SK84199A3 - Hair coloring compositions - Google Patents

Abstract

A hair coloring composition present in a single package suitable for direct application to the hair wherein the hair coloring mixture comprises: a) an oxidising agent; and b) an oxidative hair coloring agent; and wherein the combined mixture of a) and b) has a pH in the range of from about 1 to about 5 and wherein the resultant color delivered to the hair (Delta E), after at least about 1 month of storage at room temperature, is up to about 75 %, preferably up to about 85 %, more preferably up to about 90 % and most preferably up to about 95 % of the total color delivered to the hair (Delta E) from a mixture of a) and b) on application. The products are storage stable, re-usable and can provide both excellent hair coloring and in-use efficacy benefits as well as improved color development potential after storage at room temperature.

Description

Technical field

The present invention relates to hair dye compositions and hair dye processes, and in particular hair dye compositions comprising either

(a) a separate storage-stable oxidizing agent component in combination with a separate storage-stable, oxidative hair coloring component, each having an acid pH in the range of about 1 to about 6, which, when combined, results in a combined storage stable a reusable coloring composition having a pH from about 1 to about 5, or

b) a stable, reusable mixture of an oxidizing agent and an oxidizing hair coloring agent having a combined acidic pH of from about 1 to about 5 when stored.

BACKGROUND OF THE INVENTION

The desire to change the color of human hair is not an aspect of modern times. Since the time of the Roman Empire, the color of human hair has been routinely alternated to accommodate fashion and style changes. However, achieving the exact initial colors that remain on the hair during the desired period has remained a difficult to achieve goal. Problems in developing hair dye compositions that can deliver accurate long-lasting dyes are partly due to the inherent structure of the hair itself and partly due to the necessary conditions of effective hair dyeing procedures.

For many years, considerable efforts have been made to eliminate the many problems associated with human hair coloring. Various approaches have been developed for hair dyeing, including direct-acting dyes, natural dyes, metallic dyes and oxidative dyes.

Dyeing of human hair or animal hair using oxidative hair dyeing technology is generally accomplished by a mixture of an oxidizing, hair coloring agent and an oxidizing agent.

Oxidizing, hair coloring agents and oxidizing agents can be used to impart a range of colors to the hair. However, a substantial improvement is needed in the application properties of the coloring compositions, such as preparation time of the coloring composition, application complications, product waste that is not used, packaging waste (from multi-component system), storage stability (coloring composition after mixing) and the ability to reuse the mixed coloring composition. Re-use of a coloring composition as defined herein means error correction, coloring or root coverage, and future re-dyeing of hair with the same product as well as color and / or strand tests on small areas of hair.

In order to improve the application properties, as discussed in detail above, a substantial improvement in the area of coloring properties such as color saturation, color development, exact initial color consistency, improved color fastness to washing, improved hair conditions and the degree of hair damage is required.

Conventional oxidative hair coloring compositions generally comprise at least two separately packaged ingredients. These components typically include an oxidizing agent (low pH), such as hydrogen peroxide, and a coloring agent (high pH), such as oxidizing, hair coloring agents. To facilitate the process of coloring the hair, these individually packaged ingredients are generally mixed just prior to application of the coloring composition. Upon mixing, such high pH compositions tend to degrade, which may lead to reduced or weaker staining ability. High pH hair coloring compositions are typically used immediately after mixing. Generally, any excess of the mixed colorant composition is decomposed upon application of the necessary amount to the hair. Furthermore, such conventional coloring compositions cannot be stored and / or reused after mixing since the activated oxidation color system deteriorates rapidly over time. Thus, it is desirable to provide an oxidative hair coloring composition that includes both an oxidizing agent and an oxidative hair coloring agent that are stable and / or reusable upon storage.

As described in detail, conventional hair color oxidation compositions generally include at least two separately packaged ingredients. In doing so, the two components require effective mixing, the mixing process itself may be contaminated and waste, as well as causing extra work for the user. Therefore, it is desirable to develop a convenient and simple to use method by which oxidative hair coloring compositions will be delivered to the hair that do not require mixing of the oxidizing and coloring ingredients.

It is also desirable to develop a hair coloring composition comprising an oxidizing agent and an oxidizing hair coloring agent that can be stored as individually packaged, stable, low pH ingredients that, upon mixing, provide a permanently stable low pH composition suitable for direct application to hair. This low pH mixture can be stored and reused. This allows the consumer to correct mistakes, coat the roots of hair or re-apply the product without having to buy it again.

It has been found that mixtures of oxidizing agents and low pH oxidizing hair coloring agents can be packaged together, in a single package, and their storage is stable and reusable. It has also been found that such mixtures of low pH oxidizing agent and low pH hair coloring agents have improved initial hair coloring properties over conventional high pH. It has also been found that mixtures of an oxidizing agent and low pH oxidative hair coloring agents that have been stored at room temperature have improved color development potential over conventional coloring compositions.

It has also been found that both the oxidizing agent and the low pH oxidizing hair coloring agents are stable over time and can be stored as such.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide low pH hair coloring compositions comprising oxidizing agents as well as oxidative hair coloring agents that are in one package, are fast-acting, easy to use, storage stable, and reusable.

It has been found that the above objectives can meet the storage-stable, reusable low pH hair coloring compositions of the present invention.

All percentages of the resulting composition are by weight in the form to be used unless otherwise stated.

It is an object of the present invention to provide a hair coloring composition suitable for treating human hair or animal hair.

According to one aspect of the present invention, there is provided a hair coloring composition wherein the coloring composition is provided in a single package suitable for direct application to the hair and wherein the hair coloring composition comprises:

(a) oxidizing agent; and

b) an oxidative hair coloring agent;

wherein the combined mixture a) and b) has a pH in the range of about 1 to about 6 and wherein the resulting hair color (Delta E) after at least 1 month of storage at room temperature is up to about 75%, preferably up to about 85%, more preferably up to about 90% and most preferably up to about 95% of the total color delivered by the hair (Delta E) of the composition

and (b) on first application.

According to a further aspect of the present invention there is provided a method for coloring hair wherein the coloring composition contained in a single package is suitable for direct application to the hair and wherein the coloring composition comprises:

(a) oxidizing agent; and

b) an oxidative hair coloring agent;

wherein the combined mixture a) and b) has a pH in the range of about 1 to about 5 and wherein the resulting hair color (Delta E) after at least 1 month of storage at room temperature is up to about 75%, preferably up to about 85%, more preferably up to about 90% and most preferably up to about 95% of the total color delivered by the hair (Delta E) of the composition

and (b) after mixing. .

DETAILED DESCRIPTION OF THE INVENTION

As used herein, the term "hair being treated" may mean hair "living", i.e., on a living body or "inanimate, i.e. wig, hairpiece or other non-viable fibers such as those used in textiles or fabrics. Mammalian, preferably human hair is preferred. However, wool, fur or other melanin-containing fibers are suitable substrates for the compositions of the present invention.

As used herein, the term "hair dye composition" is used broadly to be intended to include compositions comprising those low pH combinations (from about 1 to about 6) of a mixture of an oxidizing agent and an oxidizing coloring agent. In addition, it is also contemplated to include complex compositions that contain other ingredients that may or may not be active ingredients. Thereafter, the term "hair coloring composition is contemplated as the use of compositions which contain, in addition to a mixture of active oxidizing agents and oxidizing coloring agents, substances such as oxidizing aids, sequestrants, stabilizers, thickeners, buffers, carriers, surfactants, solvents , antioxidants, polymers, non-oxidising dyes and conditioners.

As discussed above, the low pH, single-stable, color stable hair coloring compositions and / or re-usable according to the present invention include an oxidizing agent a) which is packaged in combination with an oxidizing, hair coloring agent b), wherein the combined mixture (a) and (b) is stable in storage at a pH of from about 1 to about 5. Preferably, the pH of the combined mixture (a) and (b) is within a range of from about 1.5 to about 5, more preferably from about 1.8 to about 4.7 most preferably from about 2.5 to about 4.5, and in particular from about 2.7 to about 8.

Procedures for bleaching oxidation and hair dye

It will be apparent to those of skill in the art that for a successful color of human hair or animal hair with oxidative dyes, it is generally necessary for the hair to be treated with a mixture of an oxidizing agent and an oxidizing hair coloring agent. As discussed herein, the most common oxidizing agent is hydrogen peroxide.

The hydrogen peroxide has a pKa in the range of about 11.2 to about 11.6 and as such is generally understood to be most effective as a bleaching oxidizing agent having a pH in the range of about 9 to about 12.

Surprisingly, it has now been found that low pH, oxidative, hair coloring compositions that are stable to storage and / or reusable have been developed. Further, it has also been found that improved hair coloring characteristics, such as initial color development and improved color fastness, are accomplished by low pH, single-pack, storage stable and / or reusable oxidative hair coloring compositions of the present invention, with a pH in the range of from about 1 to about pH 6, preferably from about pH 1.5 to about pH 5.8, more preferably from about pH 1.5 to about pH 5.5, most preferably from about pH 2 to about pH 5, and in particular from about pH 2.5 to about pH 4.5.

Color stable compositions packaged in one low pH, stable storage

The single color hair coloring compositions of the present invention comprise, as an essential feature, a mixture of an oxidizing agent and a low pH oxidizing hair coloring agent in the range of about pH 1 to about pH 5.

As described previously, in one package, the combined blend of oxidizing agent and coloring components of the hair coloring composition of the present invention has improved storage stability under low pH conditions (about pH 1 to about pH 5) over conventional high pH coloring compositions.

On storage, stable, in one package, hair coloring composition as defined herein means one-component hair coloring compositions suitable for direct application to the hair, comprising a premixed combination of an oxidizing agent and an oxidizing hair coloring agent, while the coloring composition retains the ability to develop consistent / determined initial hair color immediately after the first formulation (preforming) or after purchase and after storage.

In consumer perception, a consistent / determined initial color means that the color delivered to the hair stored composition (Delta E stored) is not visibly different from the color of the delivered composition on first use (first application after purchase). Initial hair dyeing and hair dyeing after storage, as further detailed below, can be measured by the terms Delta E (Delta E Target, Delta E Stored). Preserved color development potential, as defined herein, means that the color developed by the first color application hair coloring composition (Delta E target) is substantially delivered to the hair after prolonged storage of the composition.

In the compositions of the present invention, the hair color is provided after a minimum of 1 hour (60 minutes) storage (Delta E stored) at room temperature (25 ° C) of greater than about 75%, preferably greater than about 80%, more preferably greater than about 85 %, most preferably greater than about 90%, and in particular greater than about 95% of the total hair color delivered at first application (Delta E target).

In preferred compositions of the present invention, the color delivered to the hair after at least one day (24 hours) of storage (Delta E stored) at room temperature (25 ° C) is greater than about 75%, preferably greater than about 80%, more preferably greater than about 85 %, most preferably greater than about 90%, and in particular greater than about 95% of the total hair color delivered at first application (Delta E target).

In highly preferred compositions of the present invention, the color delivered to the hair after at least one month (720 hours) of storage (Delta E stored) at room temperature (25 ° C) is greater than about 75%, preferably greater than about 80%, more preferably greater than about 85%, most preferably greater than about

90% and in particular greater than about 95% of the total hair color delivered at first application (Delta E target).

According to one aspect of the present invention, there is provided a single, storage-stable, reusable hair coloring composition comprising:

(a) oxidizing agent; and

b) an oxidative hair coloring agent;

wherein the combined mixture of a) and b) has a pH in the range of about 1 to about 5 and wherein the mixture

a) and b) has the ability to be stored at low pH for at least 1 month and wherein the resulting hair delivered color (Delta E stored) is greater than about 75%, preferably greater than about 80%, more preferably greater than about 85%, most preferably greater than about 90%, and in particular greater than about 95%, of the total hair delivered color (Delta E target) of the mixture a) and b) on the first application.

It is generally accepted that the pH of the hair fiber of a human hair is about pH 5.5 to pH 6 (C.R. Robbins, Chemical and Physical Behavior of Human Hair, 2nd Ed., P.157) and that the human hair has an inherent buffer capacity. Certain oxidizing agents such as hydrogen peroxide are known to be stable at about pH 4 when stored. Without wishing to be bound by any particular theory, it is believed that at a pH in the range of about 1 to about 5, preferably in the range of about 1 5 to about 5, more preferably from about 1.8 to about 4.7, most preferably from about 2.5 to about 4.5, and in particular from about 2.7 to about 3.8, is the degree of oxidation bond between the oxidizing agent and the oxidizing agent. , hair coloring agents relatively small. It is proposed here that at low pH mixtures of oxidative, hair coloring agents and oxidizing agents can be stored stably without significantly affecting the color development potential of the resulting hair coloring composition.

In a single reusable, low pH, hair coloring composition of the present invention, they are also suitable for use in a multi-application format (ie, the consumer may use one package for several dye applications over a period of time), giving the consumer the ability to reuse mixed dye a defect correction composition, hair root entrapment, subsequent re-dyeing of hair with the same product / color, and / or sliver tests on small areas of hair. In one package, as defined herein, a hair coloring composition comprising a single-package component comprising an oxidizing agent and an oxidizing coloring agent in a stable low pH composition.

Parts of the components of hair dye compositions

As described in detail, it has been found that low pH oxidizing hair coloring agents can be stored with excellent retained color potential. As defined, the coloring potential of the oxidative colorant is maintained

b) means that the color developed after mixing the oxidative hair coloring component b) with the oxidizing agent a) at time zero (i.e. the Delta E target) is approximately equivalent to the color developed from the oxidative hair colorant mixture

b) with an oxidizing agent a) after a storage period (Delta E stored) at room temperature, 25 ° C, for X hours.

In preferred, low pH storage stable, single pack compositions of the present invention, the Delta E (X hours) is greater than about 90%, preferably greater than about 93%, more preferably greater than about 95%, and most preferably greater than about 98 % Delta E (target).

Thus, according to another aspect of the present invention, it is provided in a single, low pH, storage-stable, reusable hair coloring composition comprising:

(a) oxidizing agent; and

b) an oxidative hair coloring agent;

wherein the combined mixture of a) and b) has a pH in the range of about 1 to about 5 and wherein the mixture

(a) and (b) has the ability to be stored at low pH at room temperature (about 25 ° C) for at least one month and wherein the hair dye potential (Delta E) is greater than about 75%, preferably greater than about 85%, more preferably greater more than about 90%, most preferably greater than about 95%, of the total hair color delivered (Delta E) of the mixture a) and b) at the first application.

Oxidizing agents

The compositions of the invention include as an essential feature at least one oxidizing agent. The oxidizing agent should be safe and effective for use in said compositions. Preferably, the oxidizing agents suitable for use will be soluble in the compositions of the present invention when used in liquid form and / or in the form contemplated for use. Preferably, the oxidizing agents suitable for use will be water-soluble. Water-soluble oxidizing agents as defined herein means reagents having a solubility of about 10 g in 1000 ml of deionized water at 25 ° C ("Chemistry" C.E. Mortimer., 5th Ed., P. 227).

Suitable oxidizing agents are selected from inorganic peroxygen oxidizing agents, preformed organic peroxyacid oxidizing agents, and organic peroxygen oxidizing agents, or mixtures thereof.

Inorganic oxidizing agents

The compositions of the invention may include at least one inorganic oxidizing agent (hereinafter "inorganic peroxygen oxidizing agent") to be safe and effective for use in the composition. Preferably, inorganic peroxygen oxidizing agents suitable for use will be soluble in the compositions of the present invention when used in liquid form and / or in the form contemplated for use. Preferably, the inorganic peroxygen oxidizing agents suitable for use are water-soluble. Water-soluble inorganic peroxygen oxidizing agents as defined herein means reagents having a solubility of about 10 g in 1000 ml of deionized water at 25 ° C ("Chemistry" CE Mortimer., 5th Ed., P. 227) .

The inorganic peroxygen oxidizing agents used herein are generally inorganic peroxylates allowing the recovery of peroxide in aqueous solution. Inorganic peroxygen oxidizing agents are well known in the art and include hydrogen peroxide, inorganic alkali metal peroxides such as sodium periodate, sodium hypobromite and sodium peroxide, and inorganic perhydrate salt of oxidizing compounds such as alkali metal salts of perborates, percarbonates, perphosphates, percarbonates and so on. These inorganic perhydrate salts may be incorporated as monohydrates, tetrahydrates, etc. If desired, mixtures of two or more of such inorganic peroxygen oxidizing agents may be used. Alkali metals of bromates or iodates are suitable for use herein, and bromates are preferred. Highly preferred for use in the compositions of the present invention is hydrogen peroxide.

It has also been found that under the low pH conditions of the present invention, improved initial color, color consistency, color fastness to wash, and color intensity over conventional high pH systems (using equivalent amounts of peroxide and dye), as well as equivalent color (in detail) furthermore, in Experimental Data (Delta E) versus conventional high pH systems using substantially less oxidant (less than 75%) as well as delivering an equivalent color to conventional high pH systems using substantially less oxidant , hair coloring agent (less than 50%). Then, the low-pH, stable and / or reusable hair coloring compositions of the present invention may be formulated to reduce the level of hair damage and the level of skin irritation and discoloration. Furthermore, since the low pH storage stable and / or reusable low pH coloring compositions of the present invention can be formulated without ammonia, these compositions do not induce ammonia-induced negatives regarding skin irritation or odor.

When the inorganic peroxygen oxidizing agent is present in the compositions of the present invention, it is present in a molar amount of from about 0.0003 moles (per 100 g of composition) to less than 0.2 moles (per 100 g of composition), preferably the inorganic peroxygen oxidizing agent present in a molar amount of from about 0.003 moles to about 0.15 moles, more preferably from about 0.006 moles to about 0.1 moles, and in particular from about 0.05 moles to about 0.09 moles (per 100 g of composition).

When an inorganic peroxygen oxidizing agent is present in the compositions of the present invention, it is present in an amount of from about 0.01 wt. % to about 1 wt. %, preferably from about 0.01 wt. % to about 0.8 wt. %, more preferably from about 0.01 wt. % to about 0.75 wt. %, most preferably from about 0.01 wt. % to about 0.55 wt. % and in particular from about 0.01 wt. % to about 0.5 wt. %.

Preformed organic peroxyacids

The compositions of the present invention may comprise one or more preformed organic peroxyacid oxidizing agents.

Suitable organic peroxyacid oxidizing agents for use in the dye compositions of the present invention have the general formula: RC (O) OOH wherein R is selected from saturated or unsaturated, substituted or unsubstituted, straight or branched chain alkyl, aryl or alkaryl groups of 1 to 14 atoms atoms.

A class of organic peroxyacid compounds suitable for use herein are the amide substituted compounds of the following general formula: ^R1 - C - N - ^R2 - C - OOH ^{R1-N-C-R 2} -C -OOH

OR ⁵ O or R ⁵ OO wherein R ¹ is a saturated or unsaturated alkyl or alkaryl group, or an aryl group having 1 to 14 carbon atoms, R ² is a saturated or unsaturated alkyl or alkaryl group, or an aryl group having 1 to 14 atoms and R ⁵ is hydrogen, or a saturated or unsaturated alkyl or alkaryl group, or an aryl group having 1 to 10 carbon atoms. Amide substituted organic peroxyacid compounds of this type are described in EP-A0170 386.

Other suitable organic peroxyacid oxidising agents include peracetic, pernanoic, nonylamidoperoxycaproic (NAPCA), perbenzoic, m-chloroperbenzoic, isophthalic, mono-perphthalic peroxylauric, hexanesulphonyl, N, N-phthaloylamino, monoper succinic, nonanoyloxybenzoic, dodecanedioylmonoperoxybenzoic, nonylamide of peroxyadipic acid, diacyl and tetraacylperoxides, in particular diperoxydodecanodioic acid, diperoxytetradecanedioic acid and diperoxyhexadodecanodioic acid and derivatives thereof. Mono- and diperazelaic acid and mono- and di-perbrasylic acid and N-phthaloylaminoperoxycaproic acid and derivatives thereof are also suitable for use in the invention.

Preferred peroxyacids suitable for use in the invention are selected from peracetic and pernanoic acids and mixtures thereof.

The preformed organic peroxyacid oxidizing agents must be safe and effective for use in the compositions. Preferably, the preformed organic peroxyacid oxidizing agents suitable for use herein are soluble in the compositions of the present invention when used in liquid form and / or in the form contemplated for use. Preferably, the preformed organic peroxyacid oxidizing agents suitable for use are water-soluble. Water-soluble organic peroxyacid oxidizing agents as defined herein means reagents having a solubility of about 10 g in 1000 ml of deionized water at 25 ° C ("Chemistry" C.E. Mortimer., 5th Ed., P. 227).

Where a preformed organic peroxyacid oxidant is present, it is in a molar amount of from about 0.00013 moles to about 0.105 moles (per 100 g of the composition), more preferably from about 0.0013 moles to about 0.05 moles, most preferably from about 0.002 moles to about 0.105 moles. 0.04 moles, and in particular from about 0.004 moles to about 0.03 moles (per 100 g) of the hair coloring compositions of the present invention.

The preformed organic peroxyacid oxidizing agent is preferably present in an amount of from about 0.01 wt. % to about 8 wt. %, more preferably from about 0.1 wt. % to about 6 wt. %, most preferably from about 0.2 wt. % to about 4 wt. % and in particular from about 0.3 wt. % to about 3 wt. % hair coloring composition. The weight ratio of the inorganic peroxygen oxidizing agent to the preformed organic peroxyacid is preferably from about 0.0125: 1 to about 500: 1, more preferably from about 0.0125: 1 to about 50: 1.

The preformed organic peroxyacid oxidizing agents and inorganic peroxygen oxidizing agents suitable for said use in the compositions of the present invention may include other organic peroxides such as urea peroxide, melamine peroxide, and mixtures thereof. When an amount of organic peroxide is present, it is in an amount of from about 0.01 wt. % to about 3 wt. %, preferably from about 0.01 wt. % to about 2 wt. %, more preferably from about 0.1 wt. % to about 1.5 wt. % and most preferably from about 0.2 wt. % to about 1 wt. % of the composition.

Hair coloring

When hair is to be dyed, it is desirable that the color be resistant to fading satiety, causing hair washing (also known as color fastness), sweating, hair spray, and other external factors such as exposure to the sun and that the color is retained in a consistent state for a specified period of time. Further damage to the hair, which may lead to irregular dye binding as discussed above, may lead to increased fading of damaged hair portions and consequently to irregular color fading over time. Another problem commonly associated with coloring human hair is the need for dye systems that avoid the deleterious effect on the hair and skin of the user, such as broken hair or skin irritation or skin coloring.

It is then desirable to develop a hair coloring composition that is characterized by reduced fading, provides improved washout resistance under a regular hygiene regime, can provide hair with substantially consistent hair color results having reduced irritating effect on the skin having reduced staining and has reduced harmful effects on the user's hair.

It has now been found that the combination of an oxidizing agent with one or more oxidative hair coloring agents at a pH lower than the internal hair pH, between about pH 1 to about pH 5, can provide excellent hair coloring compositions in combination with improved hair coloring compositions. color and durability to wash hair dye over a period of time, desirable color saturation and color intensity, reduced hair damage, reduced skin irritation, reduced skin coloring, and more effective staining. Furthermore, it has been found that the color utilization efficiency (color change) of the oxidizing agent and oxidative hair coloring agents is improved under the low pH conditions of the present invention. It has been found that the hair coloring compositions of the present invention can impart these excellent attributes as a result of hair coloring with minimal hair damage at low pH (about 1 to about 6).

It is an object of the present invention to provide storage stable, reusable, low pH hair coloring compositions that provide a combination of improved hair coloring attributes such as longer color durability (reduced fading), initial color formation, enhanced color bonding, and color consistency for hair types . Hair types as defined herein mean different age and conditions, i. not chemically modified, gray, treated, faded, etc.

Yet another object of the present invention is to provide storage-stable, reusable, low pH hair coloring compositions having reduced levels of skin irritation and / or skin discoloration over conventional high pH systems, leaving minimal hair fiber damage and reduced skin discoloration in the skin. in combination with an acceptable odor.

Yet another, further object of the present invention is to provide storage-stable, reusable low pH hair coloring compositions having improved efficacy (improved color utilization). The use of a color as defined herein means a change in hair color, expressed in terms of Delta E, as defined in the Experimental Section below. Yet another object of the present invention is to provide hair dye compositions with reduced skin and / or hair damage that can impart an equivalent use of color (as opposed to conventional high pH systems) in combination with improved color fastness and consistency using less dye and / or less oxidizing agent.

Hair coloring agents

The low pH hair coloring compositions of the present invention include as an essential feature an oxidative hair coloring agent. Such oxidative hair coloring agents are used in combination with the oxidation systems of the present invention to form low pH, stable, semi-permanent, partially permanent or temporary hair dye compositions.

Permanent hair coloring compositions as defined herein are compositions whose application to the hair is substantially wash resistant. Semi-permanent hair coloring compositions as defined herein are compositions that are substantially washed out of the hair after application to 24 hair washes upon application. Partially stable hair coloring compositions as defined herein are compositions that are substantially washed out of the hair after application to 10 hair washes upon application. Temporary hair coloring compositions as defined herein are compositions that are substantially washed from the hair after application to 2 hair washes upon application. These different types of hair coloring compositions can be formed by a specific combination of oxidant and / or colorant with varying amounts and ratios. Washing as defined herein is the process by which hair is removed from the hair during the period during which the normal hair wash regime is in progress. Color fastness to washing as defined herein means the resistance of colored hair to washing. Color fastness as defined herein can be measured in relative color change values on stained hair (Delta E) after several washes (shampoo). Substantial hair dye removal as defined herein means a color change in the dyed hair (Delta E) greater than about 2 to 10 washes.

The concentration of each oxidizing hair coloring agent in the low pH coloring compositions of the present invention is from about 0.001 wt. % to about 3 wt. % and preferably from about 0.01 wt. % to about 2 wt.%.

The total combined amount of oxidative hair coloring agents in the compositions of the present invention is from about 0.001 wt. % to about 5 wt. %, preferably from about 0.01 wt. % to about 4 wt. %, more preferably from about 0.1 wt. % to about 3 wt. %, most preferably from about 0.1 wt. % to about 1 wt. %.

t _t v

In conventional hair coloring compositions, the total amount of oxidative hair coloring agents present in the compositions ranges from about 0.2 wt. % to about 3.5 wt. %. Accordingly, the compositions of the present invention may exhibit improved hair coloring attributes, such as initial color development and initial color consistency, in combination with improved color fastness over time compared to conventional high pH systems having similar amounts of colorant. Color consistency, as used herein, means the relative predictability of initial color development and improved color retention over time for different hair types.

The efficiency of the oxidative dyes is improved at low pH so that the compositions of the present invention are highly valuable for delivering good, high-intensity dyes (dark colors) with reduced amounts of dye. In particular, good hair coloring results in combination with equivalent color development (as opposed to high pH systems) using the inorganic peroxygen oxidizing agents of the present invention and substantially less dye than conventional high color hair coloring compositions can be achieved.

Then, according to another aspect of the present invention, there is provided a hair dye composition comprising:

(a) oxidizing agent;

b) an oxidative hair coloring agent; and

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

wherein the pH of each of a) and b) is in the range of about 1 to about 6 and wherein the combined mixture of a) and b) has a pH in the range of about 1 to about 5 and wherein a) and b) can be stored at low pH either alone or mixed for at least 1 month at room temperature and wherein the resulting hair color (Delta E) is greater than about 75%, preferably greater than about 85%, more preferably greater than about 90% and most preferably greater than about 95% of the total the color delivered by the hair (Delta E target) from mixture (a) and (b) after mixing.

As described herein, it has been found that the combination of an oxidizing agent with an oxidizing, low pH hair coloring agent is highly valuable for imparting excellent hair coloring attributes in combination with reduced levels of hair damage, skin irritation and skin coloring in combination with improved odor profile. (as opposed to conventional high pH compositions). A further benefit of the low pH color compositions of the present invention is that reduced levels of skin discoloration can be observed with such compositions compared to conventional high pH compositions.

Then, according to another aspect of the present invention, there is provided a hair dye composition that imparts a light chestnut color to pale brown hair having 40% gray, comprising:

(a) oxidizing agent;

b) an oxidative hair coloring agent; and

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

wherein the pH of each of a) and b) is in the range of about 1 to about 5 and wherein the combined mixture of a) and b) has a pH in the range of about 1 to about 6 and wherein a) and b) can be stored at low pH either alone or mixed for at least 1 month at room temperature and wherein the change in skin color upon application of the product (Delta E) is less than about 4, preferably less than about 3, more preferably less than about 2.7. Light brown hair having a 40% gray coverage is defined by L, a, b data values having a "L" value in the range of about 35 to about 37, an "a" value in the range of about 4.5 to about 5.5, and "b" a value ranging from about 11.5 to about 12.7.

Without being limited by any particular theory, it is believed that these improvements (relating to reduced skin irritation and / or skin discoloration) are the result of a combination of a) reduced colorant and low pH; b) reduction of contact sensitization of paraphenylenediamine (PPD) at low pH (higher amounts of PPD have been shown to exhibit contact sensitization at higher pH but not at low pH); c) eliminating the formation of a nitrobenzene contact sensitiser (which may occur with high pH compositions); d) reduced skin staining levels at low pH versus high pH; and e) reducing skin irritation and negative odor as a result of ammonia elimination and the use of alternative oxidizing agents in the low pH dye compositions of the present invention.

Procedures for oxidative hair dyeing

Any oxidative hair coloring agent may be used in the compositions of the present invention. Typically, but not limited to, oxidative hair coloring agents basically comprise at least two components, both referred to as dye-forming intermediates (or precursors). The dye forming intermediates may react in the presence of a suitable oxidant to form a color molecule.

Dyes forming intermediates used in oxidative hair dyes include: aromatic diamines, aminophenols, various heterocycles, phenols, naphthols, and various derivatives thereof. These dye-forming intermediates can be broadly classified as: primary intermediates and secondary intermediates. The primary intermediates, which are also known as precursors to oxidative dyes, are chemical compounds that become active after oxidation and can then react with each other and / or with binding members to form colored dye complexes. Secondary intermediates, also known as modifiers or binding members, are generally

Even 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 suitable for use in the compositions and processes herein include: aromatic diamines, polyhydrogen 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 suggested herein that the process by which the dye is formed from the primary intermediates and secondary binding compounds generally comprises a sequence of sequences so that the primary intermediate can become activated (oxidized) and then, when coupled to the binding member, dimerically conjugated color mixtures which in turn can be combined with another "activated" primary intermediate to form a trimeric conjugated color molecule.

Chemistry of oxidative hair dyeing through pH

Without wishing to be bound by any particular theory, it is generally understood that conventional oxidative staining occurs between oxidation precursor molecules, oxidation binding member molecules, and a peroxygen oxidizing agent at high pH (8-10). Typical precursors. include 1,4-disubstituted benzene derivatives and typical binding members include 1,2-or 1,3-disubstituted benzene derivatives.

It is generally accepted that the pH of the hair fiber of a human hair is about 5.5 to 6 (C.R. Robbins, Chemical and Physical Behavior of Human Hair, 2nd Ed., P. 157) and that the hair has an inherent buffer capacity.

Surprisingly, it has now been found that oxidative hair coloring, with a pH of 5 or less, oxidizing agents and an oxidizing hair coloring agent is highly valuable for providing it with an excellent initial hair color in combination with improved color and color fastness during periods of desirable color saturation and clarity of the color, reduced hair damage, reduced skin irritation, reduced skin discoloration, and more effective staining. It has further been found that the coloring efficiency (i.e., increased color change) of the inorganic peroxygen oxidizing agents and oxidative hair coloring agents of the present invention is improved under the low pH conditions of the present invention. It has been found that the low pH hair coloring compositions of the present invention can impart these excellent attributes through hair coloring with minimal hair damage.

It has also been found that at pH values less than pH 5, preferably from about pH

1.5 to about pH 5.8, more preferably from about pH 1.5 to about 5, even more preferably from about pH 1.8 to about 4.7, most preferably from about pH 2.5 to about 4.5, and especially from about about pH 2.7 to about 3.8, improvements in color development are achieved.

Oxidative dye precursors

In general conditions, the primary oxidation dye intermediates include those monomeric substances which, upon oxidation, form oligomers or polymers having extended conjugated electron systems in their molecular structure. Due to the new electron structure, the resulting oligomers and polymers show a shift to the visible region in their electron spectrum and appear colored. For example, oxidative primary intermediates capable of forming colored polymers include substances such as aniline which has one functional group and which upon oxidation produces a series of conjugated imines and quinone dimers, timers, and tTTs. lying in the color range from green to black. Compounds such as p-phenylenediamine, which has two functional groups, are capable of oxidative polymerization to produce higher molecular weight colorants having extended conjugated electron systems. Oxidative dyes known in the art can be used in the low pH compositions of the present invention. A list of representatives of primary intermediates and secondary binding members suitable for use herein has been found by Sagarin, " Cosmetic Science and Technology ", Interscience Special Ed., Vol. 2, p. 308 to 310. It is to be understood that the primary intermediates detailed below are by way of example only and are not intended to limit the compositions and methods herein.

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

Examples of suitable aromatic diamines, aminophenols, polyhydrogen phenols and derivatives thereof are compounds having the general formulas (I), (II) and (III) below:

- N— R

• f (l) or

HX wherein Y is hydrogen, halogen, (i.e., fluoro, chloro, bromo or iodo), nitro, amino, hydroxyl,

ABOUT

II - CH, I

-COOM or -SO 3 M (where M is hydrogen or an alkaline earth metal, ammonium or substituted ammonium in which one or more of the hydrogens on the ammonium ion is replaced by 1 to 3 carbon atoms of the alkyl or hydroalkyl radical), wherein R ¹ , R ² , 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, aralkyl and R ⁵ is hydrogen, C 1 -C 4 unsubstituted or substituted alkyl or alkenyl; wherein the substituents are selected from those defined as Y above, or a C 6 to C 8 unsubstituted or substituted aryl, alkaryl or aralkyl group wherein the substituents are selected from those defined as Y above. Since the precursors of formula (I) are amines, they can be used herein in the form of peroxide-compatible salts, as noted, in which X represents peroxide-compatible anions of the type already detailed herein. The general formula of the indicated salt is understood to include those salts having mono- and trine-negative anions.

Specific examples of compounds of formula (I) are: o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2-chloro-p-phenylenediamine, 2-iodo-phenylenediamine, 4-nitro-o-phenylenediamine, 2-nitro-p- phenylenediamine, 1,3,5-triaminobenzene, 2-hydroxy-p-phenylenediamine, 2,4-diaminobenzoic acid, sodium 2,4-diaminobenzoate, calcium di-2,4-diaminobenzoate, ammonium 2,4-diaminobenzoate, trimethylammonium, 2,4-diaminobenzoate, tri- (2-hydroxyethyl) ammonium

2,4-diaminobenzoate, 2,4-diaminobenzaldehyde carbonate, 2,4-diaminobenzenesulfonic acid, potassium 2,4-diaminobenzenesulfonate, N, N-diisopropyl-p-phenylenediaminobicarbonate, N, N-dimethyl-p-phenylenediamine, N-ethyl- N '- (2-propenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, N-phenyl-N-benzyl-p-phenylenediamine,' N-ethyl-N '- (3-ethylphenyl) -phenylenediamine, 2,4 -toluenediamine, 2-ethyl-p-phenylenediamine, 2- (2-bromomethyl) -phenylenediamine, 2-phenyl-p-phenylenediamine laurate, 4- (2,5-diaminophenyl) benzaldehyde, 2-benzyl-p-phenylenediamine acetate, 2- (4 -nitrobenzyl) -p-phenylenediamine, 2- (4-methylphenyl) -phenylenediamine, 2- (2,5-diaminophenyl) -5-methylbenzoic acid, methoxyparaphenylenediamine, dimethyl-p-phenylenediamine, 2,5-dimethylparaphenylenediamine, 2-methyl-5 -methoxy.paraphenylenediamine, 2,6-methyl-5-methoxy-paraphenylenediamine, 3-methyl21

4-amino-NN-diethylaniline, N, N-bis (p-hydroxyethyl-paraphenylenediamine, 3-methyl-4-aminoN, N-bis (p-hydroxyethyl) aniline, 3-chloro-4-amino-N, N- bis (p-hydroxyethyl) aniline, 4-amino-N-ethyl-N- (carbamethyl) aniline, 3-methyl-4-amino-N-ethyl-N- (carbamethyl) aniline, 4-amino-Netyl- (p-piperidonoethyl) aniline, 3-methyl-4-amino-N-ethyl- (p-piperidonoethyl) aniline, 4-amino-N-ethyl-N- (β-morpholinoethyl) aniline, 4-amino-N-ethyl-N- (p- acetylaminoethyl) aniline, 4-amino-;

N- (β-methoxyethyl) aniline, 3-methyl-4-amino-N-ethyl-N- (β-acetylaminoethyl) aniline, 4-amino N-ethyl-N- (β-mesylaminoethyl) aniline, 4-amino-N -ethyl-N- (p-sulfoethyl) aniline, 3-aminophenyl) morpholine, N- (4-aminophenyl) piperidine, 2,3-dimethyl-p-phenylenediamine, isopropyl-p-phenylenediamine, N, N-bis- (2- hydroxyethyl) -p-fenyléndiamínsulfát.

or

wherein X and Y are the same as in formula (I), R ¹ and R ² 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 ^e is hydrogen or C 1 to C 4 substituted or unsubstituted alkyl or alkenyl, wherein the substituents are selected from those defined as Y in formula (I).

Specific examples of compounds of formula (II) are:

o-aminophenol, m-aminophenol, p-aminophenol, 2-iodo-p-aminophenol, 2-nitro-p-aminophenol,

3,4-dihydroxyaniline, 3,4-diaminophenol, chloroacetate, 2-hydroxy-4-aminobenzoic acid, 2-hydroxy-4-aminobenzaldehyde, 3-amino-4-hydroxybenzenesulfonic acid, N, N-diisopropyl-p-aminophenol, N-methyl-N- (1-propenyl) -p-aminophenol, N22 phenyl-N-benzyl-p-aminophenol sulfate, N-methyl-N- (3-ethylphenyl) -p-aminophenol, 2-nitro-5-ethyl- p-aminophenol,

2-nitro-5- (2-bromomethyl) -p-aminophenol, (2-hydroxy-5aminophenyl) acetaldehyde, 2-methyl-p-aminophenol, (2-hydroxy-5-aminophenyl) acetic acid, 3- (2- hydroxy-5-aminophenyl) -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) -paminophenol, p-methoxyaniline, 2-bromomethyl-4-aminophenylether phosphate, 2-nitroethyl-4-aminophenyl ether bromide, 2-aminoethyl-4-aminophenyl ether, 2-hydroxyethyl-4-aminophenyl ether, (4-aminophenoxy) acetaldehyde, (4-aminophenoxy) acetic acid, (4aminophenoxy) methanesulfonic acid, 1-propenyl-4-aminophenyl ether isobutyl ether (2-chloro) -1-propenyl-4-aminophenyl ether, (2-nitro) -1-propenyl-4-aminophenyl ether, (2-amino) propenyl-4-aminophenyl ether, (2-hydroxy) -1-propenyl-4- aminophenyl ether, N-methyl-paminophenol, 3-ethyl-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, 2-hydroxymethyl-4-aminophenol, 3-hydroxymethyl-4-aminophenol.

R

(III) wherein Y, R ⁵ and R ⁶ are as defined in formula (II) above.

Specific examples of compounds of formula (III) are: o-hydroxyphenol (catechol), m-hydroxyphenol (resorcinol), p-hydroxyphenol (hydroquinone),

4-methoxyphenol, 2-methoxyphenol, 4- (2-chloroethoxy) phenol, 4- (2-propenoxy) phenol, 4- (3-chloro-2-propenoxy) phenol, 2-chloro-4-hydroxyphenol (2-chlorohydroquinone), 2-nitro-4-hydroxyphenol (2-nitrohydroquinone), 2-amino-4-hydroxyphenol, 1,2,3-trihydroxybenzene (pyrogalol), 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-nitrophenyl-4-chlorophenyl) -4-hydroxyphenol, 3-methoxy-4-hydroxybenzaldehyde, 2-methoxy-4- (1-propenyl) phenol, 4-hydroxy-3-methoxycinnamic acid, 2,5- dimethoxyaniline, 2-methylresorcinol, alpha-naphthol and salts thereof.

Secondary binding compounds (color modifiers), such as those detailed below, are preferably used in conjunction with primary intermediates and are considered to be placed in the color polymers during their formation and cause shifts in the Connected Electron Spectrum, resulting in subtle color changes.

Secondary binding compounds that are suitable for incorporation into the dye compositions and methods previously described herein include certain aromatic amines and phenols and derivatives thereof that do not form a single color but can modify the color, shade, or color intensity produced by the primary oxidized dye intermediates. Certain aromatic compounds of amines and phenols and their derivatives, including some aromatic diamines and polyhydrogen phenols of the types described in formulas (I), (II) and (III) above, but which are well known in the art, are not suitable primary intermediates, are suitable as binding compounds.

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

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

or

ΗΧ

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

ABOUT

I

- CH

-COOM or -SO3M (where M is hydrogen, or an alkaline earth metal, ammonium or substituted ammonium in which one or more of the hydrogens on the ammonium ion is replaced by 1 to 3 carbon atoms of the alkyl or hydroalkyl radical), wherein R ¹ and R ² are 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 8 -C 8 aryl, alkaryl, aralkyl and R ⁷ is hydrogen, C 1 -C 4 unsubstituted or substituted alkyl or alkenyl wherein the substituents are selected from those or C 1 -C 8 unsubstituted or substituted aryl, alkaryl or aralkyl, wherein the substituents are selected from those defined as Z above and X is as defined in formula (I).

Specific examples of compounds of formula (IV) are: aniline, p-chloroaniline, p-fluoroaniline, p-nitroaniline, p-aminobenzaldehyde, paminobenzoic acid, lithium p-aminobenzoate, calcium di-p-aminobenzoate, ammonium aminobenzoate, trimethylammonium-p- aminobenzoate, tri (2-hydroxyethyl) -paminobenzoate, p-aminobenzenesulfonic acid, potassium p-aminobenzenesulfonate, N-methylaniline, N-propyl-N-phenylaniline, N-methyl-N-2-propenylaniline, N-benzylaniline, N (2 -ethylphenyl) aniline, 4-methyianiline, 4- (2-bromomethyl) aniline, 2- (2-nitroethyl) aniline, (4aminophenyl) acetaldehyde, (4-aminophenyl) acetic acid, 4- (2-propenyl) aniline acetate, 4 (3-bromo-2-propenyl) aniline, 4-phenylaniline chloroacetate, 4- (3-chlorophenyl) aniline, 4benzylaniline, 4- (4-iodobenzyl) aniline, 4- (3-ethylphenyl) aniline, 4- (2- chloro-4-ethylphenyl) aniline.

wherein Z and R ⁷ are as defined in formula (IV) and R ⁸ is hydrogen or C 1 -C 4 substituted or unsubstituted alkyl or alkenyl, wherein the substituents are selected from those defined as Z in formula (IV).

Specific examples of compounds of formula (V) are:

phenol, p-chlorophenol, p-nitrophenol, p-hydroxybenzaldehyde, p-hydroxybenzoic acid, p-hydroxybenzenesulfonic acid, ethylphenyl ether, 2-chloroethylphenyl ether, 2-nitroethylphenyl ether, phenoxyacetaldehyde, phenoxyacetic acid, 3-phenoxy-3-phenoxy-1-phenoxy-1 -1-propene, 3-phenoxy-2-bromo-1-propene, 4-propylphenol, 4- (3-bromopropyl) phenol, 2- (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-3hydroxypyridine, tetraaminopyrimidine, 1,2,4-trihydroxybenzene, 1,2,4-trihydroxy -5 (C 1 -C 6 alkyl) benzene, 1,2,3-trihydroxybenzene, 4-aminoresorcinol, 1,2dihydroxybenzene, 2-amino-1,4-dihydroxybenzene, 2-amino-4-methoxyphenol, 2,4-diaminophenol, 3-methoxy -1,2-dihydroxybenzene, 1,4-dihydroxy-2- (N, N-diethylamino) benzene, 2,5-diamino-4-methoxy-1-hydroxybenzene n, 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) amino] benzene and their salt.

Other primary intermediates suitable for use include mixtures of catechol, and in particular mixtures of catechol "dopa", which include dopa itself, as well as homologues, analogs and DOPA derivatives. Examples of suitable catechol species include cysteinyl dopa, alpha-alkyl dopa having 1 to 4, preferably 1 to 2 carbon atoms in the alkyl group, epunephrine and dopa alkyl esters having 1 to 6, preferably 1 to 2 carbon atoms in the alkyl group.

Generally, suitable catechols represented by formula (VI) below are:

wherein R ¹ , R ² and R ³ , which may be the same or different, are substituents of electron donors or acceptors selected from hydrogen, · 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 ⁵ , which may be the same or different, are hydrogen, lower (C 1 -C 6 alkyl, wherein the substituent may be OH, OR, NHCOR ⁶ , NHCONH 2, NHCO 2 R ⁶ , NHCSNH 2, CN, COOH, SO ₃ H, SO ₂ NR) ^6, SO 2 NR ⁶ or CO 2 R ^6, R ⁶ is a lower (Ci-6) alkyl, lower (C -C) hydroxyalkyl fenylviazaný to the nitrogen by an alkylene chain, phenyl or substituted phenyl with the substituent defined as ^R1, and R is C -C alkyl, or C Cehydroxyalkyl.

Also included are oxidative hair coloring agents according to the formula below:

wherein R ¹ is substituted or unsubstituted benzene ring, tertiary butyl, etc .; R is a substituted or unsubstituted benzene ring of the formula:

wherein R is aminoalkyl, amidoalkyl, aminobenzene (substituted or unsubstituted), alkyl, substituted or unsubstituted benzene ring; R ¹ is a substituted or unsubstituted benzene ring.

Primary intermediates herein may be used alone or in combination with other primary intermediates, and one or more may be used in combination with one or more binding members. The choice of primary intermediates and binding members will be determined by the color, shade, and color intensity that is desired. Preferably, nineteen primary intermediates and couplers may be used herein, singly or in combination, to provide dyes having a variety of shades ranging from blond to black; these are: pyrogalol, resorcinol, p-toluenediamine, p-phenylenediamine, ophenylenediamine, m-phenylenediamine, o-aminophenol, p-aminophenol, 4-amino-2-nitrophenol, nitro-p-phenylenediamine, N-phenyl-p-phenylenediamine , m-aminophenol, 2-amino-3-hydroxypyridine, 1-naphthol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 4-amino-2-hydroxytoluene, 1,5-dihydroxynaphthalene, 2-methylresorcinol and 2,4- diaminoanisol. These can be used in molecular form or in the form of peroxide compatible salts as described above.

The primary intermediates and binding compounds as mentioned herein may be combined to impart a wide variety of colors to the hair. Hair colors can vary according to color depth and color intensity. As already described, the compositions of the present invention are highly valuable for providing them with high intensity colors. Color intensity as defined herein means the quantity of color compound formed on and remaining on the hair. Generally, high intensity as defined herein means dark and rich colors such as dark red, dark brown or black, etc. Accordingly, it is possible to formulate hair dyes of different color intensity by adjusting the initial amounts of each of the oxidative dyes.

f, '

For example, low intensity dyes, such as natural blond, generally contain from about 0.001 wt. % to about 5 wt. %, preferably from about 0.1 wt. % to about 2 wt. %, more preferably from about 0.2 wt. % to about 1 wt. % of the coloring composition of the total dye oxidizing agents and 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 binding members such as resorcinol,

2-methylresorcinol or 4-chlororesorcinol.

Similarly, the combination of said primary intermediates with binding members such as 5-amino-2-methylphenol and 1,3-diaminobenzene derivatives such as 2,4-diaminoanisole with amounts of from about 0.5% to about 1% of total coloring agents may result in medium intensity of red colors. High intensity dyes such as blue to bluish violet shade can be formed by combining said primary intermediates with binding members such as 1,3-diaminobenzene or derivatives thereof such as 2,5-diaminotoluene with values from about 1 wt. % to about 6 wt. % of the total coloring agent composition. Black hair dyes may be obtained by combining said primary intermediates with binding members such as 1,3-diaminobenzene or derivatives thereof.

However, objections have been raised to the physiological compatibility of paraaminophenol, which is commonly used to deliver red hair. Similarly, the physiological compatibility of some black-promoting agents such as paraphenylenediamine (PPD) has raised questions. Thus, there is a need for oxidative hair coloring compositions having an improved safety profile, and in particular oxidative hair compositions for delivering dark colors, i. high color intensity dyes having an improved safety profile. As discussed herein, the low pH compositions of the present invention provide excellent hair dye attributes in combination with reduced levels of hair damage and skin discoloration and / or irritation.

As such, the compositions of the present invention are highly valuable for imparting attributes to improve hair conditions in combination with good initial coloring and consistency and improved color fastness to wash over time at reduced levels of hair damage and skin irritation and / or coloration.

Non - oxidising and other coloring matter

The hair coloring compositions of the present invention may optionally include non-oxidizing and other coloring agents for the basic oxidative hair coloring agents. Optional and other dyes suitable for use in hair dye compositions and methods of the present invention include semi-permanent, temporary or other dyes. Non-oxidative dyes as defined herein include so-called dyes. 'Direct-effect dyes', metallic dyes, metal chelate dyes, reaction fiber dyes and other synthetic and natural dyes. Various types of non-oxidative dyes have been described in detail by Clarence Robbins in "Chemical and Physical Behavior of Human Hair", 3rd Ed., (Pp. 250-259); G. S. Kass in "The Chemistry and Manufacture of Cosmetics", Vol. IV, 2nd ed. Maison G. De Navarre, Chapter 45, (pp. 841-920); F. E. Wall in "Cosmetics: Science and technology", 2nd ed. II Balsam Sagarin, Chapter 23 (pp. 279-343); C. Zviak in "The Science of Hair Line", Chapter 7 (pp. 235-261) and JCJohnson in "Hair Dyes", Noes Data Corp., Park Ridge, USA (1973), (pp. 3-91 and 113-139).

Direct-acting dyes which do not require an oxidative effect to form the dye are also determined by the color tone of the hair and have long been known in the art. They are usually applied to the hair in a base matrix that includes surfactants. Direct acting dyes include nitro-dyes such as nitroaminobenzene derivatives or nitroaminophenol; disperse dyes such as nitroarylamines, aminoanthraquinones or azo dyes; anthraquinone dyes, naphthoquinone dyes; base dyes such as acridine orange C.l. 46,005th

Nitra dyes are added to the dye compositions to enhance the color of the dye and to add a suitable aesthetic color to the dye mixture prior to application.

Other examples of direct acting dyes include Arianor dyes base brown 17, C.I. (Color Index) - # 12,521; Base Red 76, C.I. - 12 245; base brown 16, C.l. - 12 250; base yellow 57, C.I. - 12 719 and base blue 99, C.l. - 56 059 and other direct-acting dyes such as acid yellow 1,

C.I. - 10,316 (D&C yellow no. 7); acid yellow no. 9, C.I. - 13,015; basic violet C.l. - 45 170; disperse yellow 3, C.I. - 11 855; base yellow 57, C.l. - 12,719; disperse yellow 1, C.I. 10 345; basic violet 1, C.l. - 42,535; basic violet 3, C.l. 42,555; green-blue, C.l. - 42,090 (FD&C blue no. 1); yellow-red, C.l. 14,700 (FD & C Red no. 4); yellow, C.l. 19,140 (FD & C yellow no. 5); yellow-orange, C.l. - 15,985 (FD&C yellow no. 6); blue-green, C.l. - 42,053 (FD&C green no. 3); yellow-red, C.l. 16,035 (FD&C red no. 40); blue-green, C.l. - 61,570 (D&C green no. 3); orange, C.l. 45,370 (D&C orange no. 5); red, C.l. 15,850 (D&C red no. 6); blue-red, C.l. 15,850 (D&C red no. 7); light blue red, C.l. 45,380 (D&C red no. 22); blue-red, C.l. 45,410 (D&C red no. 28); blue-red, C.l. 73,360 (D&C red no. 30); reddish purple, C.I. 17,200 (D&C red. No. 33); off-blue-red, C.l. 15808 (D&C red no. 34) bright yellow red, C.I. 12,085 (D&C red no. 36); bright orange, C.l. 15,510 (D&C orange no. 4); green-yellow, C.l. 47,005 (D&C yellow no. 10); blue-green, C.l. 59,040 (D&C green no. 8), blue violet, C.I. 60,730 (Ext. D&C violet no. 2); green-yellow, C.l. 10,316 (Ext. D&C yellow no. 7);

Reaction fiber dyes include Procion (RTM), Drimarene (RTM), Cicacron (RTM), Levafix (RTM), and Remazol (RTM) dyes available from ICI, Sandoz, Ciba Geigy, Bayer and Hoechst.

Natural dyes and plant dyes as defined herein include henna (Lawsonia alba), chamomile (matricaria chamomila or Anthenis nobilis), indigo, campus cup extract and nut.

Temporary hair dyes or tinted hair dyes are generally composed of dye molecules that are too large to diffuse into the hair fiber and act on the outside of the hair. They are usually applied by a deposition process in which the dye solution can dry on the hair surface. As such, these dyes are typically less resistant to the effects of hair wash and hygiene with surfactants and are washed out of the hair with relative ease. Each temporary hair dye may suitably be used in the compositions of the invention, and examples of temporary hair dyes are illustrated below:

Sat ₃ ch ₃

SO ₃ CH ₃

purple

Red

^SO 3 ^H SX 2> Z ^CH 3

-.n

O N

O OH

Blue-violet

yellow

Semi-permanent hair dyes are dyes that are generally smaller in size and are effective for temporary hair tinting, but are generally larger than permanent (oxidative) dyes. Typically, semi-permanent dyes act in a similar manner to oxidative dyes in that they have the potential for diffusion into the hair fiber. However, semi-permanent dyes are generally smaller in size than the above-mentioned conjugated oxidative dye molecules and as such are redistributed for gradual re-diffusion from the hair. Simple hair washing and hygiene will show this process and, in general, semi-permanent dyes are washed more extensively out of the hair after 5 to 8 washes. Any semi-permanent dye system may be suitable for use in the compositions of the present invention. Suitable semi-permanent dyes for use in the compositions of the present invention are HC Blue 2, HC Yellow 4, HC Red 3, Disperse Purple 4, Disperse Black 9, HC Blue 7, HC Yellow 2, Disperse Blue 3, Disperse Purple 1 and mixtures thereof. Examples of semi-permanent dyes are illustrated below:

^ *. ^^ c ₂ h ₄ oh nh ₂ 0 nh ₂ A IN ^ΝΗ 2 ' ^Ζ ^ ^ϊΧ ίί ^Χ N (C ₂ H ₄ OH) ₂ 0 nh ₂ blue blue

N (C ₂ H ₄ OH) ₂

yellow yellow ^H ' _N - ^ ₄ OH Χν ° ₂ no ₂ h ψ A I no ₂ nh ₂

Red

Red

Typical semi-permanent dye systems incorporate mixtures of larger and smaller color molecules. Since the hair dimension from the root to the hair end is not uniform, small molecules will diffuse at the root and at the end of the hair but do not retain at the end of the hair, while larger molecules will generally be capable of diffusion only to the hair ends. This combination of dye molecule size is used to help deliver consistent color results from the root to the end of the hair in the initial staining procedure and in the partial wash.

Buffering agents

The coloring compositions of the present invention have a pH in the range of about 1 to about 5, preferably 1.5 to about 5, more preferably from about 1.8 to about 4.7, most preferably from about 2.5 to about 4.5, and especially from about about 2.7 to about 3.8.

As described herein, the pH of the preferred coloring compositions of the present invention are maintained within the desired pH range through the action of an inorganic peroxygen oxidizing agent. However, if desired, the compositions may comprise one or more optional buffering agents and / or hair volume increasing agents. Some modifiers of varying pH can be used to adjust the pH of the resulting composition or the portion of which it is composed.

This pH adjustment may be effective using well known acidifying agents in the field of keratin fiber treatment, and in particular human hair, such as inorganic and organic acids such as hydrochloric acid, tartaric acid, citric acid, succinic acid, phosphoric acid and carboxylic or sulfonic acid, such as ascorbic acid, acetic acid, lactic acid, sulfuric acid, formic acid, ammonium sulphate and sodium dihydrophosphate / phosphoric acid, disodium hydrogen phosphate / phosphoric acid, potassium chloride / hydrochloric acid, potassium dihydrophthalate / hydrochloric acid, sodium citrate / hydrochloric acid, potassium / hydrochloric acid, potassium dihydrocitrate / citric acid, sodium citrate / citric acid, sodium tartrate / tartaric acid, sodium lactate / lactic acid, sodium acetate / acetic acid, dipotassium hydrogen phosphate citric acid and sodium chloride / glycine / hydrochloric acid, succinic acid and mixtures thereof.

Examples of alkaline buffering agents are ammonium hydroxide, ethylamine, dipropylamine, triethylamine and alkanediamines such as 1,3-diaminopropane, anhydrous alkaline alkaloamines such as mono- or diethanolamine, preferably those which are fully substituted on an amino group such as dimethylaminoethanol, polyalkylene polyamines such as diethylenetriamine or heterocyclic amine such as morpholim, as well as alkali metal hydroxides such as sodium or potassium hydroxide, alkaline earth metal hydroxides such as magnesium and calcium hydroxides, essential amino acids such as L-argenine, lysine, alanine , leucine, isoleucine, oxylysine and histidine and alkanoamines such as dimethylaminoethanol and aminoalkylpropanediol and mixtures thereof. Also suitable for use herein are compounds that form HCO 3 'by dissociation in water (hereinafter referred to as "ion-forming compounds"). Examples of suitable ion-forming compounds are Na ₂ CO ₃ , NaHCO _3, K ₂ CO ₃ , (NH ₄ ) ₂ CO ₃ , NH ₄ HCO ₃ , CaCO ₃ and Ca (HCO ₃ ) and mixtures thereof.

Preferred for use as buffering agents are organic and inorganic acids having a base pK a below about pH 6, and conjugation bases thereof. As defined herein, the base pKa means the negative logarithm (to base 10) of the equilibrium constant K, where K is the acid dissociation constant. Suitable organic and inorganic acids for use 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 acids and mixtures thereof.

The low pH coloring compositions of the present invention, wherein the form of contemplated use as described below may be comprised of the resulting solution containing an oxidizing agent and an oxidizing hair coloring agent that have been mixed prior to application to the hair or single component system. Further, the optional substances may be present either in combination with the oxidizing agent / coloring agent mixture or as separately packaged units. As such, the compositions of the present invention may comprise coloring kits of a number of individual components.

In oxidation and dye kits comprising a portion of an inorganic peroxygen oxidizing agent that may be present in a solid or liquid form, such as hydrogen peroxide, the buffering agent solution may be used to stabilize hydrogen peroxide. Since the hydrogen peroxide is stable in the pH range of 2 to 4, it is necessary to use a buffering agent 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 coloring agents, the buffering agent is capable of maintaining the pH of the solution in the range of about 1 to about 5, preferably about 1.5 to about 5. 5, more preferably from about 1.8 to about 4.7, most preferably from about 2.5 to about 4.5, and in particular from about 2.7 to about 3.8. It is therefore necessary to use a buffering agent having a pH in this range.

catalyst

The coloring compositions of the invention may optionally contain a transition metal comprising a catalyst for a peroxygen oxidizing agent and an optional, preformed peroxyacid oxidizing agent (s). One suitable type of catalyst is a catalyst system comprising a heavy metal cation of defined bleaching catalytic activity, such as a copper, iron or manganese cation, a metal cation auxiliary having little or no bleaching catalytic activity, such as a zinc or aluminum cation, and a sequestrant having defined stability constants for catalytic and auxiliary metal cations, in particular ethylenediaminetetraacetic acid, (methylenephosphonic acid) and their water-soluble salts. Such catalysts are described in US-A-4,430,243.

Other types of suitable catalysts include the manganese complexes disclosed in US-A5 246 621 and US-A-5 244 594. Preferred examples of such catalysts include Mn ^IV 2 (µO) 3 (1,4,7-trimethyl-1,4,7- triazacyclononane) 2- (PF6) 2, Mn ^11, 2 (µO) i (µ-OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 4- (CIO 4) 2, Mn ^1v 4 (µO) 6- (1,4,7-triazacyclononane) 4- (CIO 4) 2, Mn ^III Mn ^IV 4 (µO) i (µ-Oac) 2 (1,4,7-trimethyl-1,4,7 -triazacyclononane) 2- (C104) 3, and mixtures thereof. Others are described in EP-A-0 549 272. Other ligands suitable for use herein include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 1,2, 4,7-tetramethyl-1,4,7-triazacyclononane and mixtures thereof.

For examples of suitable catalysts, see US-A-4,246,612 and US-A-5,227,084. Also see US-A-5,194,416, which teaches monatomic manganese (IV) complexes such as Mn (1,4,7). trimethyl-1,4,7-triazacyclononane) (OCH 3) 3 (PF 6). Yet another type of suitable catalyst, as described in US-A-5,114,606, is a water soluble manganese (III) and / or (IV) complex with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups. Other examples include diatomic Mn in complexes with tetra-N-dentate and bi-N35 dentate ligands, including N ₄ Mn ^{1 H} (u-0) 2 Mn ^{1 in} N 4) ⁺ and [Bipy 2 (Mn ^m (µO) 2 Mn ^{1 in} bipy 2] _{(ClO4) 3rd}

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 (metalloporphyrin catalysts), US-A-4 728 455 (manganese) (multidentate ligand catalysts), US-A-4 711 748 and EP-A-0 224 952 (absorbed manganese on an aluminosilicate catalyst), US-A-4 601 845 (aluminosilicate carrier with manganese and zinc or magnesium salt), US- A-4 626 373 (manganese / ligand catalyst), US-A-4 119 557 (iron complex catalyst), DE-A-2 054 019 (cobalt chelate catalyst), CA-A-866 191 (transition metal containing salts) US-4,430,243 (manganese cation chelates and non-catalytic metal cations) and US-A-4,728,455 (manganese gluconate catalysts).

Heavy metal ion sequestrants

The dye compositions of the invention may contain optional heavy metal ion sequestrant components. Heavy metal ion sequestrants herein are components that act to separate (chelate or purify) heavy metal ions. These compounds may also contain a chelating capacity of calcium and magnesium, but preferably show selectivity for binding heavy metal ions such as iron, manganese and copper. Such sequestering agents are highly valuable in the hair coloring compositions herein to provide them with a controlled oxidative action as well as to provide good storage stability of the hair coloring products.

Heavy metal ion sequestrants are generally present in amounts of from about 0.005 wt%. % to about 20 wt. %, preferably from about 0.01 wt. % to about 10 wt. %, more preferably from about 0.05 wt. % to about 2 wt. % of the composition.

Various separating agents are known for this use, including aminophosphates, available as Dequest (RTM) from Monsanto, nitroacetates, hydroxyethylethylene triamines and the like. Suitable heavy metal ion sequestrants for use herein include organic phosphonates such as aminoalkylene poly (alkylene phosphonates), alkali metal ethane-1-hydroxydiphosphonates and nitrilotrimethylene phosphonates.

Preferred among the above are diethylenetriamine penta (methylene phosphonate), ethylenediamine tri (methylene phosphonate), hexamethylenediamine tetra (methylene phosphonate) and hydroxyethylene 1,1-diphosphonate.

Preferred biodegradable, non-phosphorous heavy metal ion sequestrants suitable for use herein include nitriloacetic acid and polyaminocarboxylic acids such as ethylenediaminotetraacetic acid, ethylenetriaminepentaacetic acid, ethylenediamine disuccinic acid, ethylenediamine disodium, dihydroxylenediamine, dihydroxylenediamine, dihydroxylenediamine, dihydroxylenediamine, dihydroxylenediamine, dihydroxylenediamine or dihydroxylenediamine. Particularly preferred is ethylenediamine-N, N'-disuccinic acid (EDOS), see US-A-4 704 233, or its alkali metals, alkaline earth metals, ammonium, or substituted ammonium salts, or mixtures thereof.

Other heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives, such as 2-hydroxyethyldiacetic acid or glyceryliminodiacetic acid, described in EP-A-317 542 and EP-A-399 133. Iminodiacetic acid sequestrants-N-2-hydroxypropylsulfonic acid are also suitable. and aspartic acid N-carboxymethyl-N-2-hydroxypropyl-3-sulfonic acid as described in EP-A-516 102. Also suitable are sequesterants of β-alanine-N, N'-diacetic acid, aspartic acid-N, N'- di-acetic acid, aspartic acid-N-monoacetic acid, and iminodisuccinic acid as described in EP-A-509 382.

EP-A-476 257 discloses suitable amino-based sequestrants. EP-A-510,331 i

describe suitable sequestrants derived from collagen, keratin or casein. EP-A528 859 discloses suitable alkyl imino diacetic acid sequestrants. Also suitable are dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid. Also suitable are glycine-N, N'-disuccinic acid (GADS), ethylenediamine-N-N'-glutaric acid (EDDG) and 2-hydroxypropylenediamine-N, N'-disuccinic acid (HPDDS).

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

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

thinners

A preferred diluent for the compositions of the present invention is water. However, the compositions of the present invention may include one or more solvents as additional diluents. In general, solvents suitable for use in the compositions of the present invention are selected to be miscible with water and harmless to the skin. Preferred solvents suitable for use as additional diluents include C1-C20 mono- or polyhydric alcohols and their ethers, glycerin with monohydric or dihydric alcohols and their ethers. Alcohol radicals containing 2 to 10 carbon atoms are preferred in these compounds. Thus, a preferred group includes ethanol, isopropanol, n-propanol, butanol, polypropylene glycol, ethylene glycol monoethyl ether, and mixtures thereof. In the compositions of the invention, the preferred major diluent is water. The principal diluent as defined herein means that the amount of water present is greater than the total amount of all other diluents.

The diluent is present in amounts preferably from about 5 wt. % to about 99.98 wt. %, preferably from about 15 wt. % to about 99.5 wt. %, more preferably at least about 30 wt. % to about 99 wt. %, in particular from about 50 wt. % to about 98 wt. % of the compositions herein.

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, cellulases, pectinases, lactases and peroxidases conventionally incorporated in detergent compositions. Suitable enzymes are discussed in U.S. Patents 3,519,570 and 3,533,139.

Peroxidases are peroxide-specific hemoproteins, but using a wide range of substances as donors. Catalase, which breaks down peroxide, is included here in view of the fact that it is generally similar in structure and properties and is capable of introducing certain oxidations with hydrogen peroxide. The decomposition of hydrogen peroxide may refer to the oxidation of one molecule to another. It is widespread in aerobic cells and may have some important function. Consensus peroxidases are not hemoproteins and at least one is flavoprotein. Other flavoproteins such as xanthine oxidase will also use hydrogen peroxide among other acceptors, and coenzyme peroxidases resemble these more than conventional peroxidases in that they are not specific for hydrogen peroxide. Suitable peroxidases for the compositions of the present invention include horseradish peroxidase, Japanese radish peroxidase, cow's milk peroxidase, rat liver peroxidase, linginase, and haloperoxidase such as chloro- and bromoperoxidase.

The enzymes are optionally included in amounts sufficient to provide a maximum of about 50 mg by weight, more typically about 0.01 mg to about 10 mg, of active enzyme per gram of hair treatment composition. Stated otherwise, peroxidase enzymes may be incorporated into the compositions of the invention in amounts of from about 0,000 wt. % to about 5 wt. %, preferably from about 0.001 wt. % to about 1 wt. %, more preferably from about 0.01 wt. % to about 1 wt. % of active enzyme by weight of the composition.

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

Amylases include, for example, α-amylases obtained from a special strain of B licheniformis, described in more detail in GB-1,269,839 (Novo). Preferred commercially available amylases include, for example, those sold under the tradename Rapidase from Gist-Brocades, and those sold under the tradename Termamyl and BAN from Novo Industries A / S. Amylase enzymes may be included in the composition in accordance with the invention in an amount of from 0.0001 wt. % to 2 wt. % of active enzyme by weight of the composition.

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

The lipase may be derived from fungi or bacteria, for example, from a lipase-producing strain of Humicola sp., Thermomyces sp. or Pesudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipases from chemically or genetically modified mutants of these strains are also useful. A preferred lipase is derived from Pseudomonas pseudoalkaligenes as described in European patent EP-B-0218272.

Other preferred lipases are obtained by cloning the Humicola lanuginosa gene and the expression gene in Aspergilus oryza as a guest, 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. Patent 4,810,414, Huge-Jensen et al., Issued Mar. 7, 1989.

Surfactants

I

The compositions of the present invention may additionally comprise a surfactant system. Suitable surfactants for incorporation into the compositions of the invention generally have a lipophilic chain of from about 8 to about 22 carbon atoms and can be selected from anionic, cationic, nonionic, amphoteric, oboionic surfactants and mixtures thereof.

(a) Anionic surfactants

Anionic surfactants suitable for incorporation into the compositions of the invention include alkyl sulfates, ethoxy alkyl sulfates, alkyl glyceryl ether sulfonates, methylacyl tartrates, fatty acylglucinates, N-acylglutamates, acylisothionates, alkylsulfosuccinates, alkylsulfonates, sulfonates, sulfonates, sulfonates, sulfonates, sulfonates, sulfonates, sulfonates, sulfonates, sulfonates, esters, alkyl ethoxycarboxylates, alkyl phosphate esters, ethoxy alkyl phosphate esters, alkyl sulfates, acyl sarcosinates and fatty acids / protein condensates, and mixtures thereof. The alkyl and / or acyl chain lengths for these surfactants are C12-C22, preferably C12-C18, most preferably C12-C14.

(b) Non-ionic surfactants

The compositions of the invention may also comprise a water-soluble nonionic surfactant (s). Surfactants of this class include C12-C14 fatty acids of mono- and diethanolamides, sucrose polyester surfactants, and polyhydroxy fatty acid amide surfactants having the general formula

OR ⁹

R ⁸ - C - N - Z ²

Preferred amides surfactants of the N-alkyl, N-alkoxy or N-aryloxy, polyhydroxy fatty acids of the above formula are those wherein R ⁸ is C 5 -C 31 hydrocarbyl, preferably C 6 -C 19 hydrocarbyl, including straight chain alkyl and alkenyl and branched chain, or mixtures thereof, and R ⁹ is typically hydrogen, C 1 -C 6 alkyl or hydroxyalkyl, preferably methyl, or a group of the formula -R ¹ -OR ² , wherein R ¹ is a C 2 -C 8 straight chain, branched hydrocarbyl and cyclic (including aryl), and is preferably C 2 -C 4 alkylene, R ² is C 1 -C 6 straight chain, branched, and cyclic with a hydrocarbyl moiety including aryl and oxyhydrocarbyl, and is preferably C 1 -C 4 alkyl, especially methyl or phenyl. Z ² is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain in at least 2 (in the case of glyceraldehyde) or at least 3 hydroxyls (in the case of other reducing sugars) directly linked to the chain, or an alkoxylate derivative thereof (preferably ethoxylate or propoxylate). Z ² is preferably derived from a reducing sugar in a reductive amination reaction, more preferably Z ² is a glycityl moiety. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose, as well as glyceraldehyde. As raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup, as well as the individual sugars listed above, may be used. These corn syrups can provide a mixture of sugar components for Z ² . This means that other suitable raw materials are not excluded. Of the ^{2, it} will preferably be selected from the group consisting of -CH ₂ - (CHOH) _n -CH ₂ OH, -CH (CH ₂ OH) - (CHOH) _n . _{1 -CH2} OH _l CH ₂ (CHOH) ₂ - (CHOR ') (CHOH) - (CH CH2OH-, wherein n is an integer from 1 to 5 inclusive, and R' is H or a cyclic mono- or polysaccharide, and alkoxylate derivatives thereof As mentioned above, glycityls are most preferred, wherein n is 4, especially CH ₂ - (CHOH) 4 -CH ₂ OH-.

The most preferred polyhydroxy fatty acid amide has the formula R ⁸ (CO) N (CH 3) CH 2 (CHOH) ₄ CH ₂ OH-, wherein R ® is a straight chain C ₆ H ₉ alkyl or alkenyl group. In the compounds of the above formula, R ⁸ -CO-N napríklad can be, for example, cocoamide, stearamide, oleaamide, lauramide, myristamide, caproamide, palmiamide, tallowamide, and the like.

Suitable nonionic surfactant oil derivatives for use herein include water-soluble plant and animal derived plasticizers, such as polyethylene glycol chain-inserted triglycerides, etolylate mono diglycerides, polyethoxylate lanolines, and ethoxylate butter derivatives. One preferred group of oil-derived nonionic surfactants for use herein has the general formula:

ABOUT

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

Suitable ethoxylate oils and fats of this class include polyethylene glycol derivatives of glyceryl cocosate, glyceryl caproate, glyceryl caprylate, glyceryl malate, glycerylearate, glycerylurate, glyceryl oleate, glycerylricinoleate, glycerylricinoleate, glycerylricinoleate, glycerylricinoleate, glycerylricinoleate, glycerylricinoleate, glycerylricinoleate, glycerylricinoleate;

Preferred for use herein are the polyethylene glycol C9-C15 polyethylene glycol surfactant surfactants containing on average from about 5 to about 50 proportions of ethyleneoxy per mole of surfactant.

Suitable polyethylene glycol C 9 -C 15 fatty alcohols for use herein include C 9 -C 11 Pareth-3, C 9 -C 11 Pareth-4, C 9 -C 11 Pareth-5, C 9 -C 11 Pareth-6, C ₉ -C ₁₁ Pareth-7 , -CN, C ₉ Pareth-8, C11-C15 Pareth-3, C11-C15 Pareth-4, C11-C15 Pareth-5, C11-C15 Pareth-6, C11-C15 Pareth-7, C11-C15 Pareth- 8, C11-C15 Pareth-9, C11-C15 Pareth-10, C11-C15 Pareth-11, C11-C15 Pareth-12, C11-C15 Pareth-13, C11-C15 Pareth-14. PEG 40 hydrogenated castor oil is commercially available under the tradename Cremophor (RTM) from BASF. PEG 7 glyceryl cocosate and PEG 20 glyceryl laurate are commercially available under the trade names Cetiol (RTM) HE and Lamacit (RTM) GML 20. C ₉ -Cn Pareth-8 is commercially available from Shell Ltd under the trade name Dobanol (RTM) 91-8. Particularly preferred for use herein are polyethylene glycol ethers of ceteryl alcohol such as Ceterareth 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 butyrospermum Karkii Kotschy fruit and derivatives thereof Similarly, ethoxy derivatives of mango, cocoa and ellip butter may be used in the compositions of the invention. Although these are classified as ethoxyyl nonionic surfactants, it is understood that some portion may remain as nonethoxyyl vegetable oils or fats.

Other suitable oil-based surfactants include ethoxylated almond oil, peanuts, rice bran oil, germinate oil, linseed oil, jojoba oil, apricot stones, nuts, palm nuts, pistachios, sesame seeds, rapeseed, corn peach stone, poppy oil, pine oil, castor oil, soybean oil, avocado oil, safflower oil, coconut oil, peanut oil, olive oil, grape seed and sunflower seed oil.

c) Amphoteric surfactants

Amphoteric surfactants suitable for use in the compositions of this invention include:

(a) imidazoline surfactants of formula (VII)

C2H4OR ²

CH ₂ Z

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

C2H4OH

R ¹ CONH (CH 2) 2 N ⁺ CH 2 Z

R ² 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 iminoalkanoates of formula (X)

R ¹ N [(CH ₂ ) _m CO ₂ M] ₂ and iminopolyalkanoates of formula (XI)

R ¹ '[N (CH ₂ ) _p ] _q N [CH ₂ ) CO ₂ M] ₂

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 group specified above; and

(c) mixtures thereof.

Suitable amphoteric surfactants of type a) are sold under the trade names Miranol and Empigen and are understood to contain a complex mixture of species. Traditionally, Miranols have been described as having the general formula (VII), although the CTFA Cosmetic Ingredient Dictionary, 3rd edition lists a non-cyclic structure (VIII), with

Edition 4 discloses yet another structural isomer in which R ² is with an O-bond rather than an N-bond. In practice, there is probably a complex mixture of cyclic and non-cyclic species and both definitions are given for the sake of completeness. Preferred for use herein are non-cyclic mixtures.

Examples of suitable amphoteric surfactants of type a) include compounds of formula XII and / or XIII wherein R ¹ is C 6 H 17 (especially isocapryl), C 8 H 18 and C 11 H 6 alkyl. Particularly preferred are those compounds wherein R ¹ is C 8 H 18, 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 23, Z is CO ² M and R ² is hydrogen.

In the CTFA nomenclature, materials suitable for use in the present invention include cocosamphospharboxypropionate, cocosamphocarboxypropionic acid, and in particular cocosamfooctane and cocosamphodioctane (otherwise corresponding to cocosamphocarboxyglycinate). Specific commercial products include those sold under the trade names Ampholak 7TX (Sodium Carboxymethyllo-Polypropylamine), Empigen CDL60 and CDR 60 (Albright & Wilson), Miranol H2M Conc. Miranol C2M Conc. N.P., Miranol C2M Conc. O.P., Miranol c2M SF, Miranol CM Special (RhônePoulenc); Alcateric 2COB (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 include Octoxynol-1 (RTM), polyoxyethylene (1) octopropyl ether Nonoxynol-4 (RTM), polyoxyethylene (4) nonylphenyl ether and Nonoxynol-9, polyoxyethylene (9) nonylphenylether.

It is understood that a number of commercially available amphoteric surfactants of this type are manufactured and marketed in the form of electroneutral complexes with, for example, a hydride moiety or an anionic sulphate or sulphonate of a surfactant, in particular a sulphate Ca-Cie alcohol, CbCib ethoxylated alcohol or CaCia acyl glyceride. It should be noted that the concentration and weight ratios of the amphoteric surfactants are based here on uncomplexed surfactant forms, each proportion of anionic surfactant being considered to be part of the total content of the anionic surfactant component.

Examples of preferred amphoteric surfactants of type b) include N-alkylpolytrimethylene poly-, carboxymethylamines 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-beta-aminopropionic acid and N-lauryl -imino-dipropionic acid. Such substances are sold under the tradename Deriphat of Henkel and Mirataine of Rhône-Poulenc.

I ₍

(d) Oionic surfactants

Water soluble oboionic auxiliary surfaces of the active substance suitable for incorporation into the compositions of the present invention alkyl betaines of formula R ⁵ R ⁶ R ⁷ N ⁺ (CH 2) _n CO 2 M and amidobetaines of formula (XII) below:

R ⁶

R ⁵ CON (CH 2) _m N (CH ₂ ) n CO ₂ M

R ⁷ wherein R ⁵ is C 11 -C 22 alkyl or alkenyl, R ⁶ and R ⁷ are independently C 1 -C 3 alkyl, M is hydrogen, alkali metal, alkaline earth metal, ammonium or alkanolammonium, and n are m from 1 to 4 Preferred betaines include cocosamidopropyldimethylcarboxymethyl betaine, laurylaminopropyldimethylcarboxymethyl betaine and Tego betaine (RTM).

Water-soluble sulfide surfactant excipients suitable for incorporation in the compositions of the present invention include alkyl sulfates of formula (XIII) below:

R ²

I

R ¹ CON (CH 2) m N ⁺ (CH 2) CH (OH) CH ₂ SO 3 M ⁺

I

R ³ wherein R ¹ is Ογ-Ο ₂₂ alkyl or alkenyl, R ² and R ³ are independently C 1 -C 3 alkyl, M is hydrogen, alkali metal, alkaline earth metal, ammonium or alkanolammonium amine are numbers from 1 to 4. Preferred for use herein, it is coconut propylhydroxysultain.

The water-soluble amine oxide surfactants for inclusion in the compositions of the present invention include the alkylamine oxides R ⁵ R ⁶ R ⁷ NO and the amidoamine oxides of formula (XIV) below:

R ⁶

I

R ⁵ CON (CH ₂ ) _m N → O t ¹ ».

I

R ⁷ wherein R ⁵ is C 11 -C ₂₂ alkyl or alkenyl, R ⁶ and R ⁷ are independently C 1 -C 3 alkyl, M is hydrogen, alkali metal, alkaline earth metal, ammonium or alkanolammonium and m is a number from 1 to 4. Preferred amine oxides include cocosamide propylamine oxide, lauryldimethylamine oxide and myristyldimethylamine oxide.

Optional substances

The number of additional optional substances may be added to the coloring composition described herein in an amount of from about 0.001 wt. % to about 5 wt. %, preferably from about 0.01 wt. % to about 3 wt. %, more preferably from about 0.05 wt. % to about 2 wt. % by weight of the composition. Such agents include proteins and polypeptides and derivatives thereof; water-soluble or soluble additives such as DMDM Hydantoin, Germall 115, hydroxybenzoic acid methyl, ethyl, propyl abutyl esters. EDTA, Euxyl (RTM) K400, natural ingredients such as benzyl alcohol, potassium sorbate and bisabalol, benzoic acid, sodium benzoate and 2-phenoxyethanol antioxidants such as sodium sulfite, hydroquinone, sodium metabisulfite, sodium metadisulfite and thioglycolic acid, sodium dithionate, erythrobic acid and other mercaptans; coloring agents such as oxalic acid, castor oil, salicylic acid and sodium thiosulfate; hydrogen peroxide stabilizers such as tin compounds, for example sodium tin, tin hydroxide, tin octocat, acetanilide, phenacetin colloidal essential oils such as magnesium silicate, oxyquinoline sulfate, sodium phosphate and tetrasodium pyrophosphate; and phydroxybenzoates; wetting agents such as hyaluronic acid, chitin, and starch-linked sodium polyacrylates such as Sanwet (RTM) IM-1000, IM-1500 and IM-2500 available from Celanese Superabsorbent materials, Portsmith, VA, USA and described in US- A-4 076 663 as well as methylcelluloses, starch, higher fatty alcohols, paraffin oils, fatty acids and the like; solvents; antibacterial agents such as Oxeco (phenoxyisopropanol); low temperature phase modifiers such as ammonium ion sources (e.g., NH 4 Cl); viscosity control agents such as magnesium sulfate and other electrolytes; quaternary amine compounds such as distearyl-, dilauryl-, dihydrogenated bovine tallow, dimethylammonium chloride, dicetyldiethyl ammonium methyl sulfate, disiodoadimethylammonium chloride and dicocosodimethylammonium chloride; hair conditioners such as silicones, higher alcohols, cationic polymers and the like; enzyme stabilizers such as water-soluble sources of calcium or borane; coloring agents; titanium dioxide and titanium dioxide coated mica; perfumes and perfume dissolvers; zeolites such as Valfour BV400 and its derivatives and Ca ² 7Mg ²⁺ sequestrants such as polycarboxylates, aminopolycarboxylates, polyphosphonates, aminopolyphosphonates, etc. and water softening agents such as sodium citrate.

The present invention is represented by the following non-limiting examples. In these examples, all concentrations are on a 100% active basis and all percentages are by weight unless otherwise indicated and the abbreviations have the following determination:

Oxidizing agent

Oxidizing agent

Oxidant dye

Oxidant dye 2

Oxidative dye 3

Oxidative dye 4

Oxidizing dye 5 Non-oxidizing dye Hydrogen peroxide peracetic acid para-phenylenediamine para-aminophenol meta-aminophenol

2-Amino-3-hydroxypyridine 4-Amino-2-hydroxytoluene Base Red 76

Chelating agent

Surfactant

Surfactant

Thickener 1

Thickener 2

antioxidant

Buffering agent ethylenediaminetetraacetic acid Ceteareth-25 cocosamidopropyl betaine cetyl alcohol steraryl alcohol f

sodium sulfite acetic acid

Examples 1-VII

The following examples are hair styling compositions in the form of hair coloring compositions presented in the present invention.

component 1 II H! IV IN vi_ vii Oxidizing agent 0.7 0.7 0.7 0.7 0.7 - 0.7 Oxidizing agent - - - - - 2.0 0.5 Oxidant dye 0.24 0.14 0.24 0.15 0.24 0,475 0.24 Oxidant dye 2 0.09 0.05 0,009 0.5 0,09 · 0.18 - Oxidative dye 3 0,006 0,004 0,006 - 0,006 0,012 0,006 Oxidative dye 4 0.06 0.03 0.06 0.1 0.06 0.11 0.06 Oxidative dye 5 - - - 0.5 - - Non-oxidising dye - - - - - - 0.1 Surfactant 1.5 1.7 1.5 1.5 1.5 3.0 - Surfactant - - - - - - 1.5 Chelating agent 0.1 0.06 0.09 0.2 0.1 0.2 0.1 Thickener 1 2.3 2.6 2.3 2.3 2.3 4.5 2.3 Thickener 2 2.3 2.6 2.3 2.3 2.3 4.5 2.3 antioxidant 0.1 0.06 0.1 0.2 0.1 0.2 0.1 buffer - - - 0.5 0.5 - - Water ..to balance ... pH 4.0 3.8 3.9 4.6 2.7 2.4 -

In the examples, water is used as the diluent. However, in variations of the above, the water may be partially replaced from about 0.5 wt. % to about 50 wt. % of the total water content of the above examples 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-2-oleyl ether and mixtures thereof.

Experimental methods

I. Determination of the initial color and color change

The apparatus used to measure both the initial color and the color change on substrates (hair / skin) stained with low pH coloring compositions in one package according to the present invention is a Hunter Colorquest spectrophotometer. The value used to express the degree of color change on a particular substrate is Delta E ( ^Δ Ε). Delta E, as defined herein, is represented by the true sum of the values L 1, a and b such that:

^A Ε = ( ^A L ² + ^A and ² + ^A b ² ) ^1/2 and L is a measure of lightness or darkness (color intensity), where L = 100 is equivalent to white, and = 0 is equivalent to black. Furthermore, "a" is the rate of red and green (color shades) so that positive equals red and negative is equal to green, and "b" is the rate of yellow and blue (color shades) such that positive is yellow and negative equals blue.

Hunter Colorquest measurements can be performed on a Hunter Labscam colorimeter, which is a complete scanning spectro colorimeter with a wavelength of 400 to 700 nanometers, which records the color of the hair extensions tested in terms of "L", "a" and "b". The machine is set to: mode - 0/45; canal size - 1 inch (2.54 cm); view size - 1 inch; light - D65; area of view - 10 °; UV lamp / filter - none. The hair is placed in a sample holder designed to hold the hair when measured in a uniform direction. Equivalent colorimeters may be used, but it must be ensured that the hair does not move when measured. The hair must be positioned so that it occupies a 1 inch (2.54 cm) channel when measuring color. There are dots on the hairpiece holder to guide the positioning of the holder in the channel. The dots are lined up along with the mark on the channel, and values are taken at each point.

Eight measurements are made for each hairpiece, four on each side, and three hairpieces for adjustment.

//. Determination of color retention potential

The device used to measure the initial color potential (Delta E target) and the color development potential after the storage period (Delta E stored) for each, in one package, the hair coloring composition is already described, is it Hunter

Colorquest spectrophotometer.

Target Delta E, ^Δ ΕΤ, represents the color developed by the composition when it is first applied to the hair. Stored Delta E, ^A ES1 represents the color developed by this composition after a storage period (at about room temperature, 25 ° C). The beginning of the storage period X is defined here as zero time, ie from the point of initial use of the low pH hair coloring composition. The storage period can range from several days to several months.

The color retention potential ^δ Ερ can be expressed as the difference between the initial color development ^Δ Ε _Τ and the color formation after storage of ^A Es as illustrated by the following formula:

^{Δ ΕΡ} = ^{δ Ετ} - ^{δ Ε} ₈

The smaller the difference between ^Δ Ετ and ^A Es, the higher the potential for color development ^Δ Ερ.

In preferred compositions according to the present invention, the ^{Δ Ερ} of at least 1 hour (60 minutes) of storage is less than about 2, preferably less than about 1, preferably less than about 0.2. After at least one day (24 hours), ^Δ Ε _{Ρ is} less than about 2, preferably less than about 1, more preferably less than about 0.3. After at least 1 month, ^Δ Ερ is less than about 3, preferably less than about 1.5, more preferably less than about 0.3.

The relative change in color development potential after the storage period (X),% ^δ Ερ can be expressed as a percentage of the initial target color ^Δ Ετ that is delivered to the hair after storage. As such, the percentages of color formation potential for each given composition may be expressed by the following formula:

% ^δ Ερ = ^Δ ΕΤ - ^and Es / ^a Et X 100

In preferred compositions of the present invention, the color delivered to the hair after at least 1 hour (60 minutes) of storage (Delta E stored) at room temperature (25 ° C) is greater than about 75%, preferably greater than about 80%, more preferably greater than about 85 %, most preferably greater than about 90%, and in particular greater than about 95% of the hair color delivered at first application (Delta E initial)

In preferred compositions of the present invention, the color delivered to the hair after at least 1 day (24 hours) of storage (Delta E stored) at room temperature (25 ° C) is greater than about 75%, preferably greater than about 80%, more preferably greater than about 85 %, most preferably greater than about 90%, and in particular greater than about 95% of the hair color delivered at first application (Delta E initial)

In preferred compositions of the present invention, the color delivered to the hair after at least 1 month of storage (Delta E stored) at room temperature (25 ° C) is greater than about 75%, preferably greater than about 80%, more preferably greater than about 85%, most preferably greater more than about 90%, and in particular greater than about 95% of the hair color delivered at first application (Delta E initial) ///. standard hair strand

The compositions of the present invention can be used to dye hair of all colors, types and conditions. For purposes of illustration, two types of test hair pieces, light brown and light brown with 40% gray coverage, were tested. These standard hairpieces were measured by their approximated values of L, a, b.

light brown

9

Light brown with 40% gray 35 - 37

4,5-5,5 11,5-12,7

IV. Hair dyeing method

For hair dyeing, a 4 gram hairpiece with about 8 inches (20.32 cm) long hair was passed through a suitable container. The test dye product is then prepared (i.e., the application ingredients in separate bottles are mixed together) and about 8 grams of the product is applied directly to the test hairpiece. The color is massaged into the hairpiece for about 1 minute and then the hairpiece is allowed to rest for about 30 minutes. After rinsing under running water for 1 or 2 minutes, the colored hairpiece was washed (according to the shampoo procedure) and dried. Drying can be carried out either naturally (without the aid of heat) or by using a dryer. The color formation (initial color) of the dyed, washed and dried hairpiece can then be determined using a Hunter Colorquest spectrophotometer.

For delivering a red shade (staining) with a persistent, discolored light brown hair (having L, a, b values of approximately 60, 9 and 32), the preferred initial shade of the colored hair will have a coloring value (are tangens (b / a)) ranging from about 25 to about 70, preferably from about 30 to about 65, more preferably from about 35 to about 60, and the initial color intensity (L) is greater than about 10 and less than about 70, preferably greater than about 15 and less than about 65, more preferably greater than about 20 and less than about 60.

To deliver a brown or black shade (staining) with a persistent, bleached light brown hair (having L, a, b values of approximately 60, 9 and 32), the preferred initial shade of the dyed hair will have a shade value (b / a) of less than about 25, preferably less than about 20, and the initial color intensity (L) will be greater than about 1 and less than about 50, preferably greater than about 5 and less than about 45.

To deliver a light brown shade (staining) with a persistent, bleached light brown hair (having L, a, b values of approximately 60, 9 and 32), the preferred initial shade of the colored hair will have a coloring value (are tangens (b / a)) of about 70 to about 110 and the initial color intensity (L) will be greater than about 20 and less than about 95, preferably greater than about 25 and less than about 90.

V. A method of washing the hairpiece

The hair combs are subjected to a repeated wash cycle, the following procedure being repeated 10 times.

The 4-gram 8 inch (20.32 cm) hairpiece is attached to a suitable container and thoroughly washed for about 10 seconds using warm water (at about 37 ° C in about 1.5 gallons, i.e. 3.03 liters / pressure per minute). minute). The shampoo (about 0.4 ml without conditioner) can then be applied directly to the wet test hair using a syringe. After foaming the hair for about 30 seconds, the hair was washed with running warm water for about 30 seconds. The shampooing and foaming process is then repeated with a final 60 second wash. Excess water can be removed (squeezed) from the test hair using fingers. The test hairpiece is then dried either naturally or by using a heated drying box at about 58 ° C (for about 30 minutes). The stained, washed, dried test hairpiece was then stained (Delta E faded).

For each one test cycle, each of the different hairpieces to be determined will be tested in water with an equivalent value of temperature, pressure and hardness.

Delta E results paled for persistent, bleached light brown hair (having L, a, b values of about 60, 9, and 32) that have been colored red (color values in the range of about 25 to about 70) are generally less than about 5 0, preferably less than about 4.5, more preferably less than about 4.0, and the color change of the% delta E after twenty washes is less than about 20%, preferably less than about 15%, more preferably less than about 10%.

Delta E results paled for persistent, discolored light brown hair (having L, a, b values of about 60, 9, and 32) that have been colored brown or black (color value less than about 25) are generally less than about 2.3 , preferably less than about 2.0, more preferably less than about 1.7, and the color change of the% delta E after twenty washes is less than about 5%, preferably less than about 4%, more preferably less than about 4%, most preferably less than about about 8%.

Delta E results paled for persistent, discolored light brown hair (having L, a, b values of about 60, 9, and 32) that have been colored with a light brown shade (color value ranging from about 70 to about 110) are generally less than about 2.6, preferably less than about 2.3, more preferably less than about

1.7, and the color change of the% delta E after twenty washes is less than about 15%, preferably less than about 12%, more preferably less than about 10%, most preferably less than about 8%.

VI. Method for testing skin discoloration

For the purposes of the present invention, skin staining results are based on pig skin data.

Skin staining measurements can be made on the ears of pigs, preferably on the ears of recently dead pigs. The ears should not be exposed to excessive heating (scalding). For coloring, the hairs are shaved from the most haired part of the ear. An area of at least 1cm x 5cm is marked on the ear (using a permanent marker) and the ear is then washed with shampoo without conditioner (0.1g / cm ² at 10% dilution). After massaging the shampoo for about 1 minute, the ear is washed for about 30 seconds and gently dried by hand with a paper towel. The determination of baseline data (L, a, b) is then made for the designated area. The test dye is then applied to the labeled test area (about 0.25 g / cm ² and massaged for about 1 minute and left for about 30 minutes. The dyed ear is then washed with about 2 liters of tap water at about 37 ° C and manually The color determination data (L, a, b) are then made for the designated area of the dried ear The total color change (Delta E) can then be calculated from the values L, a, b and • 1 expressed as relative color levels skin (as opposed to the base color line).

VII. PH measurement

For purposes of this invention, as described herein, all pH measurements were performed on a Mettler Toledo 320 pH meter. All measurements of the pH of the dye, oxidizing agents and mixtures thereof, either singly or in combination with a suitable delivery medium such as water and surfactant and / or thickeners, were made at room temperature (about 25 ° C). The pH of the dye mixtures was measured in the form to be used and before application. A preferred delivery medium for use herein comprises Ceteareth-25 emulsion in an amount of from about 1 wt. % to about 3 wt. % cetyl alcohol in an amount of from about 2 wt. % to about 5 wt. % and stearyl alcohol in an amount of from about 2 wt. % to about 5 wt. % to about the weight of the solution or composition.

Experimental data

I. Color retention potential (color delivered after storage)

The exemplary formulas I-VII provide improved color retention potential over time over similar compositions having a pH outside the scope of the present invention.

//. Initial color and color fastness to washing

Example I provides improved initial color development and fade resistance over a similar composition having a pH outside the scope of the present invention.

Example II provides improved initial color development and color fastness to washing compared to a similar high pH formula containing the same amount of oxidant and up to 60% more dye.

Example III provides improved initial color development over a high pH formula containing the same amount of dye but more inorganic peroxygen oxidizing agent.

///. Relative skin coloring

Example IV provides reduced skin dyeing values for pig ears compared to equivalent high pH compositions.

t,>>, *

Method of production

It is important that the colorant compositions are in a form that is simple and suitable for preparation and use by the consumer, as the oxidizing agent must contact the hair for a period of time and not drip or drip from the hair, which may cause eye or skin irritation.

To accomplish the above, the coloring compositions of the present invention are provided in the form of a single package comprising an oxidizing component and a coloring component. The dye compositions of the present invention may be used either to dye the hair after purchase of the dye or partially used to dye the hair and the rest of the dye may be stored for future use or may be stored entirely for future use.

As already described, the compositions of the present invention are

I made to the consumer as a one-component package. Such a package may contain one solution at pH 1 to about 5 containing the oxidizing agent as well as oxidizing dye precursors and additional, optional agents such as surfactants, antioxidants, thickeners, etc. The solution is applied directly to the consumer's hair without the need for any treatment or mixing, ensuring a simple, fast, easy to use, uncomplicated hair coloring system. A further advantage of such a one-component system is that it can be stored and reused, i. one package may contain enough coloring composition for several applications over a period of time.

Then, according to another aspect of the present invention, it is performed:

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

a) from about 0.01 wt. % to about 6 wt. % oxidizing agent; and

b) from about 0.001 wt. % to about 5 wt. wherein the combined mixture of a) and b) has a pH in the range of about 1 to about 6 and the resulting hair color (Delta E) after a minimum of 1 month storage at room temperature is greater than about 75%, preferably greater than about 85%, more preferably greater than about 90%, and most preferably greater than about 95%, of the total hair color delivered (Delta E) of composition a) and b) upon application.

Way of use

Compositions described herein in a single package are used to color hair. The coloring compositions are applied to the hair from 1 minute to 60 minutes depending on the degree of color desired. The preferred time is between 5 minutes and 30 minutes. The colorant compositions of the present invention can be applied to both dry and wet hair.

As already described, the coloring compositions are in one package, contain both an oxidizing agent and an oxidizing, hair coloring agent in a storage stable composition, have a low pH, are suitable for direct application to the hair. The hair dye compositions of the present invention can be used to dye hair in several ways, including:

(a) a pre-mixed, low pH single-component kit applied directly to the hair.

I

(b) a pre-mixed, low pH single-component kit applied directly to the hair after storage at room temperature.

The products of the present invention are stable and reusable upon storage and provide excellent initial hair coloring and impressive in-use benefits.

Claims (16)

PATENT CLAIMS A hair coloring composition, characterized in that the coloring composition contained in a single package is suitable for direct application to the hair, and wherein the hair coloring composition comprises: I (a) oxidizing agent; and b) an oxidative hair coloring agent; wherein the combined blend a) and b) have a pH in the range of about 1 to about 5 and the resulting hair color (Delta E) after at least 1 month of storage at room temperature is greater than about 75%, preferably greater than about 85%, more preferably greater more than about 90% and most preferably greater than about 95% of the total hair color delivered (Delta E) of composition a) and b) upon application. The composition of claim 1, wherein the pH of the composition is in the range of about 1.5 to about 5, more preferably from about 1.8 to about 4.7, more preferably from about 2.5 to about 4.5, and especially from about 2.7 to about 3.8. I ’I The composition of claim 1 or 2, wherein the oxidizing agent is selected from inorganic peroxygen oxidizing agents, preformed organic peroxyacid oxidizing agents, organic peroxide oxidizing agents, and mixtures thereof. The composition of any one of claims 1 to 3, wherein the oxidizing agent is an inorganic peroxygen oxidizing agent present in an amount of from about 0.01 wt. % to about 3 wt. %, preferably from about 0.01 wt. % to about 2 wt. %, more preferably from about 0.01 wt. % to about 1 wt. % and in particular from about 0.01 wt. % to about 0.7 wt. % of the total composition. The composition of any one of claims 1 to 4, wherein the inorganic peroxygen oxidizing agent is hydrogen peroxide. Composition according to any one of claims 1 to 5, characterized in that the total combined amount of the oxidative hair coloring agent is About 0.001 wt. % to about 5 wt. %, preferably from about 0.01 wt. % to about 4 wt. %, more preferably from about 0.1 wt. % to about 3 wt. %, most preferably from about 0.1 wt. % to about 1 wt. %. The composition of any one of claims 1 to 6, wherein each oxidative hair coloring agent is present in an amount of from about 0.001 wt. % to about 3 wt. %, preferably from about 0.01 wt. % to about 2 wt. %. Composition according to any one of claims 1 to 7, characterized in that it further comprises one or more buffering agents, preferably organic and / or A _t organic acid having a pKa below pH 6, selected from: acid • aspartic, maleic, tartaric, glutamic, glycolic, acetic, succinic, salicylic, benzoic, malic, lactic, malonic, oxalic, citric, phosphoric acid and mixtures thereof , more preferably selected from acetic, succinic, salicylic and phosphoric acid and mixtures thereof. I The composition of any one of claims 1 to 8, further comprising one or more surfactants selected from anionic, nonionic, cationic, oboionic, amphoteric surfactants and mixtures thereof. A composition according to any one of claims 1 to 9, further comprising thickeners, stabilizers, antioxidants and / or any other cosmetically acceptable substance. and * . Use of a hair dye composition according to any one of claims 1 to 10 for dyeing human hair or animal hair. A method of coloring human hair or animal hair with a composition according to any one of claims 1 to 10, characterized in that the composition is applied directly to the hair 13. A method according to which the hair is provided with a red shade comprising applying to the hair in a single packaged hair dye composition comprising: a) from about 0.01 wt. % to about 3 wt.% of an inorganic peroxygen oxidizing agent; and b) from about 0.001 wt. % to about 5 wt. % oxidizing hair coloring agent and mixtures thereof wherein the untreated hair is hardened, bleached light brown hair having L, a, b values of about 60, 9 and 32 and wherein the initial shade of the colored hair has a coloring value (are tangens (b / a)) of from about 25 to about 70, preferably from about 30 to about 65, more preferably from about 35 to about 60, and the initial color intensity (L) is greater than about 10 and less than about 70, preferably greater than about 15 and less than about 65, more preferably greater than about 20 and less than about 60 and wherein the Delta E faded is less than about 5.0, preferably less than about 4.5, more preferably less than about 4.0, and the hair color change% delta E is after at most 20 hair washes of less than about 20%, preferably less than about 15%, and more preferably less than about 10%. 14. A method according to which the hair is provided with a brown or black shade, comprising applying to the hair in a single packaged hair dye composition comprising: a) from about 0.01 wt. % to about 3 wt. an inorganic peroxygen oxidizing agent; and b) from about 0.001 wt. % to about 5 wt. % oxidizing hair coloring agent and mixtures thereof wherein the untreated hair is hardened, discolored light brown hair having L, a, b values of about 60, 9 and 32 and wherein the initial shade of the colored hair has a coloring value (are tangens (b / a)) of less than about 25, preferably less than about 20, and the initial color intensity (L) is greater than about 1 and less than about 50, preferably greater than about 5 and less than about 45, and wherein the Delta E faded is less than about 2, 3, preferably less than about 2.0, more preferably less than about 2.0 1.7, and the% E delta hair color change after less than 20 hair washes is less than about 5%, preferably less than about 4.5%, more preferably less than about 4%, and most preferably less than about 3.5%. 15. A method according to which a light brown shade is provided, comprising applying to the hair in a single packaged hair dye composition comprising: a) from about 0.01 wt. % to about 3 wt. an inorganic peroxygen oxidizing agent; and b) from about 0.001 wt. % to about 5 wt. % oxidizing hair coloring agent and mixtures thereof; and wherein the untreated hair is hardened, discolored light brown hair having L, a, b values of about 60, 9 and 32, and wherein the initial shade of the colored hair has a coloring value (are tangens (b / a)) in the range of about 70 to about 110 and the initial color intensity (L) is greater than about 20 and less than about 95, preferably greater than about 25 and less than about 90, and wherein the Delta E faded is less than about 2.6, preferably less than about 2.3, and the change in hair color,% delta E, after up to 20 _J and washes, is less than about 15%, preferably less than 'about 12%, and preferably less than about 10%, most preferably less than about 8%. A method of coloring hair having a pH in the range of about 1 to about 5 comprising applying to the hair in a single packaged hair dye composition comprising: a) from about 0.01 wt. % to about 3 hmon. a inorganic peroxygen oxidizing agent having a pH of from about 1 to about 6; and b) from about 0.001 wt. % to about 5 wt. a oxidizing hair coloring agent at a pH of from about 1 to about 6; c) from about 0.00.1 wt. % to about 99.98 wt. % diluent suitable for application to the hair; and wherein the combined pH of a) and b) is stored at a low pH in the range of about pH 1 to about pH 5, or is mixed for at least 1 month at room temperature.