SK84299A3 - Hair coloring compositions - Google Patents

Abstract

A hair coloring composition comprising: (a) from about 0.0003 moles (per 100 g of composition) to less than about 0.09 moles (per 100 g of composition) of an inorganic peroxygen oxidising agent; and (b) an oxidative hair coloring agent; wherein the pH of each of (a) and (b) is in the range of from about 1 to about 6 and wherein the combined mixture of (a) and (b) has a pH in the range of from about 1 to about 6. The products can provide excellent hair coloring and in-use efficacy benefits including excellent initial color and good wash fastness in combination with reduced hair damage at low pH.

Description

Hair dye products

Technical field

BACKGROUND OF THE INVENTION The present invention relates to hair dye compositions and methods for coloring hair, and more particularly to hair dye compositions which comprise an inorganic peroxygen oxidizing agent in conjunction with a hair dye oxidizing agent at an acid pH of between 1 and 6.

BACKGROUND OF THE INVENTION

People's wish to change their hair color is not just about modern times. Ever since *

In the Roman Empire, the color of human hair was routinely changed to accommodate changes in different forms and styles. However, achieving the precise initial colors that are required for hair for a desired period of time remains a more or less unattainable goal. The difficulty in developing hair coloring compositions that can deliver accurate long lasting dyes is partly attributable to the inherent structure of the hair itself and partly to the conditions under which effective dyeing methods are performed.

In general, the condition and structure of human hair is not dependent on the length of the hair and the condition of its hair tips. Human hair is subjected to various chemical and mechanical effects such as combing, brushing, shampooing, heat treatment, permanent waving, exposure to other factors such as weathering and sun exposure. Hair, and especially hair ends, generally exhibit greater signs of damage as compared to new hair growth in the scalp area. This damage can lead to hair color irregularity if the hair is colored with inadequate amounts and quality of hair dye products delivered according to the length of the hair and its ends.

Colored hair is required to be resistant to fading caused by washing (also known as color fastness to washing), sweating, hairspray, and other external factors such as exposure to the sun and other factors to keep the color adequately the time that is predetermined. In addition to damaging the hair, improper staining can lead to greater color fading in damaged hair portions and consequently to irregularly colored hair portions over time. In addition to the problems generally associated with dyeing human hair, dyeing systems need to avoid detrimental effects on the hair and skin of the user, such as hair brittleness, brittleness or skin irritation or skin staining (skin staining).

Thus, it is desirable to develop a hair coloring agent that acts to reduce fading, provides improved wash and wash resistance during the conventional wash regimen, is capable of delivering de facto consistent hair coloring results while reducing skin irritation, reducing the possibility of spotting on the skin, the harmful effects on the user's hair are reduced, and also to develop an easy method for use in applying such hair coloring composition.

For many years, great efforts have been made to eliminate many of the problems associated with coloring human hair. A variety of hair coloring approaches have been developed, including direct-effect colors, natural colors, metal-based colors and oxidative colors.

To dye human or animal hair using oxidative dye technology, the hair is generally treated with a mixture of hair dye oxidizing agents and an oxidizing agent. The most commonly used oxidizing agent is hydrogen peroxide. However, in addition to oxidizing oxidative coloring agents, hydrogen peroxide can also act on the hair to solubilize and decolour the colored melanin component in the hair, leading to undesirable effects on hair quality, brittleness, brittleness and damage. This is partly due to the conditions of normal peroxide exposure, partly also to hair dyeing when done at higher pH values (higher than pH 9), prolonged exposure time (from 10 to 60 minutes) and relatively high oxidation solution concentration (between 20% by volume up to 40% by volume of oxygen (i.e. 6% by weight to 12% by weight) to achieve sufficient delivery of the effective oxidant dye.

Various hair coloring agents and peroxygen oxidizing agents can be used to provide the hair with a variety of hair dyes. However, substantial improvements in color saturation, color development, precise initial color consistency, improved color fastness to washing, improved hair condition and less hair damage are required.

Accordingly, there is a need to find hair coloring oxidants which dye effectively but avoid or reduce hair damage, which can dye hair effectively and avoid or reduce skin irritation, which avoid skin staining, or at least reduce blemish on the user's skin.

Typically, hair coloring compositions containing oxidative hair coloring agents are formulated at high pH (from pH 9 to pH 12) and typically contain inorganic peroxygen oxidizing agent, peroxide activating agents, and a variety of adjuncts in addition to hair coloring agents. cosmetic, coloring and peroxygen oxidizing agent stabilizing agents. It is also known that improved oxidation of oxidative hair colorants can be achieved by using a hair swelling agent (HSA). This HSA improves the oxidation and dyeing process by swelling the hair fibers to achieve both diffusion of the peroxygen oxidizing agent and the oxidative hair dye into the hair and allows for faster, more penetrative oxidative dyeing and hence better hair dyeing. Usually, the HSA is in the form of an aqueous (basic) solution containing an ammonia source such as ammonium hydroxide. However, ammonia can cause skin irritation and, moreover, it has an undesirable odor and can have a tear-forming effect.

Thus, it would be desirable to provide a hair coloring composition having desirable odor properties, containing oxidative hair coloring agents, and providing improved coloring effect and / or accelerating hair coloring without the need for HSA.

It has been found that the combination of inorganic oxidizing peroxygen compositions with one or more oxidative hair coloring agents at a pH below the internal hair pH, between pH 1 to pH 6 and possibly additional oxidizing agents in the hair colorant, can provide an excellent initial hair color along with improved color and color fastness to wash hair over time, desired color saturation and fresh shine, reduces hair damage, reduces skin irritation, reduces skin formation and staining is more effective. Furthermore, it has been found that the color development efficiency (color change) with the aid of the inorganic peroxygen oxidizing agents and the particular oxidative hair coloring agents of the present invention is improved under the lower pH conditions of the present invention. In addition, it has been found that the hair dye compositions of the present invention can provide excellent dyeing results with minimal hair damage at low pH values (at pH 1-6).

SUMMARY OF THE INVENTION

It is an object of the present invention to provide hair coloring compositions at low pH values that help to combine improved hair coloring properties such as longer color duration (reduced color fading), initial color development, less color consumption and better color consistency for all hair types . Hair types as defined herein mean hair of varying age and condition, i. completely unaffected by various treatments, gray, damaged, permanently discolored, etc.

It is a further object of the present invention to provide low pH hair coloring compositions that reduce skin irritation and / or skin staining as compared to conventional high pH systems, and which have a minimal deleterious effect on hair fibers and reduce spotting on the hair. skin in conjunction with an acceptable aroma.

Yet another object of the present invention is to provide hair coloring compositions at low pH values that exhibit improved effect (improved color development). Developing a color as defined herein means a color change in hair dye, which is defined by the term Delta E, as defined in the Experimental Part below, which is the part of this material hereinafter. Yet another object of the present invention is to provide hair coloring compositions with reduced skin and / or hair damage that can occur during color development (as compared to conventional high pH systems) in conjunction with improved color fastness and consistency by using less color and / or less oxidizing agent.

It has been found that the above objects of the present invention may be suitable at low pH values for the hair coloring compositions of the present invention.

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Further, conventional high color pH hair dye compositions typically comprise at least two separately packaged components, typically an oxidizing agent (low pH) and an oxidizing hair coloring agent (high pH). These separately packaged ingredients are mixed at high pH just before application to the hair. This mixing step can be problematic for the user. Typically, conventional hair dye compositions containing an oxidizing agent and an oxidizing hair dye composition need to be used immediately after mixing due to degradation of the resulting dye composition. If there is any excess of the mixed colorant after application to the hair, it is no longer usable. It has been found that the oxidizing agent (s) and dyes of the present invention can be mixed into individually packaged low pH compositions with improved stability compared to conventional high pH oxidative dye systems. The single-packed low pH dye compositions of the present invention are suitable for use in a multiple application format (i.e., the consumer may use a single package for multiple color applications over time). It has also been found that at low pH values both the oxidizing agent and the oxidative hair coloring agents are stable over time and can be stored as such.

It is another object of the present invention to provide individually packaged hair coloring compositions that act quickly, are easy to use, and are reusable.

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It is a further object of the present invention to provide hair coloring compositions which comprise a stable, separately packaged oxidizing agent (s) and an oxidizing hair coloring agent (s) that remain stable at low pH values, even when if stored individually as well as mixed.

All percentages herein are by weight, based on the final compositions, unless otherwise indicated.

Accordingly, the present invention provides a hair coloring composition suitable for human or animal hair.

According to one aspect of the present invention there is provided a hair coloring composition comprising:

(a) from 0.0003 mol (per 100 g of composition) to less than 0.09 mol (per 100 g of composition) of an inorganic peroxygen oxidizing agent; and (b) an oxidative hair coloring agent;

wherein the pH of each of (a) and (b) is in the range of 1 to 6 and the combined mixture of (a) and (b) has a pH in the range of 1 to 6.

It is understood that the weight percent of the components in a given composition are expressed to be relative to the total composition and the composition is included in a form that is for its own use.

According to another aspect of the invention, there is provided:

A method of coloring hair, wherein the hair coloring composition is present in a single unitary package and is applied directly to the hair, wherein the hair coloring composition comprises:

(a) from 0.0003 mol (per 100 g of composition) to less than 0.09 mol (per 100 g of composition) of an inorganic peroxygen oxidizing agent; and (b) an oxidative hair coloring agent;

wherein the pH of each of (a) and (b) is in the range of from 1 to 6 and the combined mixture of (a) and (b) has a pH in the range of from 1 to 6.

According to a further aspect of the invention there is provided:

A hair coloring method wherein the hair coloring agent is present as separately packaged components (a) and (b) and wherein the hair coloring agent comprises:

(a) from 0.0003 mol (per 100 g of composition) to less than 0.09 mol (per 100 g of composition) of an inorganic peroxygen oxidizing agent; wherein the pH at (a) is in the range of pH 1 to pH 6; and (b) an oxidative hair coloring agent wherein the pH at (b) is in the range of pH 1 to pH 6;

wherein each of components (a) and (b) is stable at pH values ranging from pH 1 to pH 6, and when the combined mixture of (a) and (b) is stable over time and has a pH value ranging from pH 1 to pH 6th

According to a further aspect of the present invention there is provided a hair coloring composition comprising:

(a) an inorganic peroxygen oxidizing agent; and (b) an oxidative hair coloring agent;

wherein the pH of each of components (a) and (b) is in the range of 1 to 6 and the combined mixture of (a) and (b) has a pH in the range of 1 to 6, wherein (a) and (b) in a form which is already for its own use, and wherein the molar amount (a) is from 0.0003 mol (per 100 g of composition) to less than 0.09 mol (per 100 g of composition).

As used herein, the term "hair" is intended to be treated with either "living", i. on a living body or they may be "inanimate", i. on a wig, hairpiece or other clumps or tufts of inanimate hair fibers, such as those used in fabrics and fabrics. Mammalian hair is preferred, preferably human hair. Wool, fur and other melanin-containing fibers are also suitable substrates for the compositions of the present invention.

As used herein, the term " hair coloring agent " means a very broad field in which compositions comprising the combinations of low pH (from pH 1 to pH 6) compositions herein are included, the compositions comprising an inorganic peroxygen-based oxidizing agent for the hair. dyeing and oxidizing dyeing agent. However, it also relates to complex compositions which contain other ingredients, which may or may not be active ingredients. Thus, the term "hair coloring agent" refers to the application of compositions which contain, in addition to a mixture of active oxidizing agents and coloring agents, also other agents, which may be, for example, oxidizing aids, masking agents, stabilizers, thickeners, buffers, buffers, carriers, surfactants, solvents, antioxidants, polymers, non-oxidizing dyes and conditioners.

As discussed above, the hair coloring compositions of the present invention comprise from 0.0003 mol (per 100 g of composition) to less than 0.09 mol (per 100 g of composition) of an inorganic peroxygen-based oxidizing agent (s) in conjunction with an oxidizing agent. a hair coloring agent (b), wherein the pH of each of components (a) and (b) is in the range of from 1 to 6, and wherein the pH of the combined mixture of components (a) and (b) is in the range of pH 1 It is preferred that the pH of either (a) and / or (b) is in the range of pH from 1.5 to 5.8, more preferably from pH

1.8 to pH 5.5 and most preferably from pH 2 to pH 5 and especially from pH 3.5 to pH

4.5 and wherein the preferred pH of the combined mixture of components (a) and (b) is in the range of from pH 1.5 to pH 5.8, more preferably from pH 1.8 to pH 5.5, and most preferably from pH 2 to pH 5, and a pH of from 3.5 to 4.5 is particularly preferred. In addition to said inorganic peroxygen oxidizing agent, the compositions may optionally contain (among other ingredients) a tableted organic peroxyacid oxidizing agent. Organic peroxyacid, as used herein, refers to the field comprising any organic peroxyacid substances that may act either alone or in conjunction with a peroxygen oxidizing agent to oxidize dye precursors.

Oxidizing dyes and hair dyeing methods

It is well known in the art that for a truly successful dyeing of human or animal hair with oxidative dyes, it is generally necessary to treat the hair with a mixture of an oxidizing agent and an oxidizing hair dye. As discussed herein, the most commonly used oxidizing agent is hydrogen peroxide.

Hydrogen peroxide has a pKa in the range of 11.2 to 11.6 and is generally used as an oxidizing agent in dyeing at pH values of pH 9 to pH 12. Surprisingly, it has now been found that improved color development occurs when combined with improved with respect to color fastness, with low pH oxidation systems of the present invention, at pH values in the range of from 1 to 6, preferably from pH 1.5 to pH 5.8, more preferably from pH 1.8 to pH 5, 5, most preferably from pH 2 to pH 5 and then weigh from pH 3.5 to pH 4.5.

Inorganic oxidizing agents

The compositions of the present invention comprise as an essential feature at least one inorganic oxidizing agent (hereinafter referred to as "inorganic peroxygen oxidizing agent"). This inorganic peroxygen oxidizing agent should be safe and effective for use in the compositions herein.

It is preferred that these inorganic peroxygen oxidizing agents suitable for use herein are soluble in the compositions of the present invention when in liquid form or in a form appropriate to the method of use. Preferably, the inorganic peroxygen oxidizing agents suitable for use herein are water-soluble. Water-soluble oxidizing agents are defined herein to have a solubility of 10 g in 1000 ml of deionized water at 25 ° C ("Chemistry" C.E.Mortimer, 5th edition p. 277).

Inorganic peroxygen oxidizing agents for use herein are generally inorganic peroxygen species capable of providing peroxide in aqueous solution. Inorganic peroxygen oxidizing agents are well known in the art and include, for example, hydrogen peroxide, inorganic alkali metal peroxides such as sodium periodate, sodium hypobromite and sodium peroxide, and inorganic perhydrate salts of oxidizing compounds such as alkali metal salts, perborates, percarbonates , perphosphates, persilicates, persulphates and the like. These inorganic perhydrate salts may be incorporated as monohydrates, tetrahydrates, etc. If desired, a mixture of two or more of such inorganic peroxygen oxidizing agents may also be used. Bromates and iodates are suitable for use herein, with bromates being preferred. Highly preferred for use in the compositions herein is hydrogen peroxide.

As has now been found, under the low pH conditions of the present invention, it is possible to deliver both improved color development, color consistency, color fastness and color intensity compared to conventional high pH systems (using equivalent amounts of peroxide and dyes) as well as equivalent color development (described in more detail in the Experimental Data Section in Delta E terms) compared to conventional high pH systems using less inorganic peroxygen oxidizing agent (up to 75% less) and the equivalent color development provided compared to conventional high pH systems where the systems use considerably less oxidizing agent to dye the hair (up to 50% less). Thus, the low pH hair coloring compositions of the present invention can be formulated such that they reduce the risk of hair damage, skin irritation, and skin staining. In addition, the low pH hair coloring compositions of the present invention may be formulated without ammonia, i.e., no odor of ammonia, or negative effects on the skin associated with these compositions.

Said inorganic peroxygen oxidizing agent is present in the compositions of the invention in a molar amount of from 0.000294 * mol (per 100 g of composition) to less than 0.0882 mol (per 100 g of composition), preferably the inorganic peroxygen oxidizing agent is present in the from 0.0003 mol to 0.08 mol, more preferably from 0.0003 mol to 0.06 mol, even more preferably from 0.0003 mol to 0.04 mol, most preferably from 0.0003 mol to 0.03 mol in particular from 0.0003 mol to 0.02 mol, and most preferably from 0.0003 mol to 0.015 mol (per 100 g of composition).

In preferred compositions of the present invention, the inorganic peroxygen oxidizing agent is present in an amount of from 0.01% to less than 3%, preferably from 0.01% to 2.5%, more preferably from 0.01% to 2%, even more preferably from 0.01% to 1%, most preferably from 0.010% to 0.8%, especially from 0.01% to 0.55% and then in particular from 0.01% to 0.5% by weight of the composition.

Tableted organic peroxyacid

The compositions of the invention may optionally contain one or more tableted organic peroxyacid oxidizing agents in addition to the inorganic peroxygen oxidizing agent (or inorganic peroxygen oxidizing agents).

Suitable optional organic peroxyacid oxidizing agents for use in the coloring compositions of the present invention include those having the general formula:

R-C (O) OOH wherein R is selected from the group consisting of saturated or unsaturated, substituted or unsubstituted straight or branched chain, alkyl, aryl or alkaryl of one to fourteen carbon atoms.

A group of organic peroxyacid compounds suitable for use herein are amide substituted compounds of the following general formula:

R ¹ —C — N — R ² —C —OOH R ¹ - N - C — R ² - C - OOH

II. II. II

OR ⁵ O or R ⁵ OO wherein R ¹ is a saturated or unsaturated alkyl or alkaryl group, or an aryl group having from one to fourteen carbon atoms, R ² is a saturated or unsaturated alkyl or alkaryl group, or an aryl group having from one to 14 carbon atoms; fourteen carbon atoms, and R ⁵ is hydrogen or a saturated or unsaturated alkyl or alkaryl group, or an aryl group having from one to ten carbon atoms. Amide substituted organic peroxyacid compounds of this type are described in EP-A-0,170,386.

Other organic peroxyacid oxidizing agents include peracetic acid, pemanoic acid, nonylamidoperoxycaproic acid (NAPCA), perbenzoic, n-chlorobenzoic, diperoxyisophthalic, mono-peroxyphthalic, peroxylauric, hexanesulfonylperoxypropionic acid, N, Nphthaloyanebioperbenzoic acid, , diacyl peroxides and tetraacyl peroxides, in particular diperoxydodecanediolic acid, diperoxytetradecanediolic acid and diperoxyhexadecanediolic acid and derivatives thereof. Diperazenaonic acid, monoa diperbrasylic acid and N-phthaloylaminoperoxicaproic acid and derivatives thereof are also suitable for use herein.

For use in the compositions herein, the organic peroxyacid oxidizing agents tableted should be safe and effective. It is preferred that the tableted organic peroxyacid oxidizing agents suitable for use herein be soluble in the compositions of the present invention as long as the compositions are in liquid form and are intended to be used in such liquid form. Preferably, organic peroxyacid oxidizing agents suitable for use herein are water soluble. Water-soluble tableted organic peroxyacid oxidizing agents as defined herein means reagents having a solubility of up to 10 g in 1000 ml of deionized water at 25 ° C ("Chemistry" C.E.Mortimer, 5th Edition, p. 277).

Preferred peroxyacids suitable for use herein are selected from peracetic acid, pernanoic acid, and mixtures thereof.

The tableted organic peroxyacid oxidizing agent disclosed herein is present in a molar amount of from 0.0001 mol to 0.1 mol (per 100 g of composition), more preferably from 0.001 mol to 0.05 mol, most preferably from 0.003 mol to 0, 04 mol, and in particular from 0.004 mol to 0.03 mol, per 100 g of hair colorant.

The tableted oganic peroxyacid oxidant disclosed herein is preferably present in an amount of from 0.01% to 8%, more preferably from 0.1% to 6%, most preferably from 0.2% to 4% and especially from 0% to 0%. , 3% to 3% by weight, based on the weight of hair coloring compositions. The weight ratio of inorganic peroxygen oxidizing agent to tableted organic peroxyacid is preferably in the range from 0.0125: 1 to 500: 1, more preferably from 0.0125: 1 to 50: 1.

In addition to the inorganic peroxygen oxidizing agents and optional additional tableted organic peroxyacid oxidizing agents that are suitable for use herein, the compositions of the invention may optionally contain additional organic peroxides such as urea peroxide, melamine peroxide, and mixtures thereof. The amount of organic peroxide present is in the range from 0.01% to 3%, preferably from 0.01% to 2%, more preferably from 0.1% to 1.5% and most preferably from 0.2% to 1% by weight, % by weight of the composition.

Hair coloring agents

One of the basic features of the low pH hair coloring compositions of the present invention is that they comprise an oxidative hair coloring agent. Such oxidative hair coloring agents are used in conjunction with the peroxide-based oxidation systems of the present invention to formulate stable, partially stable, semi-permanent, or transient low pH hair coloring agents.

Permanent hair colorants are defined herein as once applied to the hair and are substantially resistant to washing (wash). Partially stable hair coloring agents are defined herein as compositions that are substantially removed from the hair up to 24 washes. Semi-permanent hair colorants are defined herein as once applied to the hair and are substantially removed up to 10 washes. Transient hair coloring agents are defined herein as being once applied to the hair and substantially removed for up to two washes. These different types of hair coloring compositions can be formulated via specific combinations of oxidizing agent and / or dyes in varying amounts and ratios. Washing is defined here as the way in which color is removed from the hair over time under normal hair washing regimes. Color fastness as defined herein means the staining resistance of colored hair. Color fastness as defined herein is determined in terms of relative color change on dyed hair (Delta E) over several hair washes (shampooing). Essentially, hair removal is defined herein as a color change on dyed hair (Delta E) greater than 2 to 10 hair washes.

The concentration of each hair coloring oxidant in the compositions of the present invention is from 0.001% to 3% by weight, preferably from 0.01 to 2% by weight.

The total level of combined hair coloring oxidizing agents in the composition of the present invention is from 0.001% to 5%, preferably from 0.01% to 4%, more preferably from 0.1% to 3%, most preferably from 0.1% to 5%. 1% by weight.

Typically, in conventional hair coloring compositions, the total level of oxidizing agents present in the composition ranges from 0.2% to 3.5% by weight. Thus, the compositions of the present invention exhibit improved hair coloring properties such as initial color development and initial color consistency in conjunction with improved color fastness for extended periods of time compared to conventional high pH systems having similar color levels. Color consistency, as used herein, means both the relative predictability of the initial color development and the improved color fastness over time for different hair types.

The efficiency of said oxidizing dyes is improved at low pH, so that the compositions of the present invention are of great value for delivering good high-intensity dyes (dark colors) using less dye. Particularly good hair dyeing results in combination with equivalent color development (as compared to high pH systems) can be achieved using the inorganic peroxygen oxidizing agents of the present invention and substantially less dye than conventional high color hair dye compositions.

Thus, according to another aspect of the present invention, a hair coloring composition is provided comprising:

(a) from 0.0003 mol (per 100 g of composition) to less than 0.09 mol (per 100 g of composition) of an inorganic peroxygen oxidizing agent; and (b) an oxidative hair coloring agent;

(c) a diluent suitable for application to the hair;

wherein the pH of each of (a) and (b) is in the range of 1 to 6, and wherein the pH of said composition is in the range of 1 to 6.

As mentioned hereinabove, it has also been found that combining inorganic peroxygen oxidizing agents with a low pH oxidizing hair coloring agent is very valuable for imparting excellent hair coloring properties along with a reduced range of hair damage, skin irritation and skin staining. , in conjunction with an improved aromatic profile (as compared to conventional high pH formulations). Another useful feature of the low pH hair coloring compositions of the present invention is that the level of skin staining is reduced when using the compositions as compared to conventional high pH compositions.

According to a further aspect of the present invention there is provided a hair dye composition capable of imparting a slightly titian (golden brown) color to a light brown hair comprising 40% gray hair, comprising:

(a) from 0.0003 mol (per 100 g of composition) to less than 0.09 mol (per 100 g of composition) of an inorganic peroxygen oxidizing agent;

(b) an oxidizing hair coloring agent; and (c) a diluent suitable for application to the hair;

wherein the pH of components (a) and (b) is each in the range of 1 to 6 and wherein the pH of said composition is in the range of 1 to 6 and wherein the change in skin staining level after application of the product (Delta E) is less than 4; preferably less than 3, more preferably less than 2.7. Light brown hair having a 40% gray hair coverage is referred to in terms L, a, b so that the "L" value corresponds to the range from 35 to 37, the "a" value corresponds to the range from 4.5 to 5.5 and "b" ”Value ranges from 11.5 to 12.7.

Without wishing to be bound by theory, it is likely that these improvements (with respect to reduced skin irritation and / or staining) resulting from the combination of (a) less color and low pH in the systems are likely to result; (b) reducing p-phenylenediamine (PPD) contact hypersensitivity at low pH values (high PPD levels showed contact hypersensitivity at high pH but not at low pH); (c) eliminating the formation of nitrobenzene contact sensitivities (which occur with high pH formulations); (d) a reduced level of skin staining at low pH as compared to high pH, and; (e) reduced skin irritation and negative odor effects as a result of ammonia elimination and the use of alternative oxidizing agents in the dye compositions of the invention having a low pH.

Oxidative methods of hair dyeing

Any oxidative hair coloring agent may be used in the compositions of the present invention. Typically, without being limited thereto, oxidative hair coloring agents consist essentially of at least two components, collectively referred to as color-forming intermediates (or precursors). The color-forming intermediates can be reacted in the presence of a suitable oxidizing agent to form a colored molecule.

Coloring intermediates which can be used in oxidative hair dyes include, for example: aromatic diamines, aminophenols, miscellaneous heterocycles, phenols, naphthols, and various derivatives thereof. These colorforming intermediates can be broadly classified as: primary intermediates and secondary intermediates. The primary intermediates, also known as oxidation dye precursors, are chemical compounds that become activated upon oxidation and can then react together with each other and / or with coupling agents to form colorant dye complexes. Secondary intermediates, also known as color modifiers or coupling agents, are generally colorless molecules that can form colors in the presence of activated precursors / primary intermediates and are used with other intermediates to produce specific color effects or to stabilize the color.

Primary intermediates for use in the compositions and methods herein include, for example: aromatic diamines, polyhydric phenols, aminophenols, and derivatives of these aromatic compounds (e.g., N-substituted amine derivatives and phenol ethers). Such primary intermediates are generally colorless molecules prior to oxidation.

Without wishing to be bound by any particular theory, it is believed that the process of developing color from said primary intermediates and secondary linking compounds generally involves a sequential stepwise sequence by which the primary intermediates become activated (oxidized) and subsequently coupled to a coupling agent to form a dimerized, conjugated dye component, which in turn can be coupled to another "activated" primary intermediate to form a trimeric conjugated dye molecule.

Chemistry of oxidative hair coloring through pH

Without wishing to be bound by any particular theory, it is generally known that conventional oxidative dyeing typically occurs between oxidative precursor molecules, oxidative linker molecules, and a peroxygen oxidizing agent at high pH (8-10). Typical precursors contain 1,4-disubstituted benzene derivatives and typical coupling agents include 1,2- or 1,3-disubstituted benzene derivatives.

It is generally accepted that the pH within the hair, here we mean the human hair, is a pH of 5.5 to 6 (C.R. Robbins, Chemical and Physial Behavior of Human

Hair, 2nd Edition, p. 157) and that the hair has an inherent buffering capacity within a given pH range.

Surprisingly, it has now been found that oxidative hair dye at pH 6 or less, with oxidizing agents in a molar amount of from 0.000294 mol (per 100 g of composition) to less than 0.0883 mol (per 100 g of composition) of an inorganic peroxygen oxidizing agent and oxidative hair coloring agents are very valuable for delivering excellent initial hair color in conjunction with improved color and color fastness to color hair wash over time, showing superior properties in terms of desired color saturation and vividness, reduced hair damage, reduced irritation skin, reduced skin staining and more effective staining. In addition, it has been found that the color development efficiency (i.e., the improvement in color change) with the inorganic peroxygen oxidizing and hair coloring agents of the present invention is better under the low pH conditions of the present invention. In addition, it has further been found that the low pH hair coloring compositions of the present invention can give these excellent hair coloring results with minimal hair damage.

It has also been found that at a pH level below pH 6, preferably from pH 1.5 to 5.8, more preferably from pH 1.8 to 5.5, most preferably from pH 2 to pH 5, and in particular from pH 3 5 to pH 4.5, further improvements in color development can be achieved.

Oxidizing color precursors

In general, oxidative dye primary intermediates include those monomeric substances which, when oxidized, form oligomers or polymers having extended conjugated electron systems in their molecular structure. Because the resulting oligomers and polymers have a new electron structure, they are shifted in their electron spectrum into the visible region and become discolored. Oxidative primary intermediates capable of forming colored polymers include substances such as e.g. aniline, which has a single functional group and which forms a series of conjugated imines and hydroquinone dimers, trimers, etc., which range from green to black in oxidation. Compounds such as β-phenylenediamine, which has two functional groups, are capable of oxidative polymerization to produce higher molecular weight colored substances having extended conjugated electron systems. For the low pH compositions of the present invention, oxidation dyes known in the art can be used. A representative list of primary intermediates and secondary coupling agents suitable for use herein can be found in Sagarina, " Cosmetic Science and Technology ", Interscience, Special Ed., Vol. 2, p. 308-310. It will be understood that the primary intermediates detailed below are intended to be exemplary only and do not imply any limitation upon the compositions and methods herein.

Typical aromatic diamines, polyhydric phenols, aminophenols, and derivatives thereof, which are mentioned herein as primary intermediates, may also have additional substituents on the aromatic ring, e.g. halogen, aldehyde, carboxylic acid, nitro, sulfonic acid and substituted or unsubstituted hydrocarbon groups, as well as additional substituents on the amine nitrogen and phenol oxygen, e.g. substituted or unsubstituted alkyl or aryl groups.

Examples of suitable aromatic diamines, aminophenols, polyhydride phenols and derivatives thereof include compounds of formulas I, Π and III, which are as follows:

wherein Y is hydrogen, halogen, (e.g., fluorine, chlorine, bromine or iodine), nitro, amino, hydroxyl,

ABOUT

II - CH

-COOM or SO3M (where M is hydrogen or an alkali or alkaline earth metal, ammonium or substituted ammonium group where one or more hydrogen atoms are replaced by an alkyl or hydroxyalkyl radical having 1 to 3 carbon atoms), wherein R1, R2 R 3 and R 4 are the same or different from each other and are selected from the group consisting of hydrogen, C 1 -C 4 alkyl or alkenyl and C 6 -C 8 aryl, alkaryl or aralkyl and R 5 is hydrogen, C 1 -C 4 unsubstituted or substituted alkyl or alkenyl, wherein the substituents are selected from those set forth for Y, or C 6 -C 9 unsubstituted or substituted aryl, alkaryl or aralkyl, wherein the substituents are selected from those set forth for Y above. Then, the prodrugs of formula (I) are amines, here they can be used in the form of peroxide-compatible salts as mentioned, wherein X is a peroxido-compatible anion of the type as detailed above. According to the general formula, salts are understood to include those having mono-, di- and tri-negative anions.

Specific examples of compounds of formula I include, for example, phenyenylenediamine, m-phenylenediamine, p-phenylenediamine, 2-chloro-p-phenylenediamine, 2-iodo-p-phenylenediamine, 4-nitro-o-phenylenediamine, 2-nitro-p-phenylenediamine , 3,5-triaminobenzene, 2-hydroxy-p-phenylenediamine, 2,4-diamine benzoic acid, sodium 2,4-diamine benzoate, calcium di-2,4-diamine benzoate, ammonium 2,4-diaminobenzoate, trimethylammonium-2,4 -diaminobenzoate, tri- (2-hydroxyethyl) ammonium-2,4-diamine benzoate, 2,4-diamine benzaldehyde carbonate, 2,4-diamine-benzenesulfonic acid, potassium 2,4-diamine-benzenesulfonate, N, N-diisopropyl-p-phenylenediamine hydrogen carbonate, N-carbonate, -p-phenylenediamine, Netyl-N '- (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-bromomethyl) -p-phenylenediamine, 2-phenyl-p20 phenylenediamine laurate, 4- (2,5-diaminephenyl) benzaldehyde, 2 -be nzyl-p-phenylenediamine acetate, 2- (4-nitrobenzyl) - _N -p-phenylenediamine, 2- (4-methylphenyl) -p-phenylenediamine, 2- (2,5-diaminephenyl) -5-methylbenzoic acid, methoxyparaphenylenediamine, dimethyl - p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 2-methyl-5-methoxy-phenylenediamine, 2,6-methyl-5-methoxy-p-phenylenediamine, 3-methyl-4-amino-N, N-diethylaniline, N, N-bis- (B-hydroxyethyl) -p-phenylenediamine, 3-methyl-4-amino-N, Nbis (B-hydroxyethyl) aniline, 3-chloro-4-amino-N, N-bis ( B-hydroxyethyl) aniline, 4-amino-N-ethyl-N- (carbomethyl) aniline, 3-methyl-4-amino-N-ethyl-N- (carbmethyl) aniline, 4-amino-N-ethyl- (B-piperidonoethyl) Aniline, 3-methyl-4-amino-N-ethyl- (B-piperidonoethyl) aniline, 4-amino-N-ethyl-N- (B-morpholinoethyl) aniline, 3-methyl-4-aminoN-ethyl-N- ( B-morpholinethyl) aniline, 4-amino-N-ethyl-N- (B-acetylaminoethyl) aniline, 4 amino-N- (B-methoxyethyl) aniline, 3-methyl-4-amino-N-ethyl-N- (Bacetylaminoethyl) aniline, 4-amino-N-ethyl-N- (B-mesylaminoethyl) aniline, 3-methyl-4-amino-N-ethyl-N- (B-mesylaminoethyl) aniline, 4-amino-N-ethyl-N- ( B-sulfonyl oetyl) aniline

3-methyl-4-amino-N-ethyl-N- (B-sulfoethyl) aniline, N- (4-aminophenyl) morpholine, N- (4aminophenyl) piperidine, 2,3-dimethyl-p-phenylenediamine, isopropyl-p -phenylenediamine, N, N-bis- (2-hydroxyethyl) -p-phenylenediamine sulfate.

In the highly preferred compositions of the present invention, the compounds of formulas Ia and Ib are preferred:

(Ia) and the salt except when R 1 = R 2 = Me, Et

νη ₂ (Ib) and a salt thereof out of the case in which R = _R2 = Me wherein Y is hydrogen, halogen (e.g. fluoro, chloro, bromo or iodo), nitro, amino, hydroxyl,

ABOUT

II - CH

-COOM or -SO 3 M (where M is hydrogen or an alkali or alkaline earth metal, ammonium or substituted ammonium, wherein one or more hydrogen atoms on the ammonium ion is replaced by an alkyl radical of 1 to 3 carbon atoms), wherein R 1, R ₂ , R 3 and R 6 are the same or different from each other and are selected from the group consisting of hydrogen, C 1 -C 4 alkyl or alkenyl and C 6 -C 5 aryl, alkaryl or aralkyl, and R 1 is hydrogen, C 1 -C 4 unsubstituted or substituted alkyl or alkenyl wherein the substituents are selected from the group indicated above as Y, or C 6 -C 9 unsubstituted or substituted aryl, alkaryl or aralkyl, wherein the substituents are selected from the group defined hereinbefore as Y. Then, the prodrugs of formula I are amines , and these may be used herein in the form of peroxide-compatible salts, as noted, wherein X is a peroxide-compatible anion of the type as described herein. According to the general formula of the salt, it is understood that those salts having mono-, di- and tri-negative anions are included.

wherein X and Y are the same as in formula I, R 1 and R a may be the same or different from each other and are the same as in formula I, R 5 is the same as in formula I and R 8 is hydrogen or C 1 -C 4 substituted or unsubstituted alkyl or alkenyl, wherein the substituents are selected from the group defined for Y in Formula I.

Specific examples of compounds of formula I include:

o-aminophenol, m-aminophenol, p-aminophenol, 2-iodo-p-aminophenol, 2-nitro-paminophenol, 3,4-dihydroxyaniline, 3,4-diaminophenol, chloroacetate, 2-hydroxy-4-aminobenzoic acid, 2-hydroxy 4-aminobenzaldehyde, 3-amino-4-hydroxybenzenesulfonic acid, Ν, Ν-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-ethyl-p-aminophenol, 2-nitro-5- (2-bromomethyl) -aminophenol, (2-hydroxy-5-aminophenyl) acetaldehyde , 2-methyl-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-paminophenol) perchlorate, 2- (4-methylphenyl) -p-aminophenol, 2- (2-amino-4-methylphenyl) p-aminophenol, p-methoxyaniline, 2-bromomethyl-4-aminophenyl ether phosphate, 2- nitroethyl-423 aminophenyl ether bromide, 2-aminoethyl-4-aminophenyl ether, 2-hydroxyethyl-4aminophenyl ether, (4-aminophenoxy) acetaldehyde, (4-aminophenoxy) acetic acid, (4-aminophenoxy) methanesulfonic acid, 1-propenyl-4-aminophenyl ether (2-chloro) -1-propenyl-4-aminophenyl ether, (2-nitro) -1-propenyl-4aminophenyl ether, (2-amino) -propenyl-4-aminophenyl ether, (2-amino) -propenyl-4aminophenyl ether (2-hydroxy) -1-propenyl-4-aminophenyl ether, N-methyl-paminophenol, 3-methyl-4-aminophenol, 2-chloro-4-aminophenol, 3-chloro-4-aminophenol,

2,6-dimethyl-4-aminophenol, 3,5-dimethyl-4-aminophenol, 2,3-dimethyl-4-aminophenol, 2,5-dimethyl-4-aminophenol, hydroxymethyl-4-aminophenol, 3-hydroxymethyl- 4aminofenol.

According to the present invention, the following are not preferred of the compounds of formula Iia:

wherein R 1 is alkyl, hydroxyalkyl, carboxyalkyl or aminoalkyl; R ₂ is hydrogen, alkyl or hydroxyalkyl group; R 3 and R 1 are hydrogen or -OR, wherein R is an alkyl or hydroxyalkyl substituent; R * is hydrogen, alkyl or NHR '; R e is hydrogen, alkyl, -OR or NHR '; R 'is hydrogen, alkyl, hydroxyalkyl; with the proviso that a) only one of R 4 and R 6 is NHR '; b) R 3 and -OR 1 are not both methoxy when R ₂ , R 5 and R 6 are hydrogen and R 1 is NH ₂ ; c) either R 3 or R 4 or R 5 or R 8 are hydrogen; d) R 3, R 4 and R 5 are not all H when R 8 is NH ₂ , R ₂ is H and R 1 is methyl; e) when R 1 is ethyl and R ₂ , R 3, R 4 and R a are H, R 4 is not NH ₂ ; f) when R 1 is carboxyalkyl or aminoalkyl, R 4 is NHR '.

Specific examples of compounds of formula III include: o-hydroxyphenol (pyrocatechol), m-hydroxyphenol (resorcinol), phydroxyphenol (hydroquinone), 4-methoxyphenol, 2-methoxyphenol, 4- (2-chloroethoxy) phenol, 4- (2-propenoxy) phenol, 4- (3-chloro-2-propenoxy) phenol, 2-chloro-4-hydroxyphenol (2-chlorohydroxyquinone), 2-nitro-4-hydroxyphenol (2-nitroquinone), 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-hydroxyphenol, 3- (2-propenyl) -4- hydroxyphenol, 3- (3-chloro-2-propenyl) -4-hydroxyphenol, 2-phenyl-4-hydroxyphenol, 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-hydroxyphenol, 3-methoxy-4-hydroxybenzaldehyde, 2-methoxy-4- (1-propenyl) Phenol, 4-hydroxy-3-methoxy-3-phenyl-2-propenoic acid, 2,5-dimethoxyaniline, 2-methylresorcinol, oc-naphthol and others salts.

In the preferred compositions herein, preferred compounds of formula ΙΠ do not include the following:

och ₃

nh ₂

The secondary binding compounds (color modifiers) detailed below are preferably used in conjunction with the primary intermediates disclosed herein and are intended to be incorporated into the color polymers during their formation, thereby causing a shift in their electronic spectrum. achieve slight color changes.

Secondary binding compounds which are suitable for inclusion in the dye compositions and methods disclosed herein include, for example, certain aromatic amines and phenols and derivatives thereof that do not produce colors alone but which modify color, shade, or color intensity developed by primary oxidative dye intermediates. Certain aromatic amines and phenolic compounds and derivatives thereof, including certain aromatic diamines and polyhydride phenols of the types described by the above formulas I, Ia, Ib, Π and ΙΠ, but which are well known in the art, are suitable as coupling agents herein. techniques as not suitable primary intermediates. Polyhydric alcohols are also suitable for use herein as coupling agents.

The aromatic amines and phenols and derivatives thereof mentioned above as coupling agents may also have other substituents on the aromatic ring, for example halogen, aldehyde, carboxylic acid, nitro, sulfonyl and substituted and unsubstituted hydrocarbon groups, as well as additional substituents on amine nitrogen or phenol oxygen, e.g. substituted or unsubstituted alkyl and aryl groups. Furthermore, their peroxide-compatible salts are again suitable for use herein.

Examples of aromatic amines, phenols and derivatives thereof are compounds of formulas IV and V below:

(IV)

R - N - R ₂ or

HX wherein Z is hydrogen, C 1 and C 3 alkyl, halogen (e.g. fluorine, chlorine, bromine or iodine), nitro,

ABOUT

II - CH

-COOM or SO 3 M (where M is hydrogen or an alkali or alkaline earth metal, ammonium or substituted ammonium, wherein one or more hydrogen atoms on the ammonium ion is replaced with an alkyl or hydroxyalkyl radical of 1 to 3 carbon atoms), wherein R 1 and R 2 are the same or different and are selected from the group consisting of hydrogen, C 1 -C 4 alkyl or alkenyl and C 6 -C 9 aryl, alkaryl or aralkyl and R 7 is hydrogen, C 1 -C 4 unsubstituted or substituted alkyl or alkenyl, wherein the substituents are selected from the group as defined above for Z, or C 6 -C 9 unsubstituted or substituted aryl, alkaryl or aralkyl, wherein the substituents are selected from the above group Z and wherein X is as defined in formula I.

Specific examples of compounds of formula IV are: aniline, p-chloroaniline, p-fluoroaniline, p-nitroaniline, p-aminobenzaldehyde, p-aminobenzoic acid, sodium p-aminobenzoate, lithium p-aminobenzoate, calcium di-p-aminobenzoate , ammonium p-aminobenzoate, trimethylammonium paminobenzoate, tri (2-hydroxyethyl) -p-aminobenzoate, paminobenzenesulfonic acid, potassium p-aminobenzenesulfonate, N-methylaniline, N-propylN-phenylaniline, N-methyl-N-2-N-2-amine , N-benzylaniline, N- (2-ethylphenyl) aniline,

4-methylaniline, 4- (2-bromomethyl) aniline, 2- (2-nitroethyl) aniline, (4-aminophenyl) acetaldehyde, (4-aminophenyl) acetic acid, 4- (2-propenyl) aniline acetate, 4- (3-bromo) -2-propenyl) aniline, 4-phenylaniline chloroacetate, 4- (3-chlorophenyl) aniline, 4-benzylaniline, 4- (4-iodobenzyl) aniline, 4- (3-ethylphenyl) aniline, 4 (2-chloro-4-ethylphenyl) aniline, (V) wherein Z and R 7 are as defined in formula IV and R e is hydrogen or C 1 -C 4 substituted or unsubstituted alkyl or alkenyl, wherein the substituents are selected from the group shown in Z in formula IV.

Specific examples of compounds of formula V include:

phenol, p-chlorophenol, p-nitrophenol, p-hydroxybenzaldehyde, phydroxybenzoic acid, p-hydroxybenzenesulfonic acid, ethylphenyl ether, 2-chloroethylphenyl ether, 2-nitroethylphenyl ether, phenoxyacetic acid, 3-phenoxy-2-nitro-1-propene, 4-propylene-1-propene 3-bromopropyl I) phenol, phenoxyacetaldehyde, acid

3-phenoxy-2-bromo-1-propene, 42- (2-nitroethyl) phenol, (4-hydroxyphenyl) acetaldehyde, (4-hydroxyphenyl) acetic acid, 4- (2-propenyl) phenol,

4-phenylphenol, 4-benzylphenol, 4- (3-fluoro-2-propenyl) phenol, 4- (4-chlorobenzyl) phenol,

4- (3-ethylphenyl) phenol, 4- (2-chloro-3-ethylphenyl) phenol, 2,5-xylenol, 2,5-diaminopyridine, 2-hydroxy-5-aminopyridine, 2-amino-3-hydroxypyridine, tetraaminopyrimidine, 1,2,4-trihydroxybenzene, 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-methoxyphenyl, 2,4-diaminophenol, 3-methoxy-1,2-dihydroxybenzene, 1,4-dihydroxy-2- (N, N-diethylamino) benzene, 2,5-diamino-4-methoxy -1-hydroxybenzene, 4,6-dimethoxy-3-amino-1-hydroxybenzene,

2,6-dimethyl-4- [N- (p-hydroxyphenyl) amino] -1-hydroxybenzene; 1,5-diamino-2-methyl-4- [N- (p-hydroxyphenyl) aminophenzene] and salts thereof.

In the preferred compositions herein, the following combinations of primary intermediates and coupling agents are not preferred:

NH ₂ wherein R 1 and R 2 are not H in combination with / n-aminophenol, resorcinol, 2-methyl-5-aminophenol, 2-methylresorcinol and mixtures thereof.

Other additional primary intermediates suitable for use herein include a pyrocatechol substance, and in particular a pyrocatechol dopa which comprises dopa itself (3- (3,4-dihydroxyphenyl) -2-aminopropanoic acid) as well as homologues, analogs and derivatives thereof. Suitable pyrocatechol compounds include, for example, cysteinyl 3- (3,4-dihydroxyphenyl) -2-aminopropanoic acid, alphaalkyl derivatives of 3- (3,4-dihydroxyphenyl) -2-aminopropanoic acid, having 1 to 4, preferably to 2 carbon atoms, adrenaline and alkyl esters of 3- (3,4-dihydroxyphenyl) -2-aminopropanoic acid having from 1 to 6, preferably 1 to 2, carbon atoms in the alkyl group.

Generally suitable pyrocatechols are represented by the following general formula VI:

(VI) wherein R 1, R 2 and R 3, which may be the same or different, are electron donors or acceptors of substituents selected from the group consisting of H, lower (C 1 -C ₆ ) alkyl, OH, OR, COOR , NHCOR, CN, COOH, halogen, NO ₂ , CF ₃ , SO ₃ H or NR 4 R 5, provided that only one of R 1, R 2 or R 3 can be CN, COOH, halogen, NO 2, CF 3, or SO 3 H: R 4 and R 3 which may be the same or different are H, lower (C 1 -C 6) alkyl or substituted lower (C 1 -C 6) alkyl in which the substituent may be OH, OR, NHCOR 4, NHCONH 2, NHCO 2 R 6, NHCSNH ₂ , CN, COOH, SO 3 H , SO ₂ NR or Choir: R 'is a lower _(Ci-6) alkyl, lower (C -C) hydroxyalkylphenyl attached to the nitrogen by an alkylene chain, phenyl or substituted phenyl with the substituent defined as R, and R is a Ci-Cio alkyl or C -Cehydroxyalkyl.

Also included are oxidative hair coloring agents having the general formula:

Ο ο

where: R 1 = substituted or unsubstituted benzene ring, tert-butyl, etc. ', R = substituted or unsubstituted benzene ring, and the general formula:

wherein: R = aminoalkyl, amidoalkyl, aminobenzene (substituted or unsubstituted), amidobenzene (substituted or unsubstituted), alkyl, substituted or unsubstituted benzene core; R 1 = substituted or unsubstituted benzene ring.

Said primary intermediates may be used alone or in combination with other primary intermediates for the purpose herein, and one or more may be used in combination with one or more coupling agents. The choice of primary intermediates and coupling agents depends on the color, shade, and intensity of the desired color. There are nineteen preferred primary intermediates and coupling agents that can be used herein, alone or in combination, to provide colors of a variety of shades ranging from ash blond to black; these are: pyrogallol, resorcinol, p-toluenediamine, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, oaminophenol, p-aminophenol, 4-amino-2-nitrophenol, nitro- / 7-phenylenediamine, N-phenylp-phenylenediamine, m-aminophenol, 2-amino-3-hydroxypyridine, 1-naphthol, N, N-bis- (2-hydroxyethyl) -p-phenylenediamine, 4-amino-2-hydroxytoluene, 1,5-dihydroxynaphthalene, 2-methylresorcinol and 2, 4-diaminoanisole. These compounds may be used in molecular form or in the form of peroxide-compatible salts, as detailed above.

The primary intermediates and coupling compounds, as mentioned above, can be combined and given a wide range of colors to the hair. Hair colors can be very different, they can be of medium color or very intense color. As described above, the compositions of the present invention described herein are of great value in providing high color intensity. Color intensity as used herein refers to the amount of color compound formed on the hair and its retention. Generally, high color intensity means darkness or depth of color such as dark to rust red, dark brown or black, etc. Accordingly, it is possible, as noted, to formulate, to varying degrees, the intensity of the dyeing by adjusting the initial level of each of the said oxidizing dyeing agents.

For example, a low color intensity, as in natural blond hair, requires from 0.001% to 5%, preferably from 0.1% to 2%, more preferably from 0.2% to 1% by weight of the colorant to color the light brown shade of the hair. the total amount of oxidizing agents for staining and results can be achieved by combining primary intermediates such as 1,4-diaminobenzene, 2,5-diaminotoluene, 2,5-diaminoanisole, 4-aminophenol, 2,5-diaminobenzyl alcohol and 2- (2 ', 5'-diamino) phenylethanol with coupling agents such as resorcinol, 2-methylresorcinol or 4-chlororesorcinol.

Similarly, the combination of the above primary intermediates with coupling agents such as 5-amino-2-methylphenol and 1,3-diaminobenzene derivatives such as 2,4-diaminomethoxybenzene with levels of from 0.5% to 1% of the total amount of coloring agents may result in medium intensive rust-red colors. High color intensities such as blue to bluish-violet shades are achieved by combining the above primary intermediates with coupling agents such as 1,3-diaminobenzene or derivatives thereof such as 2,5-diaminotoluene at levels of from 1% to 6% by weight of the composition. dyeing agents. A black hair color can be achieved by combining the above primary intermediates with coupling agents such as 1,3-diaminobenzene or derivatives thereof.

However important it is to bear in mind the psychological compatibility of paminophenol, which is generally used to deliver reddish shades to the hair. Similarly, psychological compatibility should be considered for some agents that are preferred in achieving black hair colors, such as p-phenylenediamine (PPD). Accordingly, there is a need for oxidative hair coloring agents having an improved safety profile, and in particular, oxidative hair coloring agents in the delivery of dark colors, i.e., " high intensity coloring dyes having an improved safety profile. As discussed hereinbefore, the low pH compositions of the present invention have excellent hair coloring properties along with reduced levels of hair damage and skin staining and / or skin irritation.

Thus, the compositions of the present invention are also valuable because they are delivered to the hair under better conditions for their condition, along with their good initial color development and consistency and improved color fastness over time while reducing their level of washability. skin damage and irritation and / or skin staining.

Non - oxidising and other colors

The hair coloring compositions of the present invention may contain, in addition to the basic hair coloring agents, optionally non-oxidizing and other coloring agents. Optional non-oxidizing and other coloring agents useful in hair dye compositions and methods of the present invention include both partially permanent, transient and other dyes. Non-oxidizing dyes as defined herein include so-called "direct-acting dyes", metallic dyes, metallic chelate dyes, fibrous reactive dyes, and other synthetic and natural dyes. A variety of non-oxidative dyes are detailed in the publication: "Chemical and Physical Behavior of Human Hair" 3rd Edition, Clarence Robbins Editor (pp. 250-259); 'The Chemistry and Manufacture of Cosmetics', Volume IV, 2nd Edition, edited by Maidon G. De Navarre, Chapter 45 - G. S. Kass (p. 841920); "Cosmetics: Science and Technology" 2nd Edition, Volume II Balsam Sagarin, Chapter 23 - F. E. Wall (pp. 279-343); "The Science of Hair Line", edited by C. Zviak, Chapter 7 (pp. 235-261) and "Hair Dyes", J.C. Johnson, Noyes Data Corp., Park Ridge, U.S.A. (1973), (pp. 3-91 and 113-139).

Direct-acting dyes which do not require an oxidizing action to develop color are also referred to as tinting dyes and have been known for a long time in the art. They are usually applied to the hair based on a matrix (matrix) that contains a surfactant. Direct-acting dyes include nitro dyes such as nitroaminobenzene or nitroaminophenol derivatives; dye dispersions such as nitroarylamines, aminoanthraquinones or azo dyes, anthraquinone dyes, naphthoquinone dyes; alkaline dyes such as Acridine Orange C. I. 46005.

The nitro-dyes are added to the dyeing compositions to achieve a color such as the dye and to impart a suitable aesthetic color to the dye composition prior to application.

Other examples of direct-acting dyes include Arianor basic color brown 17, C.I. (Color Index) - # 12, 251; basic red 76, C.I. -12,245; basic brown 16, C.I. - 12,250; basic yellow 57, C.I. - 12,719 and basic blue 99, C.I. 56.059 and direct-acting dyes such as acid yellow dye 1, C.I. 10.316 (D and C yellow no. 7) acid yellow 9, C.I. - 13,015; basic violet C.I. 45,170; disperse yellow 3, C.I. - 11,855; basic yellow 57, C.I. - 12,719; Disperse Yellow 1, C.I. - 10.345; basic violet 1, C.I. - 42,535; alkaline violet 3, C.I. 42,555; green-blue, C.I. 42090 (FD and C Blue no.1); yellow-red, C.I. 14700 (FD and C red no. 4); yellow, C.I. -19140 (FD and C yellow no.5); yellow-orange, C.I. -15985 (FD and C yellow no.6); cyan, C.I. 42053 (FD and C green no. 3); yellow-red, C.I. 16035 (FD and C red no. 40); cyan, C.I. - 61570 (D and C green no. 3); orange, C.I. 45370 (D and C orange no.5); red, C.I. 15850 (D and C red no. 6); blue-red, C.I. 15850 (D & C red no.7); light blue-red, C.I. - 45410 (D & C red no. 28); blue-red, C.I. - 73360 (D & C red no. 30); purple red, C.I. 17200 (D & C red no. 33); off-blue-red, C.I. - 15880 (D and C red no. 34); bright yellow-red, C.I. -12085 (D & C red no. 36); bright orange, C.I.15510 (D and C orange no. 4); greenish yellow, C.I. 47005 (D and C yellow no. 10); cyan, C.I. - 59040 (D and C green no. 8); blue-violet, C.I. 60730 (Ext. D and C violet no. 2); greenish yellow, C.I. - 10316 (Ext. D and C yellow no. 7).

Fibrous reactive dyes include, for example, Procion (RTM), Drimarene (RTM), Cibacron (RTM), Levafix (RTM) and Remazol (RTM), dyes available from ICI, Sandoz, Ciba-Geigy and Bayer and Hoechst.

Natural dyes and plant dyes as mentioned herein include henna (Lawsonia alba), chamomile (Matricaria chamomila or Anthemis nobilis), indigo, campesian extract and nutshell extract.

Transient hair dyes or tinted hair sprays generally contain dye molecules that are too large to diffuse into the hair and act on the hair surface. They are usually applied by the 'leave' method, where the dye solution is allowed to act on the surface of dry hair. These dyes are typically less resistant to washing and treating hair with surfactants and are relatively easy to wash out of the hair. Any transition hair color can be used in the compositions of the present invention, and examples of preferred transition colors are given below.

red

Sat ₃ ch ₃

blue-violet

".IN

yellow

Semi-permanent hair dyes are dyes that generally have smaller molecules compared to size and effect than transient hair dyes, but are generally larger than permanent (oxidative) dyes. Typically, semi-permanent dyes act in a similar way to oxidative dyes in that they have the ability to diffuse into the hair and cause a certain shift in the color spectrum. However, semi-stable dyes generally have a smaller molecular size than the above conjugated oxidative dye molecules and thus have the ability to gradually diffuse back from the hair. Simple washing and hair care support this way, and so largely wash out semi-permanent hair dyes from 5 to 7 washes. Any semi-permanent hair dyeing system can be used in the compositions of the present invention. Suitable semi-permanent colors 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. Examples of semi-permanent dyes are given below:

no ₂

((C ₂ H ₄ OH) ₂

blue

blue

yellow

yellow

red

red

Typical semi-stable hair dye systems contain a mixture of both large and small dye molecules. Because hair size is not uniform from root to tail, small molecules will diffuse to both hair roots and tails but will not remain in the tails, while larger molecules are able to penetrate only to the hair tips. This combination of dye molecule sizes is used to help consistently color the hair from the roots to their ends during the initial dyeing process and during subsequent washes.

Buffering agents

The hair coloring compositions of the present invention have a pH in the range of from 1 to 6, preferably from 1.5 to 5.8, more preferably from 1.8 to 5.5, most preferably from 2 to 5, and particularly from 3.5 to 5.8. 4.5.

As mentioned above, the pH of the preferred hair coloring compositions of the present invention is maintained within the desired pH range by the action of an inorganic peroxygen oxidizing agent. However, if desired, these compositions may contain one or more optional preferred buffering agents and / or hair swelling agents (HSAs). Several different pH modifiers may be used to adjust the pH of the final composition or any portion thereof.

The pH adjustment can be carried out using acidifying agents well known in the field of keratin fiber processing, and in particular human hair, such as inorganic or organic acids such as hydrochloric acid, tartaric acid, citric acid, succinic acid, phosphoric acid and carboxylic or sulfonic acids such as ascorbic acid, acetic acid, lactic acid, sulfuric acid, formic acid, ammonium sulfate and sodium phosphate / phosphoric acid, disodium hydrogen phosphate / phosphoric acid, potassium chloride / hydrochloric acid, potassium dihydrogen phthalate / hydrochloric acid, sodium citrate / hydrochloric acid, potassium dihydrogen citrate / hydrochloric acid, potassium dihydrogen citrate / citric acid, sodium citrate / citric acid, sodium tartrate / tartaric acid, sodium lactate / lactic acid, sodium acetate / acetic acid, hydrogen disodium phosphate / citric acid and sodium chloride / glycine / hydrochloric acid, succinic acid and mixtures thereof.

Basic buffering agents can be, for example, ammonium hydroxide, ethylamine, dipropylamine, triethylamine and alkanediamines such as 1,3-diaminopropane, anhydrous basic alkanolamines such as mono- or diethanolamine, of which preferably are completely substituted on an amine group such as dimethylaminoethanol, polyalkylene polyamines such as diethylenetriamine or heterocyclic amines such as morpholine and alkali metal hydroxides such as sodium and potassium hydroxides, alkaline earth metal hydroxides such as magnesium and calcium hydroxides, basic amino acids such as L-argenine, lysine, alanine, leucine, isoleucine, oxylysine and histidine, and alkanolamines such as dimethylaminoethanol and aminoalkylpropanediol and mixtures thereof. Also preferred for use herein are compounds that form HCO 3 'by dissociation in water (referred to herein as "ion-forming compounds"). Examples of ion-forming compounds include Na 2 CO 3, NaHCO 3, K 2 CO 3, (NH 4 CO 3, NH + HCO 3, CaCO 3, Ca (HCO 3) and mixtures thereof.

Organic and inorganic acids having a first pK a below pH 6 and their conjugate bases are preferred as buffering agents for use herein. As defined herein, the first pKa is the negative logarithm (based on 10) of the equilibrium constant K, where K is the dissociation constant of the acid. Suitable organic and inorganic acids for use herein are: aspartic, maleic, tartaric, glutamic, glycolic, acetic, succinic, salicylic, formic, benzoic, malic, lactic, malonic, oxalic, citric, phosphoric and mixtures thereof. Particularly preferred are acetic, succinic, salicylic and phosphoric acid and mixtures thereof.

The low pH coloring compositions of the present invention may be, as discussed below, in the form of a final solution containing both peroxide and hair coloring agents that are mixed together prior to application to the hair, or may be single component systems.

In an oxidation and dyeing kit comprising a portion of an inorganic peroxygen oxidizing agent such as hydrogen peroxide, which may be in solid or liquid form, a buffering solution may be used to stabilize the hydrogen peroxide. The hydrogen peroxide is stable in the pH range of 2 to 4, so it is necessary to use a buffer having a pH in this range. Diluted acids are suitable buffering agents for hydrogen peroxide.

In oxidation and dye kits containing an oxidizing agent (which may be in solid or liquid form) in combination with one or more dyeing agents, a suitable buffering agent capable of maintaining the pH of the solution in the range of 1 to 6, preferably 1.5 to 5.8, more preferably from 2 to 5, most preferably from 2 to 5, and especially from 3.5 to 4.5. Thus, it is necessary to use a buffer having a pH in this range.

catalyst

The dyeing compositions herein may optionally include a transition metal catalyst for an inorganic peroxygen oxidizing agent and optionally tableted peroxyacid oxidizing agent (s). A suitable type of catalyst is a catalyst system comprising a heavy metal cation having a defined bleaching catalytic activity, such as copper, iron or manganese cations, auxiliary metal cations having little or no bleaching catalytic activity, such as zinc or aluminum cations, and a masking agent having defined stability constants for catalytic and auxiliary metal cations, in particular ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid), and their water-soluble salts. Such catalysts are disclosed in US-A4,430,243.

Other types of suitable catalysts include the manganese-based complexes disclosed in US-A-5,246,621 and US-A-5,244,594. Preferred types of these catalysts include Mn ^IV 2 (µO) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (PFe) 4 Mn ⁿⁱ 2 (µO) i (µ-OAc) ₂ (1). 4,7-trimethyl-1,4,7-triazacyclononane) _2- (ClO4) ₂ , Mn ^IV 4 (µO) δ (1,4,7-triazacyclononane) 4- (ClO4) 2> Mn ⁱⁿ Mn ^IV 4 (µO) 1 (µ-OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ - (ClO 4) 3 and mixtures thereof. Others are described in EP-A-0,549,272. Other ligands suitable for use herein include e.g. 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane and mixtures thereof.

Examples of suitable catalysts are disclosed in US-A-4,246,612 and US-A5,227,084. See also US-A-5,194,416 for mononuclear manganese (IV-ie manganese) complexes such as Mn (1,4,7-trimethyl-1,4,7 triazacyclononan) (OCH 3) 3 - (PFe). Yet another type of catalyst disclosed in US-A-5,114,606 is a water-soluble manganese (III - ie, manganese) and / or (IV - ie, manganese) complex with a ligand having a non-carboxylate polyhydroxy compound having at least three consecutive of the C-OH group. Other examples include binuclear Mn complexing with tetra-N-dentate and bi-Ndentate ligands, including N ₄ Mn ^ui (µO) 2 Mn ^IV N 4) ⁺ and / Bipy 2 Mn ⁿⁱ (u-0) 2 Mn ^IV bipy 2 / - (C10 ₄ ) ₃ .

Other suitable catalysts are described, for example, in EP-A-0,408,131 (cobalt complex catalysts), EP-A-0,384,503, and EP-A-0,306,089 (mataloporphyrin catalysts), US-A-4,728,455 (manganese / multidentate ligand catalyst), US- A-4,711,748 and EP-A-0,224,952 (absorbed manganese on aluminosilicate catalyst), US-A-4,601,845 (aluminosilicate carrier with salts of manganese and zinc or magnesium), US-A-4,626,373 (manganese / ligand catalyst), US-A- No. 4,119,557 (ferric complex catalyst), DE-A-2,054,019 (cobalt chelation catalyst), CA-A-866,191 (transition metal containing salts), US-A-4,430,243 (manganese cationic chelators with non-catalytic metal cations), and US-A -4,728,455 (manganese gluconate catalysts).

Masking agents for heavy metal ions

The coloring compositions of the present invention may contain, as a suitable component, an optional masking agent for heavy metal ions. As heavy metal ion masking agents, it is meant herein compounds which act to mask (chelate or ions trap) heavy metal ions. These compounds may also have a calcium and magnesium chelating capacity, but preferentially exhibit selectivity with respect to the binding of heavy metal ions such as iron, manganese, and copper. Such masking agents are highly appreciated in hair coloring compositions herein, to impart oxidative control. also to contribute to good storage stability of hair dye products.

Heavy metal ion sequestrants are generally present in an amount of from 0.005% to 20%, preferably from 0.01% to 10%, more preferably from 0.05% to 2% by weight of the composition.

A variety of masking agents, including aminophosphites, available as Dequest (RTM) from Monsanto, nitriloacetates, hydroxyethylethylene triamines and the like are known for use herein. Suitable masking agents for use herein include organic phosphonates such as aminoalkylene poly (alkylene phosphonates), an alkali metal salt and ethane-1-hydroxyhydroxy diphosphite and nitrilotrimethylene phosphonates.

Of the above, diethylenetriamine penta (methylene phosphite), ethylenediamine tri (methylene phosphite), hexamethylenediamine tetra (methylene phosphite) and hydroxyethylene-1,1-diphosphite are preferred.

Preferred biodegradable, non-phosphorous heavy metal ion sequestrants for use herein include nitriloacetic acid and polyaminocarboxylic acids such as ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic acid, ethylenediaminindibutanedioic acid, ethylenediaminediaminediaminediaminediaminediaminediaminediaminodipanediamine. Particularly preferred is ethylenediamine-N, N'dibutanedioic acid (EDDS), see US-A-4,704,233, or an alkali metal salt, an alkaline earth metal salt, an ammonium salt, a substituted ammonium salt, or mixtures thereof.

Other suitable heavy metal masking agents for use herein are iminodiacetic acid derivatives, such as 2-hydroxyethyldiacetic acid or glyceryliminodiacetic acid, as disclosed in EPA-317,542 and EP-A-399,133. The iminodiacetic acid-N-2-hydroxypropylsulfonic acid and 2-aminobutanedioic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid, which are disclosed as masking agents described in EP-A-516,102, are also suitable for use herein. Balanine-N, N'-diacetic acid, 2-aminobutanedioic acid-N, N'-diacetic acid, 2-aminobutanedioic acid-N-monoacetic acid and iminodibutanedioic as camouflage agents as described in EP-A-509,382 are also suitable .

EP-A-476,257 discloses suitable amine-based masking agents. EPA-510,331 discloses suitable masking agents derived from collagen, keratin or casein. EP-A-528,859 discloses suitable alkyl imino diacetic acid masking agents. Also suitable are dipyridine-2-carboxylic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid. Also suitable are glycine-N, N'-dibutanedioic acid (G AD S), ethylenediamine-N, N 'diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N, N'-dibutandioic acid (HPDDS).

The heavy metal ion sequestering agents of the present invention can be used as their alkali metal or alkaline earth metal salts.

thickeners

The coloring compositions of the invention may further comprise a thickening agent in an amount of from 0.05% to 20%, preferably from 0.1% to 10%, more preferably from 0.5% to 5% by weight. The thickeners for use herein are selected from the group consisting of oleic acid, cetyl alcohol, oleyl alcohol, sodium chloride, cetearyl alcohol, stearyl alcohol, synthetic thickeners such as Carbopol, Aculyn and Acrosyl, and mixtures thereof. Preferred thickeners for use herein are Aculyn 22 (RTM), a steareth-20 methacrylate copolymer; Aculyn 44 (RTM), polyurethane resin and Acusol 830 (RTM), acrylate copolymers available from Rohm and Haas, Philadelphia, PA, USA. Additional thickeners for use herein include sodium alginate or acacia, or cellulose derivatives such as methylcellulose or sodium carboxymethylcellulose or acrylic polymers.

thinners

Water is the preferred diluent for the compositions of the present invention. However, the compositions of the invention may contain one or more diluents as additional diluents. Typically, solvents suitable for use in dye compositions are selected from those that are miscible with water and harmless to the skin. Among the solvents suitable for use as co-solvents, C1-C20 mono- or polyhydride alcohols and ethers thereof, glycerin, with monohydride and dihydride alcohols and ethers thereof are preferred. Of these compounds, alcohol residues containing from 2 to 10 carbon atoms are preferred. Thus, preferred groups include ethanol, isopropanol, n-propanol, butanol, propylene glycol, ethylene glycol, monoethyl ether, and mixtures thereof. Water is the preferred major diluent in the compositions of the present invention. The principal diluent, as defined herein, means that the amount of water present is greater than the total amount of any other diluent.

The diluent is present in an amount of from 5% to 99.98%, preferably from 15% to 99.5%, more preferably from at least 30% to 99%, and particularly preferably from 50% to 98% by weight, based on the total weight of the device.

enzyme

Another additive useful in the hair coloring compositions of the present invention is one or more enzymes.

Suitable enzymes include commercially available lipases, cutinases, amylases, neutral and alkaline proteases, esterases, celluloses, pectinases, lactases, and peroxidases commonly incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.

Peroxidases are peroxide-specific hemoproteins but used in a wide range of substances as donors. The peroxide decomposition catalase is included here in view of the fact that it is generally similar in structure and properties and is able to induce some oxidation of H2O2. The decomposition of H2O2 can be considered as oxidation of one molecule by another. This is widespread in aerobic cells and may have some important fimulation. Coenzyme peroxidases are not hemoproteins and at least one is flavoprotein. Other flavoproteins such as xanthine protease also use H2O2, and coenzyme peroxidases are more similar to classical peroxidases not specific to H2O2. Suitable peroxidases for the compositions of the present invention include horseradish peroxidase, Japanese reddish peroxidase, cow's milk peroxidase, rat liver peroxidase, linginase, and haloperoxidase such as chloro- and bromoperoxidase.

The enzymes are preferably incorporated in amounts up to 50 mg by weight, more typically 0.01 mg to 10 mg active enzyme per gram of hair treatment composition of the invention. Alternatively, said peroxidase enzymes may be incorporated into such compositions so that the amount thereof is from 0.0001% to 5%, preferably from 0.001% to 1%, more preferably from 0.01% to 1% of the active enzyme, relative to to the weight of the composition.

Commercially available protease enzymes include those sold under the trade names Alcalase, Savinase, Primase, Durazy and Esperase by Novo Industries A / S (Denmark), and further sold under the trade names Maxatase, Maxacal and Maxapem Gist-Brocades, sold by Genecor International, and those sold under the trade names Opticlean and Optimase Solvay Enzymes. Protease enzymes may be incorporated into the compositions of the invention in an amount of from 0.0001% to 4% of the active enzyme, based on the weight of the composition.

Amylases include, for example, B-amylases obtained from special B licheniformis species, described in detail in GB-1,269,839 (Novo). Preferred commercially available amylases include, for example, those sold under the tradename Rapidase Gist-Brocades, and those sold under the tradename Termanyl and BAN by Novo Industries A / S. Amylase enzymes may be incorporated into the compositions of the invention in an amount of from 0.0001% to 2% of the active enzyme, based on the weight of the composition.

Lipolytic enzymes may be present in amounts of active lipolytic enzyme of from 0.0001% to 2% by weight, preferably from 0.001% to 1% by weight, most preferably from 0.001% to 0.5% by weight, based on the weight of the composition.

The lipase may be fungal or bacterial according to the source from which it is derived, for example, from a lipase produced by Humicola sp., Thermomyces sp. or Pseudomonas sp. including Pseudomonas pseudocaligenes or Pseudomonas fluorescens. Lipase from chemically or genetically modified mutants of these species is also useful for use herein. A preferred lipase is derived from Pseudomonas pseudoalcaligenes as described in European Patent Grant EP-B-0218272.

Another preferred lipase for use herein is obtained by cloning the gene from Humicola lauginosa and expressing the gene in Aspergillus oryza as a host, as described in European Patent Application EP-A-0258 068, which is commercially available from Novo Industri A / S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Pat. No. 4,810,414, HugeJensen et al., issued Mar. 7, 1989.

Surfactants

The compositions of the present invention may further comprise a surfactant system as an additive. Suitable surfactants for inclusion in the compositions of this invention generally have a lipophilic chain f of from 8 to 22 carbon atoms and can be selected from anionic, cationic, nonionic, amphoteric, zwitterionic surfactants and mixtures thereof.

(i) Anionic surfactants

Anionic surfactants suitable for incorporation into the compositions of this invention include alkyl sulfates, ethyxylated alkyl sulfates, alkyl glyceryl ether sulfonates, methyl acyl-2-aminoethanesulfonates, fatty acyl glycinates, N-acylglutamates, acyl isethethates, alkylsulfobutanedioates, alkyl ethoxy sulfonates, alkyl ethoxy sulfonates, alkyl ethoxy sulfonates, alkyl ethoxylate sulfonates. and / or their esters, alkyl ethoxycarboxylates, alkyl phosphate esters, ethoxylated alkyl phosphate esters, alkyl sulfates, acyl-2-methylaminoethanes and fatty acid / protein condensates and mixtures thereof. The alkyl and / or acyl chains have a length of C 12 -C 22, preferably C 11 -C 18, more preferably Cu-Ch.

(ii) Non-ionic surfactants

The compositions of the invention may also contain a water-soluble nonionic surfactant (s). Surfactants of this group include Cn-C14 fatty acids of mono- and diethanolamides, sucrose polyester surfactants, and polyhydroxy fatty acid amides having the general formula:

OR ₉ II I Rs - C - N - Z ₂

Preferred N-alkyl, N-alkoxy or N-aryloxy, polyhydroxy fatty acid amide surfactants according to the above formula are those wherein R 8 is a C 1 -C 31 hydrocarbon group, preferably a C 6 -C 19 hydrocarbon group, including alkyls and alkenyls with straight or branched chain, or mixtures thereof, and R 9 is typically hydrogen, C 1 -C 8 alkyl or hydroxyalkyl, preferably methyl, or a group of the formula -R 1 -OR ² , wherein R ¹ is a C 2 -C 8 hydrocarbon group including straight hydrocarbon groups and is preferably a C ₂ -C 4 alkylene, R ² is a C 1 -C 8 straight hydrocarbon chain, a branched hydrocarbon chain, and a cyclic hydrocarbon chain including aryl and a hydrocarbon group having an oxygen atom, as preferably it is C 1 -C 4 alkyl, especially methyl or phenyl. Z2 is a polyhydroxy hydrocarbon moiety having a linear hydrocarbon chain having at least 2 (in the case of glyceraldehyde) or at least 3 hydroxyl groups (in the case of other reducing sugars) directly attached to the hydrocarbon chain, or an alkoxylated derivative thereof (preferably ethoxylated or propoxylated). Z 2 is preferably derived from a reducing sugar in a reductive amination reaction, most preferably Z 2 is a glycityl moiety. Suitable reducing sugars include, for example, glucose, fructose, maltose, galactose, mannose, xylose, and glyceraldehyde. As raw starting materials, high dextrose corn syrup, high fructose corn syrup, high maltose corn syrup and the individual sugars listed above may be used. These corn syrups can provide a mixture of sugar components for Z2. However, this does not mean that other suitable substances are excluded. Z 2 may preferably be selected from the group consisting of -CH 2 (CHOH) _n -CH ₂ OH, -CH (CH ₂ OH) - (CHOH) _n -CH ₂ H, CH ₂ (CHOH) ₂ (CHOR ') (CHOH) -CH 2 OH, wherein n is an integer from 1 to 5 inclusive, and R 1 is hydrogen or a cyclic mono- or polysaccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, especially -CH 2 - (CHOH) 4 -CH 2 OH.

The most preferred polyhydroxy fatty acid amide has the general formula R 8 (CO) N (CH ₃ ) CH ₂ (CH OH) 4 CH ₂ OH, wherein R 8 is a straight chain C ₆ -C ₁₉ alkyl or alkylene group. In the compounds of the above formula, R 8 -CO-N may be, for example, cocoamide, stearamide, aleamide, lauramide, myristamide, caprinamide, palmiamide, lujamide and the like.

For use herein, suitable oil-derived nonionic water-soluble plant and animal-based surfactants include derived emollients such as triglycerides having an inserted polyethylene glycol chain; ethoxylated mono- and di-glycerides, polyethoxylated lanilines and ethoxylated butter derivatives. A preferred group of oil-derived nonionic surfactants for use herein has the following general formula:

ABOUT

II

RCOCH 2 CH (OH) CH 2 (OCH 2 CH ₂ ) n OH wherein n is from 5 to 200, preferably from 20 to 100, more preferably from 30 to 85, and wherein R represents an aliphatic radical having an average of 5 to 20 carbon atoms, preferably 7 up to 18 carbon atoms.

Suitable ethoxylated oils and fats of this group include polyethylene glycol derivatives of cocoa glyceryl ester, caproic acid glyceryl ester, caprylic acid glyceryl ester, tallow glyceryl ester, palmitic acid glyceryl ester, stearic acid glyceryl ester, glyceryl laurate, glyceryl oleate, glyceryl oleate, glyceryl oleate, , almond oil and corn oil, preferably tallow glyceryl ester and cocoa glyceryl ester.

Preferred for use herein are polyethylene glycols based on polyethoxylated C 9 -C 15 fatty alcohols of nonionic surfactants containing, on average, from 5 to 50 ethyleneoxy moieties per mole of surfactant.

Suitable polyethylene glycol based polyethoxylated C9C15 fatty alcohols suitable for use herein include C9-C11 Patreth-3, C9-C11 Pareth-4, C9-C11 Patreth-5, C9-C11 Patreth-6, C9-C11 Patreth-7 , C9-C11 Patreth-5, C11-C15 Patreth-5, Cn-Cu Patreth-5, Cn-Cu Patreth-5, C11-C15 Patreth-5, C11-C15 Patreth-5 C11-C15 Patreth-12, C11-C15 Patreth-12, C11-C15 Patreth-12, C11-C15 Patreth-12, C11-C15 Patreth-14, C11-C15 Patreth-14. PEG 40 hydrogenated castor oil is commercially available under the tradename Cremophor (RTM) from BASF. PEG 7 cocoa glyceryl ester and PEG 20 glyceryl laurate are commercially available from Henkel under the trade names Cetiol (RTM) HE and Lamacit (RTM) GLM 20. C9-C11 Patreth-8 is commercially available from Shell Ltd under the trade name Dobanol (RTM) 91-8. Particularly preferred for use herein are polyethylene glycol esters of ceteryl alcohol such as Ceteareth 25, which is available from BASF under the trade name Cremaphor A25.

Also suitable for use herein are nonionic surfactants derived from composite vegetable fats extracted from Shea Tree (Butyrospermum Karkii Kotschy) and derivatives thereof. Similarly, ethoxylated derivatives of mango, cacao and Illipe butter may be used in the compositions of the present invention. Although classified as ethoxylated nonionic surfactants, it is understood that some may be in the form of unethoxylated vegetable oil or fat.

Other nonionic surfactants include ethoxylated derivatives of almond oil, peanut oil, rice bran oil, wheat germ oil, linseed oil, jojoba oil, apricot kernel oil, nut, palm nut, pistachio nuts , sesame seeds, rapeseed, peach kernel oil, poppy oil, castor oil, soybean oil, avocado oil, safflower oil, coconut oil, hazelnut oil, olive oil, grape seed oil and sunflower oil.

(iii) Amphoteric surfactants

Amphoteric surfactants for use in the compositions of the present invention include:

(a) imidazolinium surfactants of the general formula VII:

C2H4 OR ₂

CH ₂ Z

Ri N +

N '(VII) wherein R 1 is C 7 -C 22 alkyl or alkenyl, R ₂ is hydrogen or CH ₂ Z, wherein Z independently CO ₂ M or CH ₂ CO ₂ M and M is hydrogen, alkali metal, alkaline earth metal, ammonium or alkanolammonium; and / or ammonium derivatives of formula VIII:

C2H4OH

I

Ri CONH (C Η ₂ ) ₂ Ν ⁺ CH ₂ Z

R ₂ (VIII) wherein R 1, R ₂ and Z are as defined above;

(b) Aminoalkanoates of Formula IX:

R 1 NH (CH ₂ ) _n CO ₂ M (IX) iminodialkanoates of formula X:

R ^CH CHCO CO (X) and iminopolyalkanoates of formula XI:

R 1 - [N (CH ₂ ) _p ] _q N [CH ₂ CO ₂ M] ₂ i (XI)

CH ₂ CO ₂ M wherein n, m, p and q are numbers from 1 to 4, and R 1 and M are independently selected from the above groups; and (c) mixtures thereof

Suitable amphoteric surfactants of type (a) are sold under the trade names Miranol and Empigen and it is understood that a complex mixture of ingredients is included. Traditionally, the compounds of formula VII are referred to as Miranols, although CTFA Cosmetic Ingredient Dictionary, 3rd edition, indicates the non-cyclic structure of Wines, whereas 4th edition indicates yet another structural isomer in which R ₂ is attached to an oxygen atom rather than a nitrogen atom. In fact, there is probably a complex mixture of cyclic and non-cyclic components and both definitions are valid for the complex concept. However, non-cyclic compounds are preferred for use herein.

Suitable types of amphoteric surfactants of type (a) include compounds of formula (XII) and / or (XIII) wherein R 1 is C 5 H 11 (especially isocapryl), C 9 H 19 and C 11 H 23 alkyl. Particularly preferred are compounds wherein R 1 is C 9 H 19, Z is CO ₂ M and R ₂ is hydrogen; compounds wherein R 1 is C ₁₁ H ₂₃ , Z is CO ₂ M and R ₂ is CH ₂ CO ₂ M; and compounds wherein R 1 is C ₁₁ H 7, Z is CO ₂ M and R ₂ is hydrogen.

According to the CFTA nomenclature, suitable materials for use herein include cocoamphocarboxapropionate, cocoamphocarboxypropionic acid, and in particular cocoamphoacetate and cocoamphodiacetate (otherwise also referred to as cocoamphocarboxygylcinate). Specific commercial products include those sold under the trade names Ampholak 7TX (sodium carboxamethyllojpropylamine), Empigen CDL60 and CDR60 (Albright and Wilson), Miranol H2M Conc. Miranol C2M Conc. N.P., Miranol C2M Conc. O.P., Miranol C2M Conc. 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). Other examples of amphoteric surfactants suitable for use herein are Octoxynol-1 (RTM), polyoxyethylene (1) octyl ether; Nonoxynol-4 (RTM), polyoxyethylene (4) nonylphenyl ether and Nonoxynol-9, polyoxyethylene (9) nonylphenyl ether.

It is understood that a number of commercially available amphoteric surfactants of this type are produced and sold in the form of electronutral complexes with, for example, hydroxide ions or with anionic sulfate or sulfonate surfactants, in particular of these are Ce-Cu alcohol, Cg-Cig ethoxylated alcohol or C8-C18 acylgylceride types. It should also be noted that the concentration and weight ratios of the amphoteric surfactants are here based on uncomplexed surfactant forms, sometimes anionic surfactant counterions as part of the total anionic surfactant component content are desired.

Preferred amphoteric surfactants of type (b) include, for example, N-alkylpolytrimethylene polycarboxymethylamines sold under the trade names Ampholak X07 and Ampholak 7CX by Berol Nobel, as well as salts, especially triethanolammonium salts and salts of N-lauryl-B-aminopropionic acid and N-lauryl acid. imino-dipropionic acid. Such substances are sold under the trade name Deriphat by Henkel and Mirataine by Rhone-Poulenc.

(iv) Both surfactants

The water-soluble excipients suitable for inclusion in compositions of the invention include alkyl betaines of the formula R5R6R7N ⁴ · (CH 2) _n CO2M and amido betaines of formula XII:

rho

I

R ₅ CON (CH 2) _m N (CH ₂ ) n CO ₂ M (XII)

R 7 where R 8 is C 11 -C 22 alkyl or alkenyl, R 7 and R 7 are independent C 1 -C 3 alkyl, M is hydrogen, alkali metal, alkaline earth metal, ammonium or alkanolammonium, and n, m are each 1 to 4. Among the preferred betains include cocoamidopropyldimethylcarboxymethylbetaine, laurylamidopropyldimethylcarboxymethylbetaine and Tego betaine (RTM).

Water-soluble sulfide auxiliary surfactants suitable for incorporation into the compositions of the present invention include alkyl sulfates of the formula:

R 2

I

R1CON (CH ₂ ) _m N ⁺ (CH ₂ ) n CH (OH) CH ₂ SO ₃ Tri * (XIII)

I

R a where R 1 is C 7 -C 22 alkyl or alkenyl, R 2 and R ₃ independently represent C 1 -C ₃ alkyl, M is hydrogen, alkali metal, alkaline earth metal, ammonium or alkanolammonium amine are numbers from 1 to 4. For use herein, preferred cocoamidopropylhydroxysultain.

Water-soluble amine oxide surfactants suitable for incorporation into the compositions of the present invention include the R5R / 5R7NO alkylamine oxide and the amidoamine oxides of formula XIV:

R '

I

R5CON (CH 2) _m N ---> O (XIV)

I

R 7 where R 1 is C 11 -C 22 alkyl or alkenyl, R 7 and R 7 are independently C 1 -C 3 alkyl, M is hydrogen, alkali metal, alkaline earth metal, ammonium or alkanolammonium and m is from 1 to 4. Preferred amino oxides include cocoamidopropylamine, lauryldimethylamine oxide and myristyldimethylamine oxide.

Preferred additives

A large number of preferred additives described herein can be added to the dyeing compositions herein in amounts of from 0.001% to 5%, preferably from 0.01% to 3%, more preferably from 0.05% to 2%. % by weight, based on the weight of the composition. These include proteins and polypeptides and derivatives thereof; water-soluble or solubilized preservatives such as DMDM Hydantoin, Germall 115, methyl, ethyl, propyl and butyl hydroxybenzoic acid esters, EDTA, Euxyl (RTM) K400, natural preservatives such as benzyl alcohol, potassium sorbate and bisabolol, acid benzoic acid, sodium benzoate and 2-phenoxyethanol; antioxidants such as sodium sulfite, hydroquinone, sodium bisulfide, sodium metabisulfite and thioglycolic acid, sodium dithionite, erythrobic acid and other mercaptans; paint removers such as oxalic acid, sulphated castor oil, salicylic acid and sodium thiosulfate; H2O2 stabilizers such as compounds e.g. such as sodium stannate, stannic hydroxide and stannous octoate, acetanilide, phenacetin collide silica, magnesium silicate, oxyquinoline sulfate, sodium phosphate and tetrasodium pyrophosphate; and p-hydroxybenzoates; wetting agents such as hyaluronic acid, chitin, and starch-pelleted sodium polyacrylates such as Sanwet (RTM)

IM-1000, IM-1500 and IM-2500, available from Celanese Superabsorbent Materiais, Portsmith, VA, USA and described in US-A-4,076,663 as well as methylcellulose, starch, higher fatty alcohols, paraffin oils, fatty acids and the like. ; solvents; antibacterial agents such as Oxeco (phenoxyisopropanol); low temperature phase modifiers such as ammonia sources (e.g. NH 4 Cl); viscosity-regulating agents such as magnesium sulfate and other electrolytes; quaternary amine compounds such as distearyl-, dilauryl-, dihydrogenated bovine tallow, dimethylammonium chloride, dicetyldiethylammonium methyl sulfate, dilodium dimethylammonium methyl sulfate, disojadimethylaminium chloride and dicocodimethylammonium chloride; hair conditioning agents such as silicones, higher alcohols, cationic polymers, and the like; enzyme stabilizers such as water-soluble calcium sources or borate compounds; coloring agents; T1O2 and T1O2 coated mica; fragrances and fragrance stabilizers; and zeolites such as Valfour BV400 and its derivatives and Ca ²⁺ / Mg ²⁺ masking agents such as polycarboxylates, aminopolycarboxylates, polyphosphites, aminopolyphosphites, and water softening agents such as sodium citrate.

The following are examples of embodiments of the present invention which are intended to illustrate the invention in more detail, but do not limit the scope or scope of the invention in any way. In all examples, the concentrations of the substances will be expressed on the basis of 100% active base and all percentages will be by weight unless otherwise indicated and the following abbreviations will mean:

Oxidizing agent

Oxidant dye

Oxidant dye 2

Oxidative dye 3

Oxidative dye 4

Oxidizing dye 5 Non-oxidizing dye Chelating agent Surfactant 1 Surfactant 2 Thickening agent 1 hydrogen peroxide p-phenylenediamine p-aminophenol m-aminophenol 2-amino-3-hydroxy-pyridine 4-amino-2-hydroxy-thiene Base red 76 Ethylenediamine Tetraethylenediamine Tetraethylenediamine 25

Cocoamidopropylbetaine Cetyl alcohol

Thickener 2

antioxidant

Buffer 1

stearyl

Sodium sulphite Acetic acid

Examples

Examples I to VII

The following are hair care compositions in the form of hair coloring compositions that are representative of the present invention.

component I II III IV IN VI VII Oxidizing agent 0.7 0.7 0.7 0.7 0.7 2.5 1.5 Oxidant dye 0.24 0.14 0.24 0.15 0.24 0.4 0.4 Oxidant dye 2 0.09 0.05 0,009 0.5 0.09 0.1 0.1 Oxidative dye 3 0,006 0,004 0,006 - 0,006 - - Oxidative dye 4 0.06 0.03 0.06 0.1 0.06 0.06 0.06 Oxidative dye 5 - - - 0.5 - - - Non-oxidising dye - - - - - 0.1 - Surface, nude. substance 1 1.5 1.7 1.5 1.5 1.5 1.5 - Surface, nude. substance 2 - - - - - - 1.5 Chelating agent 0.1 0.06 0.09 0.2 0.1 0.1 0.1 Thickener 1 2.3 2.6 2.3 2.3 2.3 4.0 4.0 Thickener 2 2.3 2.6 2.3 2.3 2.3 2.0 2.0 antioxidant 0.1 0.06 0.1 0.2 0.1 0.1 0.1 Buffer - - - 0.5 0.5 0.2 0.2 Water ..quantity corresponding to balance ... pH 4.0 3.8 3.9 4.6 2.7 - -

In the examples, water is used as the diluent. However, in various variations, the water may be partially replaced, from 0.5% to 50% by weight, based on the total water content, with diluents such as lower alcohols, e.g. ethylene glycol, ethylene glycol monoethyl ether, diethylene glycol, diethylene glycol monoethyl ether, propylene glycol, 1,3-propanediol, ethanol, isopropyl alcohol, glycerin, butoxyethanol, ethoxydiglycol, hexylene glycol, polyglyceryl ether, polyglyceryl ether, polyglyceryl ether, polyglyceryl ether, polyglyceryl ether, polyglyceryl ether, polyglyceryl ether, polyglyceryl ether, polyglyceryl ether, polyglyceryl ether, polyglyceryl ether.

Experimental methods

I. Determination of initial color and color change

The apparatus used to determine both the initial color and the color change on the substrate (hair / skin) by dyeing the low pH dye compositions of the present invention is a Hunter Colorquest spectrophotometer. The quantity used to express the degree of color change on any substrate is Delta E (ΔΕ). Delta E as defined herein means (specific, accurate, factual, real) the sum of L, a, and b of the quantities, such that:

=Ε = (ΔΕ ² + Aa ² + Ab ² ) ¹⁷² and L are measured for lightness and darkness (color intensity), where L = 100 is equivalent to white and L = 0 is equivalent to black. Furthermore, "a" is determined for red and green quotients (color shades) such that positive equals red and negative is equal to green, and "b" is determined for yellow and blue quotients (color shades) such that positive equals yellow and negative equals blue.

Hunter Colorqueste measurements can be performed using the Hunter Labscan Colorimeter, a full scanning spectro-colorimeter with a wavelength of 400 to 700 nanometers, which records the color of the tested hair strands at terms given as "L" and "b". This device is a set consisting of: -0/45 mode; port size - 25.4 mm (1 inch); image size 25.4 mm (1 inch); light (light) - D65; field of view - 10 °; ultraviolet lamp / filter - no. The hair is placed in a specimen holder that is adjusted so that the hair is uniform and uniform throughout the measurement. Equivalent colorimeters may be used, but care should be taken to ensure that hair does not move during measurement. The hair must be spanned to cover a 25.4 mm (1 inch) port when determining color. Mark the points on the strand holder to have a predetermined position relative to the port. These points are arranged in a row to match the markings on the port and data is recorded at any time.

Eight measurements are made per hair strand, 4 on each side and three hair strands are used for each measurement.

II. Standard application of hair dye

The compositions of the present invention can be used to dye hair of all colors, types and conditions. For purposes needed here, hair testing of the following types is shown: light brown hair and hair that is light brown with 40% gray hair. The coloring of these standard dyed hairs can be determined by the values of L, a, b.

L and b

Brown light

9

Light brown with 40% gray 35-37

4.5-5.5

11.5 to 12.7

III. Coloring method of applying hair dye

For staining, a 4 grams 8 inch (8 inch) strand of hair is fastened to a suitable container. The dye test substance is then prepared (i.e., mixed together for application to the separately packaged components) and 8 grams of product is applied directly to the test strand of hair. The coloring agent is massaged into the colored hair for up to one minute and then left to act on the hair for up to thirty minutes. After rinsing with running water for 1 or 2 minutes, colored hair is washed (following the shampoo procedure) and dried. Dyed hair can either be left for a natural effect (without the aid of heat) or a dryer can be used. The progress of color development (initial color) during dyeing, washing and drying can be tested using a Hunter Colorquest spectrophotometer.

For delivering reddish shades (colors) of previously colored light brown hair after permanent (where the values L, a, b have values of 60, 9 and 32), an initial shade of colored hair having a color value (are tangent ratio (b / a) ) in the range of from 25 to 70, more preferably from 30 to 65, most preferably from 35 to 60, and if the initial color intensity (L) is greater than 10 and less than 70, preferably greater than 15 and less than 65, more preferably greater than 20 and less than 60.

For delivering a brown or black shade (color) to a previously colored light brown hair after permanent (in which L, a, b are 60, 9 and 32), an initial shade of colored hair having a color value (are tangent ratio (b / (a)) less than 25, more preferably less than 20 and if the initial color intensity (L) is greater than 1 and less than 50, preferably greater than 5 and less than 45.

For the supply of light brown shades (color) to previously colored light brown hair after permanent (where the values L, a, b are 60, 9 and 32), an initial shade of colored hair having a color value (are tangent ratio (b / a) ) in the range of from 70 to 110 and if the initial color intensity (L) is greater than 20 and less than 95, preferably greater than 25 and less than 90.

A significant color change that can be achieved with the coloring compositions of the present invention means that the color change expressed by Delta E is greater than 8, preferably greater than 10, more preferably greater than 12, most preferably greater than 15, and particularly preferred is if greater than 20.

Method of washing strands of dyed hair

The strands of dyed hair are subjected to a repeated cycle of hair washing, repeating the following method of washing up to ten times.

A 4 gram weighing strand of dyed hair of 203.2 mm (8 inches), which is suspended in a suitable container and is rinsed vigorously with water for 10 seconds using warm water (at 32.2 ° C (100 ° F), is tested. ) and 5.68 liters per minute (1.5 gallons (am.) per minute)). Shampoo (0.4 ml shampoo without conditioner) can be applied directly to a strand of wet hair using a syringe. After foaming on the hair after 30 seconds, the hair is rinsed with running water for 30 seconds. Shampooing and foaming is then repeated with a final rinse lasting 60 seconds. Excess water is removed (squeezed) from the test strand using your fingers. The test hair strand is then dried either naturally or with the aid of a dryer at 60 ° C (140 ° F) (for 30 minutes). The stained, washed and dried strand of hair is then tested for color (Delta E fading).

During each individual test cycle, each different strand of hair is evaluated by testing in water at equivalent temperature, pressure and hardness.

Resulting values for previously colored light brown hair after permanent (having L, a, b values of 60, 9 and 32) that have been colored to a red shade (color value in the range of 25 to 70) are generally less than 5.0, preferably less than 4.5, more preferably less than 4.0 wherein the change in hair color,% Delta E, up to 20 washes, is less than 20%, and preferably less than 15%, more preferably less than 10%.

Resulting values for previously colored light brown hair after permanent (having L, a, b values of 60, 9 and 32) that have been colored to brown or black (color value less than 25) are generally less than 2.3, preferably less less than 2.0, more preferably less than 1.7, wherein the change in hair color,% Delta E, up to 20 washes, is less than 5%, and preferably less than 4.5%, more preferably less than 3.5% .

The resulting values for previously colored light brown hair after permanent (having L, a, b values of 60, 9 and 32) that have been colored to a light brown shade (color value between 70 and 110) are generally less than 2.6, preferably less than 2.3, wherein the change in hair color,% Delta E, up to 20 washes, is less than 15%, and preferably less than 12%, more preferably less than 10%, most preferably less than 8%.

In the preferred compositions herein, the color change on the dyed hair with a time (Delta E fading) is less than 15%, preferably less than 12%, more preferably less than 10%, and most preferably less than 8%.

Methods for testing skin staining

For these purposes, the test results are based on data obtained from pig skin testing.

Testing of skin staining can be done on the ears of the pig, preferably on the ears of the pigs shortly killed before. The ears are not subjected to excessive heat (scalding). The flatest part of the ear where spotting testing is to be performed is shaved to remove hair.

The 1 cm x 5 cm area is pre-marked on the ear (using a permanent marker), and the ear is then washed with shampoo without conditioner (0.1 g / cm ² at 10% dilution). After the massage, the ear is rinsed for 30 seconds with a shampoo for 1 minute and then dry gently with dry hands with a paper towel. A baseline color assessment shall be made on the pre-marked area using the records (L, a, b). A test paint (0.25 g / cm ² ) is applied to the pre-marked area, massaged for 1 minute and then allowed to act for 30 minutes. The stained ear is then rinsed with 2 liters of drinking water at 37 ° C and hand-dried as above. A color assessment is performed on the pre-marked area of the colored ear using the records (L, a, b). The total color change is then calculated from the values of L, a, b and the relative level of skin staining (compared to the basic color scale).

PH measurement

For purposes of the invention described herein, all pH measurements are made using a Mettler Toledo 320 pH meter. All pH measurements of dyes, oxidizing agents and mixtures thereof, either alone or in combination with a suitable delivery medium such as water and surfactant and / or thickeners, are made at room temperature (25 ° C). The pH of the color mixtures is determined in a form that corresponds to the use and condition prior to application. Preferred delivery media for use herein include, for example, ceteareth-25 emulsions in an amount of from 1% to 3% by weight, cetyl alcohol in an amount of from 2% to 5% by weight, and stearyl alcohol in an amount of from 2% to 5% by weight of the solution or composition.

Experimental data

I, Initial color and color fastness to washing

The formulation in Example I provides improved initial color and fade resistance compared to a similar composition having a pH outside the scope of the invention.

The formulation in Example II provides improved initial color development and color fastness as compared to a similar composition having a high pH and containing the same amount of oxidizing agent and 60% more color.

The formulation in Example III provides improved initial color development compared to a composition having a high pH and containing the same amount of color but more inorganic peroxygen oxidizing agent.

•

II, Relative skin staining

In the example referred to as IV, there is a reduced level of staining on the pig ear skin as compared to the corresponding high pH composition.

Method of preparation

It is important that the coloring agents be in a form that is light and customary to be ready for use by the consumer, the oxidizing agent must be in contact with the hair for a certain period of time and not drip or drip from the hair as it may cause eye or skin irritation. .

In addition to the above, the coloring compositions of the present invention can be provided either in individual packages or in kits where the components are separately packaged to achieve stability and, if desired, either the consumer can mix them before use. or may be mixed and stored for future use, or may be mixed and partially used and the remainder may be stored for future use.

As mentioned hereinbefore, the compositions of the invention may be used by the user as a one-component package. Such a single package comprises one solution having a pH of 1 to 6 containing both an inorganic peroxygen oxidizing agent and oxidizing dye precursors. This solution is applied directly to the hair by the consumer without requiring any prior treatment or mixing, thus providing a simple, fast, trouble-free hair coloring system. Another advantage of such a one-component system is that it can be stored and reused, i. one package may contain enough coloring agent for several applications over time.

Thus, according to another aspect of the invention, it is provided:

A method of coloring hair wherein the hair coloring composition is present in a single package and is applied directly to the hair, and wherein the hair coloring composition comprises:

(a) from 0.0003 mol (per 100 g of composition) to less than 0.09 mol (per 100 g of composition) of an inorganic peroxygen oxidizing agent; and (b) an oxidative hair coloring agent; and wherein the pH of each of (a) and (b) when in solution is in the range of 1 to 6 and wherein the combined mixture of (a) and (b), if in solution, has a pH in the range of 1 to 6 .

According to a further aspect of the invention there is provided:

A method of coloring hair wherein the coloring agent is present as separately packaged components (a) and (b) and wherein the coloring agent comprises:

(a) from 0.0003 mol (per 100 g of composition) to less than 0.09 mol (per 100 g of composition) of an inorganic peroxygen oxidizing agent, wherein the pH of (a) is in the range of 1 to 6; and (b) an oxidative hair coloring agent wherein the pH of (b) is in the range of 1 to 6;

wherein each of (a) and (b) are stable at a pH in the range of 1 to 6 and wherein the combined mixture of (a) and (b) is stable over time and has a pH in the range of 1 to 6.

Alternatively, the compositions of the invention may be packaged as follows: one component of the kit comprises an individually packaged oxidizing component, while the other components may comprise a mixture of coloring agents and, optionally, individually packaged additional preferred oxidizing agent (s), or two separate packages of oxidizing agent and coloring agent . In one embodiment of the present invention, the oxidizing component comprises a stabilized aqueous solution of an inorganic peroxygen oxidizing agent, most commonly hydrogen peroxide, in an amount such that the final concentration in the dye composition is from 0.05% to 6% by weight and the additional agents would be such as described above. The ingredients may either be mixed by the user immediately prior to application to the hair or may be applied separately. Examples of such kits are as follows:

I. The hair dyeing kit shall be composed of one package, including:

(1) a 50 ml bottle with hydrogen peroxide (1.4% by weight of H2O2) and, if applicable, additional buffering agents and / or stabilizers, and (2) a 50 ml bottle containing one or more oxidizing hair dyes, and, where appropriate, additional agents such as surfactants, stabilizers, buffering agents, antioxidants, thickeners, etc. Oxidizing hair dyeing agents can either be mixed with hydrogen peroxide to form a low pH dyeing system according to the present invention and the resulting solution can either be applied to the hair for dyeing or stored for future use or can be separately packaged ingredients stored and mixed only when necessary.

II. A hair coloring kit as described above, wherein the hydrogen peroxide-containing component is applied to the hair prior to application of the oxidative hair coloring agent and optional hair additives.

III. Other examples of the kit of hair coloring compositions of the present invention include separately packaged oxidative hair coloring agents wherein either one or both of the components are present in lump form.

Methods of use

The compositions described herein are for use in hair dyeing. The dye compositions herein are applied to the hair for a period of from 1 minute to 60 minutes, depending on the desired degree of coloring. The preferred time is between 5 minutes and 30 minutes. The dye compositions of the present invention can be applied to both wet and dry hair.

As mentioned hereinabove, hair coloring compositions described herein may be present as individual packages, at low pH, suitable for direct application to the hair. Alternatively, the coloring composition may be present in a kit wherein one component comprises an oxidizing agent and the other component comprises oxidizing hair coloring agents. The hair dye kits of the present invention can be used to dye hair in several ways, including:

(i) the components of the kit are mixed so as to form a low pH dye composition prior to application to the hair, (ii) an oxidant is applied to the hair prior to application of the oxidative hair coloring agents, (iii) oxidative hair coloring agents are applied to the hair prior to application of the oxidizing agent.

Said products provide excellent hair coloring and effective use benefits, including improved color fastness to washing, color saturation and reduced hair damage at low pH.

Industrial usability

The hair coloring compositions and dyeing methods of the present invention are, by their nature, important for the consumer industry of the service industry, respectively. for the chemical industry.

Claims (32)

PATENT CLAIMS A hair coloring composition comprising: (a) from 0.0003 mol per 100 g of composition to less than 0.09 mol per 100 g of composition of an inorganic peroxygen oxidizing agent; and - (b) an oxidative hair coloring agent; wherein the pH of each of (a) and (b) is in the range of 1 to 6 and the pH of the composition is in the range of 1 to 6. Hair coloring composition according to claim 1, characterized in that the pH is in the range from pH 1.5 to pH 5.8, preferably from pH 1.8 to pH 5.5, more preferably from pH 2 to pH 5. and most preferably from pH 3.5 to pH 4.5. Hair coloring composition according to claim 1 or 2, characterized in that said inorganic peroxygen oxidizing agent is present in a molar amount of from 0.0003 mol per 100 g of composition to 0.08 mol per 100 g of composition, preferably from 0 0003 mol to 0.06 mol, more preferably from 0.0003 mol to 0.04 mol, most preferably from 0.0003 mol to 0.03 mol, in particular from 0.0003 mol to 0.02 mol, and most preferably in particular from 0.0003 mol to 0.015 mol per 100 g of composition. Hair coloring composition according to any one of claims 1 to 3, characterized in that the inorganic peroxygen oxidizing agent is present in an amount of from 0.01% to less than 3%, preferably from 0.01% to 2.5%. more preferably from 0.01% to 2%, even more preferably from 0.01% to 1%, most preferably from 0.01% to 0.8%, in particular from 0.01% to 0.55%, and in particular thereafter from 0.01% to 0.5% by weight, based on the total weight of the composition. Hair coloring composition according to any one of claims 1 to 4, characterized in that the inorganic peroxygen oxidizing agent is hydrogen peroxide. Hair coloring composition according to any one of claims 1 to 5, characterized in that the total amount of combined hair coloring oxidizing agents is from 0.001% to 5%, preferably from 0.01% to 4%, more preferably from 0 to 5%. 1% to 3%, most preferably from 0.1% to 1% by weight. Hair coloring composition according to any one of claims 1 to 6, characterized in that each of the hair coloring oxidants is present in an amount of from 0.001% to 3%, preferably from 0.01% to 2% by weight. Hair coloring composition according to any one of claims 1 to 7, characterized in that it optionally contains a tableted organic peroxyacid oxidizing agent. Hair coloring composition according to claim 8, characterized in that the tableted organic peroxyacid agent is present in a molar amount of from 0.0001 mol to 0.1 mol per 100 g of composition, more preferably from 0.001 mol to 0.05 mol, most preferably from 0.003 mol to 0.04 mol, and in particular from 0.004 mol to 0.03 mol, per 100 g of hair colorant. Hair coloring composition according to claim 9, characterized in that the tableted organic peroxyacid agent is present in an amount of from 0.01% to 8%, preferably from 0.1% to 6%, more preferably from 0.2% to 6%. 4% and most preferably from 0.3% to 3% by weight, and wherein the weight ratio of inorganic peroxygen oxidizing agent to organic oxidizing agent is in the range of from 0.00125: 1 to 500: 1, more preferably from 0.0125: 1 to 50: first Hair coloring composition according to any one of claims 1 to 10, characterized in that it further comprises one or more buffering agents, preferably an organic and / or inorganic acid having a first pK a below pH 6, selected from the group consisting of aspartic acid, maleic, tartaric, glutamic, glycolic, acetic, succinic, salycilic, formic, benzoic, malic, lactic, malonic, oxalic, citric, phosphoric, and mixtures thereof, preferably selected from the group consisting of acetic acid, succinic acid , salycilic and phosphoric and mixtures thereof. A hair coloring composition according to any one of claims 1 to 11, further comprising one or more surfactants selected from the group consisting of anionic, nonionic, cationic, zwitterionic, amphoteric surfactants and mixtures thereof. Hair coloring composition according to any one of claims 1 to 12, characterized in that it further comprises thickeners, stabilizers, antioxidants and / or any other cosmetically acceptable substance. Use of a hair coloring composition according to any one of claims 1 to 13 for coloring human or animal hair. 15. A method for coloring human or animal hair, wherein the hair coloring composition comprises: (a) from 0.0003 mol per 100 g of composition to less than 0.09 mol per 100 g of composition of an inorganic peroxygen oxidizing agent; and (b) an oxidative hair coloring agent; (c) a diluent suitable for application to the hair; wherein the pH of said coloring agent is in the range of pH 1 to 6. 16. A hair coloring kit comprising an individually packaged oxidizing component and an individually packaged coloring component, wherein the oxidizing component comprises an aqueous solution of an inorganic peroxygen oxidizing agent in an amount of from 0.0003 mol per 100 g of composition to less than 0.09 mole per 100 g of the composition having a pH in the range of 1 to 6 and the coloring component comprises an oxidizing hair coloring agent capable of delivering a solution having a pH in the range of 1 to 6, wherein the pH of the combined oxidizing agent and coloring components is in the range of 1 to 6 . Use of a hair dyeing kit according to claim 16 for oxidation and hair dyeing, wherein the oxidizing agent, oxidative hair coloring agents and adjuvants are mixed prior to application to the hair. 18. A hair coloring method, wherein the hair coloring composition is applied directly to the hair, and wherein the hair coloring composition comprises: (a) an inorganic peroxygen oxidizing agent in a molar amount of from 0.0003 mol per 100 g of the composition to less than 0.09 mol per 100 g of the composition having a pH ranging from 1 to 6; and (b) an oxidizing hair coloring agent at a pH of from 1 to 6; wherein the pH of the combined mixture (a) and (b) has a pH ranging from 1 to 6, preferably from 1.5 to 5.8, more preferably from 2 to 5, and particularly preferably from 3.5 to 4.5. 19. A hair coloring composition suitable for delivering a red shade, comprising: (a) an inorganic peroxygen oxidizing agent in a molar amount of from 0.0003 mol per 100 g of the composition to less than 0.09 mol per 100 g of the composition having a pH ranging from 1 to 6; and (b) an oxidative hair coloring agent at a pH of from 1 to 6; where the change in the colored hair, Delta E, is less than 5 after 20 washes. 20. A hair coloring composition suitable for delivering a light brown shade, comprising: (a) an inorganic peroxygen oxidizing agent in a molar amount of from 0.0003 mol per 100 g of the composition to less than 0.09 mol per 100 g of the composition having a pH ranging from 1 to 6; and (b) an oxidative hair coloring agent at a pH of from 1 to 6; wherein the change in the colored hair, Delta E, is less than 2.6 after 20 washes. 21. Hair coloring agent suitable for delivering a brown or black shade, characterized in that it contains: (a) an inorganic peroxygen oxidizing agent in a molar amount of from 0.0003 mol per 100 g of the composition to less than 0.09 mol per 100 g of the composition having a pH ranging from 1 to 6; and (b) an oxidative hair coloring agent at a pH of from 1 to 6; where the change in the colored hair, Delta E, is less than 2.3 after 20 washes. A hair coloring composition comprising an inorganic peroxygen oxidizing agent and a hair coloring oxidant wherein the color change on the dyed hair, Delta E, is greater than 8, preferably greater than 10, more preferably greater than 12, in particular greater than 15 and most preferably greater than 20, and wherein the color change over the colored hair over time on the colored hair,% Delta E (fading) is less than 15%, preferably less than 12%, more preferably less than 10%, and in particular less than 8% after 20 washes. 23. A method capable of imparting a red shade to the hair, comprising applying to the hair a composition according to claim 1 comprising: (i) an inorganic peroxygen oxidizing agent in a molar amount of from 0.0003 mol per 100 g of the composition to less than 0.09 mol per 100 g of the composition having a pH ranging from 1 to 6; and (ii) an oxidative hair coloring agent at a pH of from 1 to 6; where the untreated hair has been colored light brown after permanent, previously colored, in which the quantities L, a, b are 60, 9 and 32, and where the initial shade of the colored hair has a color value (are tangent ratio (b / a)) to 70, preferably from 30 to 65, more preferably from 35 to 60, and wherein the initial color intensity (L) is greater than 10 and less than 70, preferably greater than 15 and less than 65, more preferably greater than 20 and less than 60 , and wherein the Delta E fading is less than 5.0, preferably less than 4.5, more preferably less than 4.0, and wherein the change in dyed hair,% Delta E, after 20 washes is less than 20%, preferably less more than 15%, more preferably less than 10%. A method capable of imparting a brown or black shade to the hair, comprising applying to the hair a composition according to claim 1, comprising: (i) an inorganic peroxygen oxidizing agent in a molar amount of from 0.0003 mol per 100 g of the composition to less than 0.09 mol per 100 g of the composition having a pH ranging from 1 to 6; and (ii) an oxidative hair coloring agent at a pH of from 1 to 6; where the untreated hair has been light-brown after permanent, previously colored, in which the quantities L, a, b have values of 60, 9 and 32, and where the initial shade * of the colored hair has a color value (are tangent ratio (b / a)) of less than 25 More preferably less than 20, and wherein the initial color intensity (L) is greater than 1 and less than 50, preferably greater than 5 and less than 45, and wherein Delta E ♦ fading less than 2.3, preferably less than 2.0, more preferably less than 1.7, and where the change in dyed hair,% Delta E, after 20 washes is less than 5%, preferably less than 4.5% more preferably less than 4%, most preferably less than 3.5%. 25. A method capable of imparting a light brown shade to the hair, comprising applying to the hair a composition according to claim 1 comprising: (i) an inorganic peroxygen oxidizing agent in a molar amount of from 0.0003 mol per 100 g of the composition to less than 0.09 mol per 100 g of the composition having a pH ranging from 1 to 6; and (ii) an oxidative hair coloring agent at a pH of from 1 to 6; where the untreated hair has been colored light brown after permanent, previously colored, in which the quantities L, a, b are 60, 9 and 32, and where the initial shade of the colored hair has a color value (are tangent ratio (b / a) of 70 to 110, and wherein the initial color intensity (L) is greater than 20 and less than 95, preferably greater than 25 and less than 90, and wherein the Delta E fading is less than 2.6, preferably less than 2.3, and wherein the change in the dyed hair,% Delta E, after 20 washes is less than 15%, preferably less than 12%, more preferably less than 10%, most preferably less than 8%. 26. A method of dyeing hair at a pH in the range of from 1 to 6, wherein the composition comprises applying to the hair a composition according to claim 1 comprising: (a) an inorganic peroxygen oxidizing agent in a molar amount of from 0.0003 mol per 100 g of the composition to less than 0.09 mol per 100 g of the composition having a pH ranging from 1 to 6; and (b) an oxidative hair coloring agent at a pH of from 1 to 6; (c) a diluent suitable for application to the hair; and wherein the pH of the combined (a) and (b) is in the range of pH 1 to pH 6. A method for coloring hair at a pH in the range of from 1 to 6, characterized in that a composition according to claim 1 is applied to the hair, comprising: (a) an inorganic peroxygen oxidizing agent in a molar amount of from 0.0003 mol per 100 g of the composition to less than 0.09 mol per 100 g of the composition having a pH ranging from 1 to 6; and (b) an oxidative hair coloring agent at a pH of from 1 to 6; (c) a diluent suitable for application to the hair; and wherein component (b) is applied to the hair, with or without the component (c), prior to application of components (a) and (c), wherein the pH of the combined (a), (b), and (c) is in the pH range from 1 to 6. 28. A method for coloring hair at a pH in the range of from 1 to 6, wherein the composition comprises: (a) an inorganic peroxygen oxidizing agent in a molar amount of from 0.0003 mol per 100 g of the composition to less than 0.09 mol per 100 g of the composition having a pH ranging from 1 to 6; and (b) an oxidative hair coloring agent at a pH of from 1 to 6; (c) a diluent suitable for application to the hair; and wherein component (a) is applied to the hair, with or without component (c), prior to application of components (b) and (c), and wherein the pH of the combined (a), (b), and (c) is in the pH range from 1 to 6. A hair dyeing method, characterized in that the hair dye composition of claim 1 is present in a single package and is applied directly to the hair. A hair dyeing method, characterized in that the hair dye composition of claim 1 is present as separately packaged components (a) and (b), wherein (a) and (b) comprise: (a) an inorganic peroxygen oxidizing agent in a molar amount of from 0.0003 mol per 100 g of the composition to less than 0.09 mol per 100 g of the composition having a pH ranging from 1 to 6; and (b) an oxidative hair coloring agent at a pH of from 1 to 6; wherein each of components (a) and (b) is stable at pH values in the range of 1 to 6 and wherein the combined mixture of (a) and (b) is stable over time and has a pH in the range of 1 to 6. 31. A hair coloring composition comprising: (a) an inorganic peroxygen oxidizing agent; and (b) an oxidative hair coloring agent; wherein the pH of each of components (a) and (b) is in the range of pH 1 to 6, wherein the combined mixture of (a) and (b) has a pH in the range of 1 to 6, wherein (a) and (b) are in and wherein the molar amount of (a) is from 0.0003 mol per 100 g of composition to less than 0.09 mol per 100 g of composition. Use of a composition according to any one of claims 1 to 13 for dyeing fabrics and / or fibers.