkylamine such as ethylamine, or triethylamine; or alkanolamines, such as ethanolamine, diethanolamine, aminomethyl propanol, aminomethyl propanediol and trishydroxymethyl aminomethane may be employed. Likewise, any other of the organic or inorganic alkalizing agents may be used, such as sodium or potassium hydroxide, sodium or potassium carbonate, sodium phosphate, sodium hydrogen phosphate, sodium silicate, guanidine hydroxide and the like. The preferred alkaline reagents are ammonium hydroxide, sodium carbonate and ethanolamine.

When the alkaline reagents listed above, or their equivalents, are employed at a is concentration of from about 0. 5% to 10%, the pH of the dye component will be from about 8 to 10.5.

Although they are not essential, buffering agents may be employed to stabilize the pH of the dye component during storage. Typically useful buffers include ammo- nium and alkali metal phosphates, bicarbonates, carbonates and, to a lesser extent, borates. Also suitable are amino buffers such as, N-12- hydroxyethyll-piperazine-N1-[2ethanesuffonic acid) (HEPES), N-12- acetamido)-2-aminoethane sulfonic acid (ACES), tris[-hydroxymethyll aminomethane (TRIS) and N-tris[hydroxymethyl]-methyl-3aminopropane suffonic acid (TAPS). The ammonium and alkali metal carbonates are also suitable. The preferred buffers are TRIS, sodium and potassium carbonate, bicarbonate and phosphate.

The dye component and the developer can be combined by mixing them directly on the hair of the user. If they are mixed on the hair, adding the dye component first is preferable. It is preferred to mix them in a mixing vessel for subsequent application to the hair.

12 The present invention also encompasses a Idt comprising at least two containers, one containing the dye component, the other the developer component, the two when mixed forming a composition of the present invention.

The method of the invention comprises applying the oxidative.dye composition of the present invention to the hair to be colored and allowing it to remain in contact with the hair until the desired hair color has been attained after which the composition is removed from the hair by rinsing.

Some typical examples of dye components and developer components are shown in Tables 1 and 2 which follow. Each of the components was mixed using conventional procedures. Table 1 records the color results on gray hair when a dye component of Table 1 was mixed With a developer of Table 2 in a 1 to 1 ratio, and the re- sultant dye composition was applied to human hair for 30 minutes employing the usual procedures for human hair dyeing.

1 13 1 T TABLE 1 EXAMPLES OF DYE FORMULATIONS Example 1 Example 2 Example 3 Example 4 Example 5 Cocamidopropyl betaine 7.00 7.00 Cocamphocarboxyglycinate 7.00 7.00 Cocoamphockpropionate 7.00 Oleic acid 5.00 1 5.00 5.00 5.00 Lauric acid 5.00 Octylpolyglycoside 5.00 8.00 1)ecylPolygiycoside 8.00 8.00 Dodecylpolyglycoside 5.00 Ammonium hydroxide 5.00 5.00 5.00 Monoethanolamine 3.00 Amirloethylpropanof 3.00 Soclum carbonate 2-50 Sodurn bicarbonate 0.50 Sodum citrate 0.50 EDTA 0.10 0.10 0.10 0.10 0.10 Sodurn suffite 0.10 0.10 0.10 0.10 0.10 Fragrance 0.50 0.50 0.50 0.50 0.50 1-acetoxy-2-methyl-naphthalene 1.20 0.20 0.50 2-methVI-11 -naphthol 0.20 4-metboxy-2-methyi-l-naphthol 1.20 4-amino-2-hydroxytoluene 0.60 0.10 0.10 2-methyi-S-hydroxyethylaminophenot 0.40 2-methyi-5-ethoxyethylaminophenoI 0.20 p-aminophenol 1.00 0.30 0.40 3-methyi-p-aminophencg 0.30 1-{(2-hydroxy-5-arnino)phenyWI,2- 1.20 ethanedol p-phenylenedamine 0.10 0.50 N.N-bis(2-hydroxyethyi)-p- 0.50 0.02 phenvienechamine 1-(ZS-criaminophenyi)-1.2-othanedioI 0.10 Water Q51:0100 QC0100 CS to 100 gs to 100 qs to 1W Developer Used 1 1 3 4 Cumulative KB Index 2.36 2.36 2.41 249 Color results on gray hair Dk burgundy Lt burgundy Bright red Copper red Red hrn 14 lq TABLE 1 COWnNUED Exa e 8 Exmoe 9 Example 10 Cocamidopmpyl betaine 7.00 7.00 Cocamphoca"3coycinate 7.00 7.00 Cocoamphodipropionate 7.00 CXeic acid 5.00 ú00 5.00 5.00 Lc acid 5.00 Oct 5.00 LOO Apolyglycoside DecylpolWycoside &oD 8.00 Dodecylpolygfde 5.00 Anum hWm)dde 5.00 5.W 5.00 Mnoethanolamine 3.00 An,i"thyfprppanot 3.00 Sodimn carbonate 2.50 Sodium bicarbonate 0.50 socrium d"e 0.50 EDTA 0.10 0.10 0.10 0.10 0.10 Sodium sulfite 0.10 0.10 0.10 0.10 0.10 Fragmnoe 0.50 O.W 0.50 0.50 0.50 1 -a oeloxy-2 Sy-k-M pht h a] en e 0.20 0.50 2-hy"-naphthot O.W 0.20 4-oxy-2-ml-naphthol 1.20 "phenylenedianne 0.02 0.10 0.10 M2-hyd"ethyW" 0.40 erKKriarrdne W2-MrwW24 02D nAenediaffine p-affinophenol 0.30 0.40 3-minophenol 0.50 0.30 1-[(2-hydS-anno)phenyq-1,2- 1.20 ethanediol p-phTyleriediarrdne 0.15 0.10 0.50 MN-Us(2-hydroxyethyl)-p. 0.02 Phenvfenediarrine 1-(ZS-darrinoúLe1,2-nediol 0.1 Water gs to 100 gstoloo Q5toloo gs to 100 to 100 Used 2 3 4 5 5 rr)ulative HLB Index Z39 241 246 2.5 2-53 RDeveloper ol M h WWr)dy M aubum Aubum bm Burgundy bm Cc Color mmfts on gray hair is M_ TABLE 1 CONTINUED Exarroe 11 ExarrOe 12 Exarffle 13 ExwOe 14 E 15 Oxarrido beWne 7.00 7.00 9999ycinate 7.00 7.00 Comafflonate 7.00 Oeic acid 5.00 5.00 5.00 5.00 Laudcadd 5.00 OcMpobgl de 5.00 8.00 Deopolygfde &oo 8.00 DPdwify 5.00 Amm6Lm hydr 5.W 5.00 5.00 Mmoaffine 3.00 Aninp 3.00 Sodum cade 2-50 Socium bicae 0.50 Socium d"e 0.50 EDTA 0.10 0.10 0.10 0.10 0.10 Sockum adfite 0.10 0.10 0.10 0.10 0.10 Fra 0.50 O.W O.W 0.50 O.W 1-""2-meffiWhatene 1.20 0.20 0.50 2-nl-mptfthol WM 4-met2-nl-na 1.20 Resadnol 0.60 Q10 0.10 n 0.40 3.mino-m 020 p-arri 1.00 0.30 0.40 3-n-dNH>arrinophenot 0.30 I-f(25-affino)1,2m 120 ethiol penecriaffine 0.10 0.50 Parrine 0.50 0.02 1-Z5-darri"p12.Wwned101 0.10 er gsto 100 Q5 to 100 gstoloo gs to 100 qs to 00 DeMoper Used 1 3 5 4 Cwdatrve HLB Index Z36 241.2.5 2-37 249 Wor on gray hair Ck a Brgft Co bm Warm ash bm 16 AWL, IF, TABLE 1 CONTINUED Example 16 Example 17 Example 18 Example 19 Example 20 Oleth-21 3.00 2.00 Laureth-23 2.00 2.50 4.00 Soytrimonnium Chloride 1.00 2.00 2.00 Oleic acid 4.50 2.00 1.20 1.50 2.00 Decylpolyglycoside 2.W 2.50 1.00 Ammonium hydroxide (28%) 5.00 4.90 5.00 8.00 Cl 8 Polycarbarnyl Poiyglycot 1.20 1.50 1.00 1.30 1.10 Ester Lauramide DEA 0.90 1.50 Fragrance 0.20 0.50 0.24 0.10 0.30 Monoethanolarnine 6.00 p-Phenylenediamine 0.50 0.05 0.60 Resorcinol 0.45 0.40 0.80 1.10 0.35 N,N-bis(2-hydroxyethyi)-p-pheny- 0.20 0.02 lenediamine 1-(2,5-diaminophenyl)-1,2- 1.40 1.30 ethanediol m-aminophenol 0.10 0.34 0.30 m-phenylenediamine 0.20 0.10 0.20 2-Methyl-l-Naphthol 0.50 0.70 3-Methyl-4-Aminophenol 0.80 0.90 Developer Used 7 7 7 7 6 Cumulative HLB Index 2.3 0.37 2.35 2.16 2.2 E-A Color Result Med Brown Lt Blonde Med Gold Brwrf Warm Brown Rich Auburn TABLE 11 ErLES OF DEVELOPERS 1 1 Example 1 Example 2 Example 3 Example 4: Example Example 6 Example 7 Hydrogen peroxide 3.00 6.00 9.00 3.00 6.00 6.00 6.00 Acr)dates Copolymer 1.50 1.50 2.50 1.00 3.50 Acrylates/steareth-20 1.50 1.50 1.50 5.0.0 3.50 MethacMate Cor)oRmer EDTA 0.10 0.10 0.10 0.10 0.10 Phosphoric acid 0.10 0.10 0.10 0.10 0.10 0.07 0.12 Nonoxynol-9 1.50 Nonoxynol-4 1.00 Oleft4 2.20 Oleth-21 2.20 Water 93.80 90.80 86.80 90.80 86.80 91.43 89.48 17

Claims (5)

WHAT IS CLAIMED IS:

1. In an aqueous oxidative hair dye composition comprising a coupler or mixture of couplers, a primary intermediate or mixture of primary intermediates, an oxidant and 5 water, wherein the improvement comprises (i) one primary intermediate is a compound of formula 1, R1 1 X Y I io wherein R1 is a C2 - C6 alkyl group or a C2 - C6 alkyl group in which one or more of the hydrogen atoms is replaced by a hydroxyl and X and Y are independently hydroxyl or amino groups, provided that, if one of X and Y is hydroxyl the other is amino, and the hair dye composition has a Cumulative HLB Index below about 2.5, or (ii) a primary in- termediate is a compound of formula It, is OH R2 R4 R311 R5 NH% 11 wherein R2 is a Ci C6 alkyl or hydroxyalkyl group and R3, R4, R5 and R6 are inde- pendently Cl - C6 alkyl or hydroxyl groups and the coupler, or one of the mixture of 20 couplers is a compound of formula Ill, 18 OH (11Z '1 R7 1 1;- ) 11ll R8 m where R7 and R8 are independently hydrogen, Cl -C6 alkyl or hydroxyalkyl, provided that one of R7 and R8 must be other than hydrogen, and the Cumulative HLB Index of io the dyeing medium is less than about 2.5.

2. The composition of Claim 1, wherein the oxidant is hydrogen peroxide.

3. The composition of Claim 1, containing from about 0.01% to about 10% by weight of is a primary intermediate of formula 1.

4. The composition of Claim 1, cohtaining from about 0.01 % to about 10% by weight of the coupler of formula Ill and from about 0.01 % to about 10% by weight of the primary intermediate of formula 11.

5. A method for the oxidative dyeing of hair comprising contacting the hair with a tinctorially effective amount of a hair dye composition in accordance with Claim 1 for a time sufficient to dye the hair.

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5. A method for the oxidative dyeing of hair comprising contacting the hair with a tinctorially effective amount of a hair dye composition in accordance with Claim 1 for a time sufficient to dye the hair.

19 Amendments to the claims have been filed as follows WHAT IS CLAIMED IS:

In an aqueous oxidative hair dye composition comprising a coupler, at least one primary intermediate, an oxidizer, water and one or more surfactants, wherein the improvement comprises (i) one primary intermediate is a compound of formula 1, X R1 1 I wherein R, is a C2-C6 alkyl group or a C2-C6 alkyl group in which one or more of the hydrogen atoms is replaced by a hydroxyl and X and Y are independently hydroxyl or amino groups, provided that, if one of X and Y is hydroxyl the other is amino, and the hair dye composition has a Cumulative HLB Index below about 2.5, or (ii) a primary intermediate is a compound of formula II, R2 R4 R3j 1 -R5 OH HN 1 R6 H wherein R2 is a Cl-C6 alkyl or Cl-C6 hydroxyalkyl group and R3, R4, Rs and R6 are independently hydrogen, Cl-C6 alkyl or Cl-C6 hydroxyalkyl, with the proviso that at least one of R3 and R5 is hydrogen and the coupler is a compound of formula Ill, 2P R7 OH R8 III where R7 and R8 are independently hydrogen, C 1 -C6 alkyl or C 1 -C6 hydroxyalkyl, provided that one of R7 and Rg must be other than hydrogen, and the hair dye composition has a Cumulative HLB Index of less than about 2.5.

2.

The composition of Claim 1, wherein the oxidizer is hydrogen peroxide.

3.

The composition of Claim 1, containing from about 0.0 1 % to about 10% by weight of a primary intermediate of formula I.

4. The composition of Claim 1, containing from about 0.01% to about 10% by weight of the coupler of formula III and from about 0. 0 1 % to about 10% by weight of the primary intermediate of formula Il.