MXPA99010756A - Hair colouring compositions and their use - Google Patents

Abstract

Hair coloring compositions comprising:(i) one or more developers selected from amino aromatic systems capable of being oxidized and thereafter undergoing a single nucleophilic attack, and (ii) one or more couplers selected from (A) (1) naphthols having an active leaving group in the para-position relative to the -OH group, or (2) phenols with an active leaving group which is hydrogen which is para to the -OH group, (B) 1,3-diketones, or (C) pyrazolones, such that in the presence of an oxidizing agent the or each developer reacts with the or each coupler substantially only at the position having the active leaving group.

Description

COMPOSITIONS TO COLOR HAIR AND ITS USE FIELD OF THE INVENTION This invention relates to new compositions for coloring the hair and to the methods for using these compositions in hair coloring processes.

BACKGROUND OF THE INVENTION Compositions are well known for providing hair with various colors by dyeing, either to change the natural color of the hair or to coat gray hair. These compositions comprise various aromatic compounds, commonly known as developers (also known as precursors or primary intermediates) together with various other aromatic compounds, commonly known as coupling agents or couplers. These are referred to as hair coloring agents by oxidation, because they require an oxidizing agent for color formation. The developers are generally 1,4-disubstituted compounds, more commonly, 1,4-diaminobenzene compounds and the coupling agents or couplers can also be disubstituted benzene compounds, such as for example, 1,3-disubstituted benzene compounds. The range of structures of the coupling agents or couplers is much more varied than that of the developers. During use, the compounds are subjected to oxidizing conditions in which the developers and couplers react to form the color. In general it is believed that this occurs by means of a sequence. gradual or stepwise, in which the developer molecules are activated by oxidation and react with the couplers to form reactive dimers. These continue reacting then to form colorful trímeros, which no longer react more. It is believed that monomeric couplers and developers and, to a lesser extent, dimers, diffuse into the hair body during the course of the reaction, which is quite slow. When they are inside the body of the hair, the dimers react to form trimers, which are very large to spread out easily and, thus, are trapped, colored or painted hair. Standard products typically include several different developers and several different couplers, for example, up to 5 developers and 5 or more couplers. It is generally accepted that 10 to 12 different compounds are required to obtain the full range of colors. Unfortunately, this system, although effective and commercially successful, has several disadvantages. First, the developers can react with each other, as well as with couplers and reactive dimers can react with the developers and couplers. In this way, the chemistry of the reaction is not defined and, it is not possible to predict precisely which compounds will be present in the hair at the end of the color-forming reaction. The exact composition of the colorful molecules formed in the hair can vary from one process to another, in accordance with the prevailing conditions. Therefore, the colors obtained may eventually vary between applications. An additional disadvantage is the discoloration of the color over time. A factor that contributes to discoloration is the lack of firmness to wash. The colorful trimeric molecules produced tend to be soluble in water and in other solvents. Consequently, they tend to be leached from the hair after repeated washing and from applications of, for example, hair sprays and other hair care products. This leads to discoloration or gradual change of the applied color. The action of other factors such as ultraviolet light, combing or brushing and perspiration also affect color. This is a problem that has existed with commercial products for several years and has not yet been resolved. An additional problem arises from the fact that the oxidation reaction involves two steps. In this way, in the hair dye composition, sufficient oxidizing agent must be present to induce the two oxidation steps. The presence of large amounts of the oxidizing agent can also have undesirable effects on the skin and hair. GB 1,025,916 discloses certain developers and couplers of different types. Describes developers that are N, N-disubstituted phenyldiamine derivatives. Three classes of coupling agents or couplers are described. It is said that the blue color originates from phenolic derivatives. It is said that the yellow color originates from certain defined derivatives of R-CO-CH2-COR and it is said that the red color originates from certain pyrazolone derivatives. These combinations are advantageous, since the developers will not react with themselves and can react with each coupler only in one way, so that the final chemistry of the dye obtained is defined P922 narrowly and is very predictable. GB 1,025,916 describes the mixing of couplers of couplers, for example, red with blue, blue with yellow, etc., so that shades are obtained between the colors that would be obtained with any of the individually used couplers. We have found that the dye combinations, described in GB 1,025,916, provide a lower fading resistance and wash resistance. We are not aware that a system of the type described in GB 1,025,916 has ever been marketed. • SUMMARY OF THE INVENTION It would be desirable to be able to provide a hair coloring system, in which the final color produced is predictable and controllable but which, also of origin, results in a fastness to washing and resistance to long-term discoloration. In accordance with a first aspect of the present invention, we provide a composition for coloring the hair, comprising: (i) one or more developers selected from aromatic amino systems that have the ability to be oxidized and, after this, is subjected to a single attack Electrophilic P922, and (ii) one or more couplers or coupling agents selected from: (A) (1) naphthols having an active leaving group in the para position, with respect to the OH group, ~~ or (2) phenols with formula wherein the H of para with respect to the OH group is an active leaving group and R1, R2, R3 and R4 are each independently selected from the group consisting of H, OH, methyl, ethyl, n-propyl, -propyl, t-butyl, NH2, C02H, C02R and COR, in which R is substituted or unsubstituted alkyl or alkenyl, (B) 1,3-diketones (1) containing the group wherein the N-phenyl group has no carboxy substituents, or (2) containing the group P922 wherein R contains an aryl group, and or (3) of the formula wherein R6 is selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, t-butyl and phenyl and R7 and R8 are each independently selected from the group consisting of methyl, ethyl, n-propyl , hydroxymethyl and hydroxypropyl, or (4) of the formula wherein R37 is alkyl Ci, in all of these, Z is an active leaving group, and (C) compounds of the formula P922 ~ wherein X is a non-salient substituent and wherein Z is an active leaving group and wherein A is H or methyl, and such that in the presence of an oxidizing agent the developer or each developer reacts with the coupler or with each coupler practically only in the position that has the active leaving group and always and ~ when the composition includes at least one coupler (B) and / or at least one coupler or (C). Thus, the compositions of the invention include at least one developer (i) and at least one coupler (ii). The coupler (ii) includes at least one coupler (B) and / or at least one coupler (C), that is, one or more couplers (B) or one or more couplers (C) or at least one of each. The coupler (B) can be selected from the couplers (B) (1), (B) (2) and (B) (3). The composition can also contain at least one coupler (a), which can be selected from the couplers (A) (1) and (A) (2).

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS In the invention, the developer is an aromatic amino compound having a structure such that it has the ability to be oxidized by an oxidizing agent. The structure is also such that the oxidized developer has the ability to be subjected to electrophilic attack by another molecule. In other words, the structure of the developer is such that it reacts practically only in one position, which is usually an amine. Suitable developers of this type include aromatic amino systems in which there is only one primary amine group, in which it occurs. the reaction, other amine groups and other reactive groups are protected by blocking substituents. The types of coupler defined are such that in the presence of an oxidizing agent they are each coupled with the developer only in one position, so that they only produce a resulting colorful dimer. The developer "defined also only reacts in one position.We believe that, the color formation is by reaction of a developer molecule with a coupling molecule to form a colorful dimer.Dimemers are not reactive and subsequently no reaction occurs. , the formation of color is extremely efficient.In addition, the colorful molecules formed are very pure.With the knowledge of the developer and coupler molecules present in the reaction system, it is possible to accurately and accurately predict the final combination of molecules These are significant advantages compared to standard oxidation coloring systems, and some of the colorful dimers formed have a significantly reduced water solubility compared to trimers. formed in coloring systems by standard oxidation, which helps to achieve an increase in the firmness to washing compared to standard oxidation coloring systems. In some cases, the structure of the developers and couplers is such that they show a greater degree of diffusion in the hair body than the coloring agents of the known systems and, consequently, lead to an improved resistance to discoloration. We have found that the reaction between the defined developer and the defined couplers is potentially very fast and efficient. This has the potential of hair coloring systems that do not require long exposure times that have been the norm to produce a deep and lasting coloration.

Additionally, we believe that the fastness to washing of the dyes containing the defined couplers, in combination with the defined developer, is improved compared to those of GB 1,025,916. ~~ Some of the right coupling molecules (A), (B) and (C) are known from the field of photography, since some are revealing. When these are reacted with a developer molecule, the couplers (A) provide a cyan color, the couplers (B) provide a yellow color and the couplers (C) provide a magenta color. Each coupler contains an entity of a specific formula, which is such that it has an active leaving group (represented as Z in the formulas in which this is not always an H) at a defined site. By "active outgoing group" we refer to any group that may be removed (to the conditions prevailing during the process of coloring or painting the hair), so that the developer reacts in that position of the coupler molecule. The bond formed between the coupler and the developer molecule is thus formed at the site of the active leaving group. Examples of active leaving groups are H, PhO, Cl, Br, alkoxy (RO), such as phenoxy PhO and RS-, where R is alkyl or aryl but any leaving group _ which comes out during __la is suitable.

P922 reaction, so as to allow the coupling between the developer and the coupler. The couplers (A) provide a cyan color. The particular color shade or intensity can be varied by varying the substituents of the phenol molecule (in the cases (A) (2)) or the naphthol molecule (in the cases (A (l)). active protrusion in the para position with respect to the OH group In case (2) this is an active proton, ie the aromatic ring is not substituted in the para position and the other ring substituents are not substituted to reduce the reactivity in this position In case (1) this can be an active proton or another active leaving group The couplers (A) can be (1) naphthols having an active leaving group in the para position with respect to the OH group. In this case, they generally have the formula I, as follows: wherein R17 is H, OH, -C02H, -C02R, F, Cl, Br, -CN, -N02, -CF_, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl, aralkyl, -NH2, -NHR, - NHCOR, -NR ,, -NHCOR, -R 'HCOR, CONHR, R' CONHR, -ROH, -S02R, S02NHR, -R'S02R, - P922 R'S02NHR S03H, -OR, -R'OR or -COR , in any of these R is H, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl or aralkyl and R 'is alkylene, alkenylene, cycloalkylene, cycloalkenylene, arylene, alkarylene or aralkylene or substituted versions of any of these. R17 can be, for example, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl, aralkyl, R 'NHCOR, R' CONHR, S02R, S02NHR, R 'S02R or R'S02NHR. R17 may include an aryl group. It is preferred that R17 is H. In this specification, unless otherwise indicated, alkyl and alkenyl are usually C1. 8, frequently C1_1, cycloalkyl 'and cycloalkenyl are usually C58, frequently C6, aryl or ar- is usually phenyl or naphthyl and the alk entity in "alkaryl is usually C_6, often C. Preferably, R17 is H. In other suitable couplers, R17 is The suitable couplers (A) (1) thus have the formula II or III, as follows: P922 When the coupler (A) is a naphthol (1), it is preferred that it has no solubilizing substituents (others other than Z), in particular, that does not have substituents -COOH or -OH. The coupler (A) (1) is preferably an unsubstituted naphthol. We find that the couplers of the formula II, in particular when R17 is H and, especially when Z is H, have an advantageous combination of properties to improve the fastness to washing, while allowing rapid coloring. We believe that this is because their molecules have a structure such as monomersThese are "small enough to diffuse into the body of the hair but, like the dimers, they are trapped inside the body of the hair, and the solubility of the hair dyes is such that they are not easily removed with the washes during the washings. Subsequent hair treatment processes These are particularly advantageous for coloring or painting of damaged hair (for example, hair that has previously been dyed or colored, bleached and / or subjected to P922 wavy permanent). In particular, these cyan couplers (A) (1) of the invention show improved properties of fade resistance or discoloration, especially in battered hair, compared to those of GB 1, 025, 916. In the above formulas, Z is any active leaving group. Suitable examples are H, PhO, Cl and Br but, any other reactive groups can be used. similar way (to the conditions of the reaction of coloring or dyeing the hair). If Z is PhO, Cl or Br, the reactivity of the coupling agent or coupler may tend to increase, as compared to couplers where Z is H. In any of the above formulas I to III, the defined groups may also contain any non-interfering substituent, that is, any group that. do not impede the coupling reaction between the developer and the coupler. In particular, phenyl and naphthyl groups can be substituted. Suitable non-interfering substituents include C02H, CH3, S02 NHCH3, S03H, C13 alkyl, such as ethyl or propyl, and CONHR, wherein R is preferably Cx_3 alkyl. The alkyl and CONHR substituents have the advantage that the solubility of the final colorful molecule is reduced. Phenyl groups can P922 contain one or more substituents, which are the same or different. If phenyl groups are substituted, mono-substitution is preferred. Preferably, the groups are not substituted, unless otherwise indicated. Alternatively, the couplers (A) can be selected from a specific defined group of phenols (2), which have the. formula IV wherein the H of para with respect to the OH group is an active leaving group and R1, R2, R3 and R4 are each selected independently from the group consisting of H, OH, methyl, ethyl, n-propyl, i-propyl, t-butyl, NH 2, CO, H, CO, R and COR, wherein R is substituted or unsubstituted alkyl or alkenyl. In this case, the active leaving group is always H. The couplers of this type include 3-aminophenol. These preferred couplers (A) (2) also show particularly good performance on battered hair. These demonstrate good color absorption and good wash fastness. These also show a good absorption of color and firmness when washing P922 in hair not mistreated. The yellow couplers (B) are 1,3-diketones. These ^ can have one of two formulas. A first set (1) contains the group and, in general, they have the formula V: In these couplers, the N-phenyl group may contain any non-interfering substituent, ie, any group which does not hinder the coloring reaction between the developer and the coupler, except that it may not contain any carboxy substituent. We found that molecules of this general type but having carboxy substituents, for example, those described in GB 1,025,916, show a reduced firmness to washing, in comparison with the couplers of the above structure. Preferably, also the n-phenyl does not contain hydroxy substituents and, particularly it is preferred that no P922 contains solubilizing substituents. What is most preferred is that it is not replaced. The group R9 can be H, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl, aralkyl, R'NHCOR, -R 'CONHR, -ROH, -R'S02R, -R'C02NHR, -NHCOR, -NR ,, -NHR, -NH2, -R'OR or -OR. In these groups, R can be H, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl or aralkyl and R 'is alkylene, cycloalkylene, alkenylene, cycloalkenylene, arylene, alkarylene or aralkylene. Substituted versions of any of these can be used. Suitable substituents include OH, -OR, Cl, Br, F, -C02H, -C02R, -NH2 and - "- COR.R9 may be, for example, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl, aralkyl, R'NHCOR, R 'CONHR, S02R, S02NHR, R' S02R or R'S02NHR Preferably, R9 is alkyl, alkenyl, alkaryl, alkenaryl, aralkyl or aralkenyl, More preferably, R9 is alkyl, aralkyl or alkaryl. Particularly preferred R9 are phenyl and C1_3 alkoxy, in particular ethyl and, especially, methyl.The yellow couplers (B) (2) contain the group P922 and, in particular, may have the following formula VI wherein R5 contains an aryl group. Rs preferably contains a phenyl group. It is preferred that the aryl group, preferably the phenyl group, does not contain any carboxy substituent. More preferably, it does not contain any hydroxy substituent, and it is particularly preferred that it does not contain solubilizing substituents. In particular, R5 contains an unsubstituted phenyl group. R36 may be, for example, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl, aralkyl, R'NHCOR, -R'CONHR, -ROH, -R'S02R, -R'C02NHR, -NHCOR, -NR2, - NHR, -NH2, -R'OR or -OR. Preferably, it is methyl. A preferred R5 group is P922 We found that the couplers of this formula also have a combination of particularly advantageous properties, to improve the firmness to washing, while allowing rapid coloring or dyeing, especially of damaged hair. In particular, these show an improved wash fastness over the couplers of GB 1,025,916. We believe that this is partially due to the presence of the aryl group in the R5 group, which increases the size of the final diameter trapped within the hair body. In the above formulas V and VI, Z can be any of the leaving groups indicated for Z in the previous coupler (A). The yellow couplers (B) (3) additionally preferred, have the formula VII "- wherein R6 is selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, t-butyl and phenyl and P922 R7 and R8 are independently selected from the group consisting of methyl, ethyl, n-propyl, hydroxymethyl and hydroxypropyl. The couplers (B) (3) are particularly advantageous for painting or coloring non-abused hair as well as "battered hair." In non-abused hair, they show rapid color absorption without loss of firmness to washing.They also show good firmness to the wash as well as resistance to fading or discoloration in battered hair In formula VII, Z may be any of the leaving groups indicated for Z on the former coupler (A), preferably Z is H. A coupler _ (B) ) (4) additional has the formula XXX wherein R37 is C4 alkyl, preferably t-butyl. In the above formulas V, VI, VII and XXX, the listed groups may also contain any non-interfering substituent group, ie, any group which does not hinder the coupling reaction between the developer and the coupler. phenyl and naphthyl Suitable non-interfering substituents include C02H, CH3, S02, NHCH3, S03H, C4 alkyl, such as ethyl or propyl, and CONHR, wherein R "is preferably C13 alkyl. In particular, the phenyl groups may contain one or more substituents, which are the same or different. If the phenyl groups are substituted, mono-substitution is preferred. Preferably, the groups are not substituted, unless otherwise indicated. The "magenta couplers (C), have the formula VIII "wherein X is a non-salient substituent and wherein Z is an active leaving group and wherein A is H or methyl.The preferred couplers (C) have the formula? x.

P922 wherein R10 is selected from the group consisting of H, methyl, ethyl, n-propyl, i-propyl, t-butyl and phenyl. In the above formulas VIII and IX, Z may be any of the leaving groups indicated for Z in the previous coupler (A). In the above formulas VIII and IX, the listed groups may also contain any non-interfering substituents, i.e., any group that does not hinder the coupling reaction between the developer and the coupler. In particular, the phenyl and naphthyl groups can be substituted. Suitable non-interfering substituents include CO, H, CH3, S02, NHCH, S03H, C13 alkyl, such as ethyl or propyl, and CONHR wherein R is preferably, alkyl C._3. In particular, the phenyl groups may contain one or more substituents which are the same or different. If phenyl groups are substituted, mono-substitution is preferred. Preferably, the groups are unsubstituted, unless otherwise indicated. The couplers of formulas VIII and IX are particularly suitable for painting or coloring undamaged hair and provide a good resistance to discoloration and color absorption in both unhampered hair and damaged hair. Specific examples of the couplers (A) include α-naphthol, 3-aminophenol and the compounds having the following structural formulas: Specific examples of the couplers (B) include benzoylacetanilide, acetoacetanilide, N, N-diethyl and N, N-dimethyl acetoacetamide and the compounds of the formulas P922 Specific examples of couplers (C) include pyrazolone with structural formula: and compounds having the same formula, except that Me is replaced by H or phenyl and / or H is replaced by methyl. The composition of the invention may also optionally contain additional couplers. For example, they may contain additional cyan couplers having the general formula X wherein R1 to R4 can be independently selected from H, OH, -CO, H, -CO, R, F, Cl, Br, -CN, -N02-, CF3, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl, aralkyl , -NH ,, -NHR, -NHCOR, -NR ,, -NHCOR, -R'NHCOR, - P922 CONHR, R 'CONHR, -R'OH, -S02R, S02NHR, -R'S02R, -R'S02NHR , -S03H, -OR, -R'OR or -COR, in any of these, R is H, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl or aralkyl and R 'is alkylene, alkenylene, cycloalkylene, cycloalkenylene , arylene, alkarylene or aralkylene or substituted versions of any of these. This formula covers the couplers (A) previously analyzed. Thus, in addition to the specific couplers (A), the composition may contain additional cyan couplers, provided that they have the formula X, as defined. Additional yellow couplers are included in the preferred compositions of the invention. These are compounds of formula XI, as follows: wherein R17 and R18 are each independently selected from H, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl, aralkyl, -R'NHCOR, R 'CONHR, -ROH, -R'S02R, -R' C02NHR, -NHCOR, -NR., -NHR, -NH2, -R'OR and -OR. In these groups, R can be H, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl or aralkyl and R 'is alkylene, cycloalkylene, alkenylene, P922 cycloalkenylene, arylene, alkarylene or aralkylene. Substituted versions of any of these can be used. Suitable substituents include OH, -OR, Cl, Br, F, -CO, H, -CO, R, -NH2 and -COR. Thus, in general this formula covers some of the couplers, of which the essential couplers of the invention can be chosen but, additionally, includes additional couplers. Preferably, at least one of R17 and R18 contains an aryl group. Some preferred additional yellow couplers have the formula XII, as follows: In this formula it may be preferred that R17 is phenyl. Preferred compositions of the invention may additionally include additional magenta couplers. These are pyrazolone derivatives. In particular, these contain the group P922 wherein Z is an active leaving group and X is an active leaving group or a non-leaving substituent. Normally, X is a non-salient substituent and these have the formula XIII, as follows: R wherein R10 can be any of the groups previously listed for R10. When R11 is H or Me, then the couplers fall within the scope of the aforementioned formula, in the context of the essential components of the invention. However, R 10 R 11 may also be selected from alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkaryl, aralkyl, -R'NHCOR, -R 'CONHR, -ROH, -R'S02R, -R'S02NHR or -R 'OR where R is H, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl or aralkyl and R' is alkylene, cycloalkylene, alkenylene, cycloalkenylene, arylene, alkarylene or alkylene (or substituted versions of any of these). Substituent groups Suitable P922 include OH, -OR, Cl, Br, F, -C02H, -C02R, -NH2, and -COR. These can be selected from, for example, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl, aralkyl, R'NHCOR, R 'CONHR, S02R, S02NHR, R'S02R or R'S02NHR. R11 is advantageously lower alkyl (Cx_4), such as methyl, ethyl, n-propyl, i-propyl or t-butyl, or substituted or unsubstituted phenyl. When it is phenyl, it may be preferred that it be a phenyl free of solubilizing substituents, in particular, substituents -COOH and -OH. Substituents m-S03H and p-S03H can be used. When R 11 is phenyl, it may preferably be unsubstituted. Ru can also be, preferably, methyl. Preferably R10 is methyl. This may alternatively be -NHR or -NHCOR, where R is any of the groups listed above for R on the coupler (A). RA is preferably phenyl. It is preferred that this is a phenyl free of solubilizing substituents, in particular, substituents -COOH and -OH. R10 can be in particular The magenta couplers in which R10 is H, P922 lower alkyl (C, _.), Such as methyl, ethyl, n-propyl, i-propyl or t-butyl, or substituted or unsubstituted phenyl, in particular, H or methyl is preferred. As well . Magenta couplers are preferred in which R11 is methyl. Preferably, any couplers of the composition are only of the defined types (A), (B) and (C). However, some compositions of the invention additionally contain cyan and / or yellow and / or magenta couplers none of these defined types but, in accordance with the definitions of the above additional couplers (formulas X to XIII) in combination with one or more couplers of types (A), (B) and (C). Preferred systems include at least one of each of the couplers (A), (B) and (C). In the preferred compositions, the coupler "(A) is included in combination with at least one coupler of type (B) and / or at least one coupler of type (C)." Alternative preferred compositions contain at least one coupler of type (C). B), in combination with couplers of type (A) and / or couplers of type (C) .The particularly preferred compositions contain at least one coupler of type (A), at least one coupler of type (B) and at least a coupler of type (C) In some preferred compositions, no more than two or even only one compound of any or all are included P922 types (A), (B) and (C). If additional couplers of the formulas X to XIII are included, then preferably no more than three, in particular, only one or two of each of the additional cyan, yellow and magenta couplers are included. In particular, no more than three or even just one or more couplers of each color type (cyan, yellow or magenta) are included. A particular advantage of the use of the couplers of the invention is that it is possible to obtain the full range of colors using only three specific types of coupler and one type of developer. This allows the couplers to be supplied in the form of a mixture having the required amounts of each type of coupler to develop any desired color. Alternatively, this also makes it possible to supply the coupler materials packaged separately, so that the consumer can control the eventual color that is obtained by mixing the correct amounts of each coupler to form the composition. Typically, the coupler is present in the composition in a total amount of from 0.01% to 5 or 10% by weight, based on the total weight of the composition applied to the hair. Preferably, the total coupler amounts are at least 0.01% by weight, frequently, at least 0.1 or 1%. Preferably, these are not more than P922 6% and, in some preferred compositions, may be present in amounts up to 3%, for example, no more than 2.5%. Couplings of types (A) and (C) (and other cyan and magenta couplers, as mentioned above) can be used in particularly low quantities. For example, couplers of type (A) (and other cyan couplers discussed above) can be used in amounts by weight based on the total weight of the composition applied to the hair, from 0.001 to 1%, preferably 0.04 or 0.005 up to 0.5%, for example, no more than 0.005% • by weight. Type (C) couplers (and other magenta couplers discussed above) may be used in amounts of, for example, 0.01 to 2 or 4%, preferably 0.03 to 3 or 2% and, in some compositions, no more than 1 or 0.5%. Couplers of type (B) (and other yellow couplers previously analyzed) are frequently used in larger quantities, for example 0.05 to 3 or 4% by weight (but in some cases, up to 5 or 6%), for example, of 0.1 to 2 or 3% by weight. Any of the couplers discussed above can also be used in salt form, for example, sulfate, phosphate and hydrochloride, particularly, sulfate or hydrochloride.

P922 Compounds containing free amine groups are preferably used in the form of their salts. The salt-form of this compound forms a powder and is often more stable than the free base form. The developer is an aromatic amino compound with the ability to be oxidized and subjected to a single electrophilic attack in the oxidized state. For example, it may be an aromatic system containing a single primary amine substituent. The developer is such that it reacts practically only in one position (normally, the amine position). In some cases, the structure of the developer may be such that it is possible for it to react with other developer molecules but, preferably, it reacts with coupler molecules. Preferably, the structure of the developer is such that it practically does not undergo any reaction with other developer molecules. Suitable developers include o-nitro and p-nitro a-naphthylamines of the formula P922 Other suitable developers include o- and p-nitrophenylamines H2N-Ph-N02, N, N-disubstituted o-phenylenediamines and N, N-disubstituted p-phenylenediamines. The developer can be an N, N-disubstituted p-phenylenediamine. These developers have an amine group protected by disubstitution and which reacts only in the primary amine group. In this case, this normally has the formula XIV, as follows: wherein R20 and R are each independently H, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl, aralkyl, -R'NHCOR, -R 'CONHR, -ROH, -R'S02R, -R'S02NHR or - R'OR, wherein R is alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl, aralkyl and R 'is alkylene, cycloalkylene, alkenylene, cycloalkenylene, arylene, alkarylene or aralkylene or substituted versions of any of these. Suitable substituent groups include OH, -OR, Cl, Br, F, -C02H, -C02R, -OR and -COR. Alternatively, R20 and R21 can form P922 together a substituted or unsubstituted cycloalkyl, cycloalkenyl or aryl ring. Preferably, R20 and R21 are, independently, C1_4alkyl, preferably, -CH3, -CH2CH3 or i-propyl; C1_2 hydroxyalkyl, preferably, -CH2CH2OH; alkylene alkoxy, preferably ethyl methoxy; -CH2CH2OCH2) R22S02NHR22 or R22NHS02R22 in which R22 is C ^ alkyl, for example, -CH, CH2, SO.NHCH. or -CH2CH2NHS02CH3. The particularly preferred developers of the above formula XIV are those in which R20 and R21 are both -CH2CH3 or R20 is -CH2CH3 and R21 is -CH2CH2NHS02CH3. It is believed that the last substituent R21 contributes to the dermatological compatibility. In other suitable developers, R20 is ethyl and R21 is hydroxyethyl; or R20 is ethyl and R21 is -CH2CH, OCH3; or R20 is selected from H, methyl, ethyl and propyl and R21 is selected from methyl, ethyl and propyl. In general, the developer can be selected from compounds having the general formula XV: The group Y is a blocking group that ensures that the reaction (in the conditions of hair dyeing) P922 occurs only in the primary amine group. Group Y can be, for example, -NR20R21 (as in the previous formula XIV). Other suitable Y groups include -N02, C0, H, -C0, R, -COR and OH. R is as defined above for formula XIV. In a formula XVI of alternative developer, the blocking group or blocking group Y is in the ortho position, with respect to the amino group, providing the following formula XVI.

In this way, the group Y is positioned so that the developer only undergoes a reaction, in the primary amine group, to the reaction conditions. - R13, R14, R15 and R16 can each be, independently, any of the groups listed for R1 to R4, above. R13 and R14 together, and / or R15 and R16 together can form a substituted or unsubstituted cycloalkyl, cycloalkenyl or aryl ring. Preferably, from R13 to R16 are each, independently, H, methyl, ethyl, n-propyl, i-propyl, F, Cl, OH, N02, -C02H, -C02R or -COR.

P922 In any of the foregoing formulas, the listed groups may also contain any non-interfering substituents, i.e., any group that does not hinder the coupling reaction between the developer and the coupler. In particular, the phenyl and naphthyl groups can be substituted. Suitable non-interfering substituents include C02H, CH3, S02 NHCH3, S03H, C13 alkyl, such as ethyl or propyl, and CONHR, wherein R is preferably C1_i alkyl. The alkyl and CONHR substituents have the advantage that the solubility of the final colorful molecule is reduced. The phenyl groups may contain one or more substituents, which are the same or different. If phenyl groups are substituted, monosubstitution is preferred. Preferably, the groups are unsubstituted, unless otherwise indicated. A preferred developer has the following formula XVII, as follows: Specific examples of the developers of the invention are those of the following structural formulas: P922 CH3CH OCH-j CH 3CH 2NHS02CH3 These are especially suitable for coloring damaged hair. Additional developers of the invention are: HOCH2CH2 ^ ^ CH.CH7OH which tends to fade or fade more quickly than some others and P922 which is very reactive. Examples of additionally preferred developers, which are particularly suitable for the coloring of non-abused hair, are 2,6-dichloro-p-aminophenol, 2-chloro-p-aminophenol, 3-chloro-p-aminophenol, 2, 3- dichloro-p-aminophenol and 3,5-methyl-p-aminophenol. The above derivatives include salts, for example, sulfate, phosphate and hydrochloride, particularly, sulfate or hydrochloride. The salts are normally formed with the amine groups. The preferred developer in which R20 is -CH, CH3 and R21 is CH2CH2NHS02CH3, is frequently provided in salt form as a stable powder (more stable than in the free base form). We have found that these salt forms, such that they contain 3 moles of salt molecule to 2 moles of the free base molecule. An additional useful salt is the hydrochloride salt of developers such as 2,6-dichloro-p-aminophenol. The developer is often included in the composition in amounts of from 0.01 to 5 or 7% by weight, based on the total composition applied to the hair.

Preferred amounts of the developer are from 0.3 to 2 or P922 4%, preferably 0.4 to 1.5 or 3% .. Both for the developers and the couplers, the solubility properties can be important. The developer and coupler compounds themselves must have a solubility such that they can be formulated in the appropriate concentrations. For their high pH application, they preferably have a solubility of at least 10g, more preferably at least 15g and most preferably at least 20g / 100ml of deionized water at a pH of about 10 and 25 °. C. These may have a solubility of at least 25 g / 100 ml, and even up to 50 or 80 g / 100 ml but, usually not more than 25 g / 100 ml The developer and coupler compounds _ are also generally so that the solubility of the dimer (or trimer if it is produced) in the final coloring is low under normal conditions of the hair and, especially, in washing conditions.Thus, the solubility (at a pH of about 8) of the final colored molecule is, preferably, by, below 50 or 80 g / 100 ml of deionized water at 25 ° C, in particular, below 2 or 1 g / 100 ml and, most preferably, below 0.5 g. / 100 ml or even below 0.2 g / 100 ml We find that if the compounds developer and coupler are n sufficiently soluble in the composition, a P922 the conditions of application to the hair, these will diffuse fast enough in the body of the hair. However, the colored molecules produced must have a sufficiently low solubility, such that they resist washing of the hair. In the compositions that will be applied at high pH (for example, above pH 10), an indication of its solubility can sometimes be provided by the pKa. Thus, if one or more of the developers and couplers, in particular the developers, has an ionizable group that is ionized practically at a pH above 9, preferably above pH 10, this is an indicator of the solubility at a pH of about 10 pH. However, in the final colorful molecule at the pH in the hair body (which is usually about pH 5.5 to 6) it becomes non-ionized. This provides an indication that under normal conditions their solubility has been reduced. This can be achieved frequently by providing at least one group having a pKa of from 8 to 12 (and, thus, ionizing above that pH) in a developer or coupler molecule and in the reaction to form a final colorful molecule, also has a pKa of from 8 to 12 (and, thus, does not ionize below that pH). Solubility can. be affected by several factors but, "the pKa may be a good indicator of probable solubility in some cases.

P922 We find that an advantage of the coloring compounds of the invention is that they can provide a uniform coloration and a resistance to discoloration in both battered hair and in hair without mistreating. This is particularly useful, in cases where the hair has been dyed once and then allowed to grow, so that untreated hair appears undyed. When it is re-dyed, the hair is not mistreated and the hair is damaged, dyed and discolored, they should be colored or dyed both and show a uniform resistance to discoloration. It is particularly important to be able to provide damaged hair (for example, to discolored hair and / or with permanent waving and / or pre-dyed) the color, the firmness to washing and the resistance to discoloration). An advantage of the system of the invention is that the full range of colors can be obtained using a very small number of compounds, with the standard oxidation dyeing systems. Preferably, only one or two, developer compounds are used, particularly, only one. In particular, it is preferred that it be used in combination with no more than 3 or even only one or two compounds of each of types (A), (B) and (C), discussed above. All these couplers and developers can be classified as coloring agents "oxidative or by P922 oxidation ", since they require the presence of an oxidizing agent to initiate their reaction, preferably less than 0.1% by weight, more preferably less than 0.08% by weight or 0.05% by weight and, in particular, practically no coloring agent by oxidation, which are not of types (i), (A), (B) and (C) or of formulas X to XIII In particular, it is preferred that no non-oxidative dyes are present and , of course, preferably less than 0.1% by weight, especially 0.08 or 0.05% by weight, in particular, virtually no other coloring components are included than the developer, as defined and couplers (A), (B) and (C) and couplers of formulas XI to XIII. That is, in the composition for coloring the hair, the coloring components consist essentially of the developer (i), the couplers (A), (B) and (C), optionally, couplers of the formulas XI to XIII. Of course, trivial amounts of other coloring components can be included, provided that these do not include significantly in the final color It is preferred that the composition contains less than 0.1% by weight, especially less than 0.08% by weight and, in particular, less 0.05% by weight and, even, practically no dye material by oxidation, which has the ability to react more than once, in the P922 oxidizing conditions of hair coloring reaction. A preferred composition comprises no more than 0.1% by weight of any oxidative coloring agent, which can react with itself to the hair coloring conditions. Preferably, it comprises not more than 0.08% by weight or 0.05% by weight of any of these agents. More preferably, the total amount of these agents does not exceed these values. Typically, the coloring compositions of the invention have a pH above 6.1 or 6.5, preferably, above 7, in particular, above a pH of 8 or 9. A pH of from 9 to 12 is often suitable. Systems of the invention can also be incorporated into systems for coloring hair of low pH (for example, from pH 1 to 6), described in our co-pending application with GB No. 9626713.3. The composition of the invention may also include - an antioxidant, as described in our co-pending application number 9710754.4. For developers and couplers to be effective in color formation, they require the presence of an oxidizing agent. This oxidizing agent is usually included in the composition just before it is "applied to the hair. Typically, the composition of P922 the invention will be supplied in at least two individual packages, such as bottles, the oxidizing agent is included in one package and the developers and couplers are included in the other. A preferred oxidizing agent is hydrogen peroxide. Other oxidizing agents that can be used include other inorganic peroxide oxidizing agents, preformed inorganic peroxy acid oxidizing agents and other organic peroxides, such as urea peroxide, melamine peroxide and mixtures of any of these. Suitable oxidizing agents are preferably water-soluble, ie they have a solubility of at least about 10g in 1,000ml of deionized water at 25 ° C ("Chemistry" CE Mortimer, 5th Edition, page 277). Other suitable inorganic alkali metal peroxides other than hydrogen peroxide include sodium periodate, sodium perbromate and sodium peroxide, and perhydrate inorganic salt oxidizing compounds, such as the alkali metal salts of perborates, percarbonates, perfosphates, persilicates and persulfates. . The inorganic salts of peridrates can be incorporated as monohydrates, tetrahydrates, etc. Mixtures of two or more of these inorganic peroxygen oxidizing agents can be used if desired. Biostes and iodates are suitable P922 of alkali metals, bromates are preferred. The amounts of the peroxygenated inorganic agent or oxidant that can be used in the composition are usually 0.0003 mol, 0.2 mol per 100 g of composition, preferably, up to 0.1 mol / 100 g. Suitable preformed organic peroxyacid oxidizing agents have the general formula R13C (0) OOH, wherein R13 is selected from saturated or unsaturated, substituted or unsubstituted, straight or branched chain alkyl, aryl or alkaryl groups of 1 to 14 atoms of carbon. A class of organic peroxyacid compounds, suitable for use in the invention, is that of the substituted amide compounds of the following general formulas XX and XXI: XII XIII wherein R is an aryl group or an unsaturated saturated alkyl or alkaryl group having 1 to 14 carbon atoms, R 35 is an aryl group or a saturated or unsaturated alkyl or alkaryl group, having 1 to 14 carbon atoms carbon and R34 is H or an unsaturated or saturated aryl group or an alkyl or alkaryl group having 1 to 10 carbon atoms. The P922 substituted amido organic peroxyacid compounds of this type are disclosed in EP-A-170, 386. Other suitable organic peroxyacid oxidizing agents include paracetic, pernanoic, nonilamidoperoxycaproic (NAPCA), perbenzoic, m-clroperbenzoic, di-peroxy-isophthalic, mono -peroxyphthalic, peroxylauric, peroxypropionic hexanesulfonyl, N, N-phthaloylamino peroxycaproic, monopersuccinic, nonailoxybenzoic, dodecanedioyl-monoperoxybenzoic, peroxyadipic acid nonyliamide, diacyl and tetracylperoxides, especially diperoxydecanedioic acid, diperoxytetradecanedioic acid and diperoxyhexadecanedioic acid and derivatives thereof. The mono- and dibeperacelic acid, mono- and diperbrasyl acid and N-phthaloylaminoperoxycaproic acid and derivatives thereof, are also suitable for use in the invention. The preferred peroxyacid materials are selected from the peracetic and pernanoic acids and mixtures thereof. Suitable amounts of preformed organic peroxyacid oxidizing agents are from about 0.0001 to 0.1 moles per 100 g of the compositions, preferably from about 0.001 to 0.05 moles, more preferably from about 0.03 to 0.04 moles, especially from about 0.004 to 0.03 moles. lOOg.

P922 The preformed organic peroxyacid oxidizing agent, when present, is preferably present at the level of from about 0.01% to about 8%, more preferably ", from about 0.1% to about 6%, with the greatest preference, from about 0.2% to about 4% and, especially, from about 0.3% to about 3% by weight of the hair coloring composition. The weight ratio of the inorganic peroxygen oxidizing agent to the organic peroxyacid ... preferably preformed is in the range of from about 0.0125: 1 to about 500: 1, more preferably, from about 0.0125: 1 to about 50: 1. If additional organic peroxides are used, suitable amounts are from about 0.01% to about 3%, preferably, from about 0.01% to about 2%, more preferably, from about 0.1% to about 1.5%, and most preferably, from about 0.2% to about 1% by weight of the composition. An advantage of the systems of the invention is that very low levels of the oxidizing agent can be used if desired. These systems are described in more detail in our co-pending application 9710756.9. The composition may comprise ammonia, P922, for example, in an amount of at least 0.01% by weight, preferably at least 0.05% by weight or 0.1% by weight. In practice, the composition of the invention can be supplied to the consumer in a single package containing the developer and the couplers. It is also possible to supply the composition, so that the developers are individually packaged and the couplers are individually packaged. The couplers can be supplied as a preformed mixture, selected to provide a particular color. Alternatively, these can be supplied separately for the consumer to mix and provide a variety of different colors to the hair. In all cases, the developers and couplers are mixed to form the composition of the invention, before application to the hair. In general, the oxidizing agent, when supplied together with the coloring agents, is individually packaged separately from any of the coloring components. It is often mixed with the coloring components to form a component of the coloring composition of the hair, before application to the hair. Alternatively, it can be applied to the hair separately, either before or after the hair coloring composition. The developers, couplers and oxidizing agents and P922 Any other materials that are to be applied to the hair as components of the composition of the invention, can be supplied in any suitable physical form. A preferred physical form is liquid. The liquid can be of low viscosity, for example, it can be thinned with water or it can be of higher viscosity. The material may be suspended in a gel grid. The gel can be solid or of low viscosity. Hair coloring or painting materials are often formulated, so that when they are mixed to form the composition of the invention to be applied to the hair, they form a product with a creamy consistency, which is convenient for application to hair. The final composition that is applied to hair is often in the form of an emulsion. Each individual material may be supplied in such a way that the composition containing it has a pH above or below 7. For example, it may be from pH 1 to 11. In order to help the solubility of the various components, particularly of the developers and couplers, in a water-based carrier, the vehicle can have a pH above 7, for example, a pH of 8 or 9 at pH 10 or 11. The pH as supplied is from 1 to 6. It can help improve the stability of the components. The materials can be supplied, in such a way P922 that the pH of the final composition when mixed for its application to the hair, has a pH below 7, at a time when one of the components used to form it has a pH above 7. Alcohols such as ethanol, in amounts of from for example 5 to 10 or 25%, can be included to aid the solubility of the developers and, particularly, of the couplers in a water-based vehicle. In a second aspect of the invention, we provide a kit or set for coloring the hair, comprising as hair coloring components: (i) one or more developers, as defined above and (ii) one or more couplers, selected from ( A), (B) and (C), as defined above, provided that at least one coupler (B) and / or (C) is present. In this kit or game for coloring the hair, any of the components may have any of the features described above of the composition of the invention. In a third aspect of the invention, we provide a method for coloring hair, comprising, providing: (i) one or more developers, as defined above P922 (ii) one or more couplers, selected from (A), (B) and (C), as defined above, provided that at least one coupler (B) and / or (C) and (iii) are present; oxidizing agent. and applying (i), (ii) and (iii) to the hair to be painted or colored In the method of the invention, the components (i), (ii) and (iii) are preferably applied practically simultaneously, particularly preferably in mixed form to form a single composition and then applied together to the hair. Within the term "practically simultaneously" we also include the application to the hair of one or more components, followed by the subsequent application of the remaining components in a period of no more than 5 minutes. The components can, alternatively, be applied to the hair in a non-simultaneous manner. For example, the developer and couplers can be mixed and applied to the hair, followed or preceded by the application of the oxidizing agent. Alternatively, the oxidizing agent can be applied simultaneously either with the developer or the couplers, or the developer and the couplers being applied at different times. The conditions of the reaction are usually those that are conventionally applied to dye the P922 hair. The temperature is usually 10 to 45 ° C, frequently, 20 to 35 ° C. The pH can be low (for example, below 7 or 6) but is often high, for example, above 6.5 or 7, or, above 8 or 9 or even above 10. In This specification, when analyzing the leaving groups, as well as the compounds that react only in one position or only with certain other compounds, we refer to the reaction to the conditions in which the coloring compounds will be applied to the hair. In a fourth aspect of the present invention, we provide a hair coloring system, comprising: (i) one or more developers, as defined above, (ii) one or more couplers, selected from (A), (B) and (C), as defined above, provided that at least one coupler (B) or (C) and, optionally, compounds of the above formulas X to XIII, which do not comprise other oxidative coloring agents and The system has the ability to provide a broad spectrum of color nuances without using additional coloring agents. In the system of the fourth aspect of the invention, P922 The amounts and types of developer and coupler are selected so that the particular color desired for any application is obtained. For any different color, the same set of developers and couplers is selected to provide that color. Preferably, the system can provide at least a light chestnut hue, at least a red hue and at least a dark brown hue. More preferably, it also provides' at least one blond hue and at least one black matrix. Preferably, the system comprises no more than three, preferably only one or two compounds of each of types (i), (A), (B) and (C). Thus, in this preferred embodiment of the system of the invention, a wide range of colors is obtained from as few coloring components as four components. The system can comprise, as couplers, couplers (A) and (B), optionally together with couplers with formula 1 wherein R10 and R11 are as defined above, for example, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl, aralkyl, R'NHCOR, R'CONHR, P922 S02R, SO, NHR, R'SO, R or R'S02NHR. Preferably, R10 is alkyl, alkenyl, aryl, alkaryl, aralkyl, R'NHCOR or R 'CONHR, and R11 is alkyl, alkenyl, aryl, alkaryl or aralkyl. The system may also comprise instructions for the selection of quantities and types of components (i) and (ii), to obtain a range of colors. The system can be supplied to consumers, for example, those who wish to paint their own hair or for rooms for hair repair, together with instructions for selecting the particular amounts of each of the coloring agents, to obtain different colors. The system can also be used by the manufacturers of the hair coloring compositions. The manufacturer provides the coloring components of the four different types and selects the quantities and types needed for each individual color that is intended to be marketed. In the system of the invention, any of the materials that were discussed above can be used in the context of the composition of the invention. The invention also provides novel hair coloring compositions, containing N, N-dimethyl acetoacetamide and / or N, N-diethyl acetoacetamide and / or the compound of formula P922 wherein R is H, phenyl or C14 alkyl. These compositions may have any or all of the features described above. Any of the compositions may contain various optional ingredients as follows.

Oxidative Dye Precursors Preferably, the only oxidatively tempting materials in the composition are the materials (i) and (ii) discussed above. However, the compositions may optionally contain minor amounts of other oxidative dye materials. These may include those described in our co-pending application PCT / US97 / 22719, filed on December 9, 1997. In general terms, the primary intermediate compounds of oxidative dye, include those monomeric materials which, in oxidation, form oligomers or polymers that have extended conjugated systems of electrons in their molecular structure. Due to the new electronic structure, the resulting oligomers and polymers show a shift in their spectrum P922 electronic in the visible range and appear colorful. For example, the oxidative primary intermediates having the ability to form colorful polymers include materials such as aniline, which has a single functional group and which, in oxidation, forms a series of conjugated imines and quinoid dimers, trimers, etc., of a color that varies from green to black Compounds such as p-phenylenediamine, which has two functional groups, are capable of oxidative polymerization to produce colored, higher molecular weight materials that have extended conjugated electronic systems A representative list of primary intermediates and secondary couplers, suitable for use herein, is found in Sagarin, "Cosmetic Science and Technology ", Interscience, Edition _ Special, Volume 2 pages 308__a 310.

Non-Oxidative Dyes - Other Dyes The hair coloring compositions used in the present invention can, in addition to the essential hair coloring agents by oxidation. (i) and (ii) and optional oxidative dyes, additionally include non-oxidative dye materials and other dye materials. Non-oxidative dyes as well as other optional dyes, suitable for use in P922 hair coloring compositions and processes according to the present invention include both semi-permanent and temporary dyes as well as other dyes. Non-oxidative dyes, as defined herein, include so-called "direct-acting dyes", metallic dyes, metal chelate dyes, fiber-reactive dyes and other synthetic and natural dyes. Various types of non-oxidative dyes are detailed in: "Chemical and Physical Behavior of Human Hair" 3rd Edition by Clarence Robbins (pages 250-259); "The Chemistry and Manufacture of Cosmetics". Volume IV. 2nd Edition, Maison G. De Navarre in chapter 45 by G.S. Kass (pages 841-920); "Cosmetics: Science and Technology", 2nd Edition, Volume II, Balsa Sagarin, Chapter 23 by F.E. Wall (pages 279-343); "The Science of Hair Care" edited by C. Zviak, Chapter 7 pages 235-261 and "Hair Care" J.C. Johnson, Noyes Data Corp., Park Ridge, U.S.A. (1973), (pages 3-91 and 113-139). Direct-acting dyes, which do not require an oxidative effect to develop the color, are also designated hair dyes and have long been known in the art. These are normally applied to hair in a base matrix that includes surfactant material. Direct-acting dyes include nitro dyes, such as nitroaminobenzene derivatives or. Nitroaminophenol; disperse dyes, such as nitroarylamines.

P922 aminoanthraquinones or azo dyes; anthraquinone dyes, naphthoquinone dyes; basic dyes, such as C.l. 46005. Nitro dyes are added to the dyeing compositions to improve the color of the dye and to add an adequate aesthetic color to the dye mixture before application.Additional examples of direct-acting dyes include the basic Arianor brown dyes 17, Cl (color index) - No. 12,251; basic red 76, C.l. 12,245; chestnut core 16, C.l. - 12,250; basic yellow 57, C.l. -12,719 and basic blue 99, C.l. - 56,059 and additional direct-acting dyes, such as acid yellow 1, C.l. 10,316 (yellow D &C No. 7); acid yellow 9, C.l. - 13,015; basic violet C.l. 45,170; dispersed yellow 3, C.l. 11,855; basic yellow 57, C.l. - 12,719; dispersed yellow 1, C.l. - 10,345; violet basic 1, C.l. - 42,535, basic violet 3, "Cl-42,555, blue-green, Cl-42090 (Blue FD &C No. 1), yellowish red, Cl-14700 (red FD &C No. 4), yellow, Cl 19140 (yellow FD &C No. 5), yellowish orange, Cl 15985 (yellow FD &C No. 6), bluish green, Cl 42053 (green FD &C No. 3), yellowish red, Cl 16035 (red FD &C no. 40), bluish green, Cl 61570 (green D &C No. 3), orange, Cl 45370 (orange D &C No. 5), red, Cl 15850 (red D &C No. 6), bluish red, Cl 15850 (red D &C No. 7); P922 light bluish red, C.l. 45380 (red D &C No. 22); bluish red, C.l. 45410 (red D &C No. 28); bluish red, C.l. 73360 (red D &C No. 30); reddish purple, C.l. 17200 (red D &C No. 33); dirty blue red, C.l. 15880 (red D &C No. 34); bright yellow red, C.l. 12085 (red D &C No. 36); bright orange, C.l. 15510 (orange D &C No. 4); greenish yellow, C.l. 47005 (yellow D &C No. 10); bluish green, C.l. 59040 (green D &C No. 8); violet blue, C.l. 60730 (Ext. Violet D &C No. 2); greenish yellow, C.l. 10316 (Ext yellow D &C No. 7). Fiber-reactive dyes include Procion (RTM), Drimarene (RTM), Cibacron (RTM), Levafix (RTM) and Remazol (RTM) dyes available from ICI, Sandoz, Ciba-Geigy, Bayer and Hoechst respectively. Natural dyes and plant dyes, as defined herein, include alkane (La sonia alba), chamomile (Matricaria chamomila or Arithemis nobilis), indigo, indigo and bark extract from palo de campeche and walnut. Temporary hair dyes or hair dyes are generally comprised of dye molecules that are too large to diffuse into the body of the hair and act on the outside of the hair. These are normally applied through a procedure of leaving it applied, in which it is allowed P922 that the dye solution dries on the surface of the hair. Since these dyes are normally less resistant to the effects of washing and cleaning the hair with active surface agents and wash the hair with relative ease. Temporary hair dye can be used in the compositions of the invention and preferred examples of temporary hair dyes are illustrated below.

Yellow Blue-Violta P922. The. Semi-permanent hair dyes are dyes that generally have a smaller size and an effect to temporary hair rinses but are generally larger than permanent (oxidative) dyes normally; semi-permanent dyes act in a similar way to oxidative dyes, It has the potential to spread in the hair body. However, the semi-permanent dyes are generally smaller in size than the aforementioned conjugated oxidative dye molecules and, as such, are predisposed again to the gradual outward diffusion of the hair. The simple action of washing and cleaning the hair will encourage this process and, in general, the semi-permanent dyes are removed by washing the hair mainly after approximately 5 to 8 washes. Semi-permanent dye systems may be included in the compositions of the present invention. Semi-permanent dyes suitable for use in the compositions of the present invention are Blue 2 HC, Yellow 4 HC, Red 3 HC, Violet Dispersed 4, Black Dispersed 9, Blue 7 HC, Yellow 2 HC, Blue Dispersed 3, Violet Dispersed 1 and mixtures thereof. Examples of semi-permanent dyes are illustrated below: P922 blue Red Typical semi-permanent dye systems incorporate mixtures of both large and small color molecules. Since the size of the hair is not uniform from root to tip, the small molecules will diffuse both at the root and at the tip but will not be retained inside the tip, while large molecules will generally only be able to diffuse into the tips. ends of the hair. This combination of sizes of dye molecules is used to help provide consistent color results from the root to the tip of the hair, both P922 during the initial dyeing process as during the subsequent washings.

Regulatory Agents If desired, the compositions may contain one or more optional regulatory agents and / or hair swelling agents (HSAs). To adjust the pH of the final composition or of any constituent part thereof, several different pH modifiers can be used. This adjustment of the pH can be carried out using acidulants well known in the field of the treatment of keratinous fibers and, in particular, of human hair, such as organic and inorganic acids, such as hydrochloric acid, tartaric acid, citric acid, succinic acid, phosphoric acid and carboxylic or sulphonic acids, such as ascorbic acid, acetic acid, lactic acid, sulfuric acid, formic acid, ammonium sulfate and sodium dihydrogen phosphate / phosphoric acid, disodium hydrogen phosphate / phosphoric acid, potassium chloride / hydrochloric acid, dihydrogen potassium phthalate / hydrochloric acid, sodium citrate / hydrochloric acid, potassium citrate dihydrogen / hydrochloric acid, potassium dihydrogen citrate / citric acid, sodium citrate / citric acid, sodium tartrate / acid P922 tartaric, sodium lactate / lactic acid, sodium acetate / acetic acid, disodium hydrogen phosphate / citric acid and sodium chloride / glycine / hydrochloric acid, succinic acid and mixtures thereof. These are suitable for regulating at low pH. Examples of alkaline regulating agents are ammonium hydroxide, ethylamine, dipropylamine, triethylamine and alkanediamines, such as 1,3-diaminopropane, anhydrous alkaline alkanolamines, such as mono or di-ethanolamine, preferably those which are fully substituted in the amine group. , such as, for example, dimethylaminoethanol, polyalkylene polyamines, such as diethylenetriamine or a heterocyclic amine, such as morpholine, as well as alkali metal hydroxides, such as sodium and potassium hydroxide, alkaline earth metal hydroxides, such as magnesium and calcium hydroxide, basic amino acids, such as L-arginine, lysine, alanine, leucine, iso-leucine, oxysaline and histidine and alkanolamines, such as dimethylaminoethanol and aminoalkylpropanediol and mixtures thereof. Also suitable for use herein are compounds that form HC03"by dissociation in water (hereinafter referred to as" ion-forming compounds ".) Examples of suitable ion-forming compounds are Na2CO3, NaHCO3, 2CO3, (NH4) 2C03. , P922 NHjHC03, CaCO3 and Ca (HC03) and mixtures thereof. These are suitable for regulating at high pH. Preferred for use herein as buffering agents (at low pH) are organic and inorganic acids having a first pKa below pH 6 and their conjugate bases. As defined herein, the first pKa means the negative logarithm (base 10) of the equilibrium constant, K, where K is the acid dissociation constant. The organic and inorganic acids to be used herein are: aspartic, maleic, tartaric, glutamic, glycolic, acetic, succinic, salicylic, formic, benzoic, malic, lactic, malonic, oxalic, citric, phosphoric and mixtures thereof . Particularly preferred are acetic, succinic, salicylic and phosphoric acids and mixtures thereof.

Catalyst The coloring compositions herein may optionally contain a catalyst for any organic peroxygen oxidizing agents and optional preformed peroxyacid oxidizing agents.

Thickeners The coloring compositions of the present invention may additionally include a thickener in P922 from about 0.05% from about 20%, preferably from about 0.1% from about 10%, more preferably from about 0.5% to about 5% by weight. The "thickening agents suitable for use in the compositions herein, are selected from oleic acid, cetyl alcohol, oleyl alcohol, sodium chloride, cetearyl alcohol, stearyl alcohol, synthetic thickeners, such as Carbopol, Aculin and Acrosil and mixtures of The preferred thickeners for use herein are Aculyn 22 (RTM,) steareth-20 methacrylate copolymer; Aculyn 44 (RTM) polyurethane resin and Acusol 83O (RTM), acrylate copolymers, which are available from Rohm and Haas, Philadelphia, PA, USA. Additional thickeners suitable for use herein include sodium alginate or gum arabic or cellulose derivatives, such as methylcellulose or the sodium salt of carboxymethylcellulose or acrylic polymers.

Dilute e Water is the preferred diluent for the compositions according to the present invention.

However, the compositions according to the present invention may include one or more solvents as additional diluent materials. In general, P922 solvents suitable for use in the coloring compositions of the present invention are selected to be water miscible and skin-friendly. Suitable solvents for use as additional diluents include C1-C20 monohydric or polyhydric alcohols and their ethers, glycerin, where monohydric and dihydric alcohols and their esters are preferred. In these compounds, alcohol residues containing from 2 to 10 carbon atoms are preferred. Thus, a preferred group includes ethanol, isopropanol, n-propanol, butanol, propylene glycol, ethylene glycol monoethyl ether, 1,2-hexanediol, butoxy ethanol, benzyl alcohol and mixtures thereof. Water is the preferred primary diluent in the compositions according to the present invention. The principal diluent, as defined herein, refers to the level of the diluent present being greater than the total level of any other diluents. The diluent is present at a level, preferably from about 5% to about 99.98%, preferably from about 15% from about 99.5%, more preferably, from at least about 30% to about 99%, and especially from about 50% to about 98% by weight of the compositions herein.

P922 Enzyme Another useful additional material in hair coloring compositions, according to the present invention, is one or more enzymes. Suitable enzyme materials include the lipases, cutinases, amylases, neutral and alkaline proteases, esterases, cellulases, pectinases, lactases and peroxidases available and conventionally incorporated in the detergent compositions. Suitable enzymes are discussed in U.S. Patent Nos. 3,519,570 and 3,533,139. Peroxidases are specific hemoproteins for peroxide, but they use a wide range of substances as donors. The catalase that composes the peroxide is included here, in view of the fact that it is generally of similar structure and properties and can effect certain oxidations by H202. The decomposition of H202 can be considered as the oxidation of one molecule by the other. It is widespread in aerobic cells and may have some more important function. Coenzyme peroxidases are not haemoproteins and one is at least one flavoprotein. Other flavoproteins such as oxidized xanthine, will also use H202 among other acceptors and coenzyme peroxidases resemble these rather than the classical peroxidases in that they are not P922 ~ -specific for H, 02. Suitable peroxidases for the compositions of the present invention include horseradish peroxidase, horseradish peroxidase, cow's milk peroxidase, rat liver peroxidase, linginase, and haloperoxidase such as chlorine and bromo-peroxidase. The enzymes are optionally incorporated at levels sufficient to provide up to about 50 mg by weight, more commonly, from about 0.01 mg to about 10 mg of active enzyme per gram of the hair treatment composition of the invention. Stated otherwise, the enzyme peroxidase can be incorporated into the compositions according to the invention, at a level of from about 0.0001% to about 5%, preferably from about 0.001% to about 1%, more preferably, about 0.01. % to about 1% active enzyme by weight of the composition. Commercially available protease enzymes include those sold under the trademarks Alcalase, Savinase, Primase, Durazym, and Esperase from Novo Industries A / S (Denmark), which are sold under the trademark Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the Opticlean and Optimase brand by Solvay Enzimes. The protease enzyme can P922"" -, J. "0" incorporated into the compositions according to the invention, at a level of from 0.0001% to 4% of the active enzyme by weight of the composition.Amylases include, for example, α-amylases obtained of 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 trademark Rapidase from Gist-Brocades, and those sold under the trademark Termamyl and BAN from Novo Industries A / S. The amylase enzyme can be incorporated in the composition according to the invention at a level of 0.0001% to 2% of the active enzyme by weight of the composition. The lipolytic enzyme may be present at active lipolytic enzyme levels of from 0.0001% to 2% by weight, preferably from 0.001% to 1% by weight, more preferably from 0.001% to 0.5% by weight _ of the compositions. The lipase can be of fungal or bacterial origin, when obtained, for example from a producing strain of Humicola sp. , Thermomyees sp. or Pseudomonas sp. Including Pseudomonas pseudoalcaligenes or Pseudomonas fluorescens. The lipase of chemically or genetically modified mutants of these strains are also useful in the present. A preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is described in the patent P922"- -" - -. "" European granted, EP-B-0218272. Another preferred lipase herein is obtained by cloning the Humicola lanuginosa gene and expressing the gene in Aspergillus oryza, as a host, as described in the European Patent Application EP-A. -0258 068, which is obtained commercially from Novo Industri A / S, Bagsvaerd, Denmark, under the trade name Lipolase This lipase is also described in U.S. Patent No. 4,810,414, Huge-Jensen et al, granted on March 7, 1989.

Surfactants The compositions of the present invention may additionally contain a surfactant system. Suitable surfactants for inclusion in the compositions of the invention generally have a lipophilic chain length of from about 8 to about 22 carbon atoms and may be selected from anionic, cationic, nonionic, amphoteric, zwitterionic surfactants and mixtures thereof. (i) Anionic surfactants Suitable anionic surfactants for inclusion in the compositions of the invention include P922 alkyl sulphates, ethoxylated alkyl sulphates, alkyl glyceryl ether sulfonates, methyl acyl taurates, fatty acyl glycinates, N-acyl glutamates, acyl isethionates, alkyl sulfosuccinates, alkyl ethoxysulphosucinates, alpha-sulphonated fatty acids, their salts and / or esters, alkyl ethoxy carboxylates, alkyl phosphate esters, ethoxylated alkyl phosphate esters, alkyl sulphates, acyl sarcosinates, hydrotropes, such as alkyl xylene sulfonate and fatty acid / protein condensates and mixtures thereof. The alkyl and / or acyl chain lengths of these surfactants are C12-C12, preferably C12-C1S, and more preferably, C12-C14. (ii) Nonionic surfactants The compositions of the invention may also comprise water-soluble nonionic surfactants. Surfactants of this class include C12-C14 fatty acid mono- and diethanolamides, sucrose polyester surfactants and polyhydroxy fatty acid amide surfactants having the following general formula.

The preferred acid amide surfactants P922 polyhydroxy fatty N-alkyl, N-alkoxy or N-aryloxy, preferred, according to the above formula, are those in which R8 is C5C31 hydrocarbyl, preferably C6-C19 hydrocarbyl, which includes straight-chain alkyl and alkenyl and branched or mixtures thereof and R9 is normally hydrogen, alkyl or Cj-C8 hydroxyalkyl, preferably methyl or a group of formula -R1-0-R2 wherein R1 is C2-C8 hydrocarbyl, which includes straight chain, branched chain and cyclical (including aryl) and, preferably it is C2-C4 alkylene, R2 is straight-chain, branched chain and C-C8 cyclic hydrocarbyl, including aryl and oxyhydrocarbyl, and is preferably C ^ C ^ alkyl, especially methyl or phenyl. Z2 is a polyhydroxyhydrocarbyl entity having a linear hydrocarbyl chain with at least 2 hydroxyls (in the case of glyceraldehyde) or at least 3 hydroxyls (in the case of other reducing sugars) directly connected to the chain or an alkoxylated derivative (preferably ethoxylated or propoxylated) of the same Z2 will preferably be derived from a reducing sugar in a reductive amination reaction and, more preferably, Z2 is a glycityl entity. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose, as well as glyceraldehyde. High-dextrose corn syrup, high-grade corn syrup can be used as raw materials P922 fructose and high maltose corn syrup, as well as the individual sugars listed above. These corn syrups can produce a mixture of sugar component for Z2. It should be understood that for no reason is it intended to exclude other suitable raw materials. Z2 will preferably be selected from the group consisting of -CH2- (CHOH) n -CH, OH, -CH (CH2OH) - (CHOH) ^ -C ^ H, CH, (CHOH), (CHOR ') CHOH) -CH, OH, wherein n is an integer from 1 to 5, inclusive and R' is H or a cyclic mono- or polysaccharide and the alkoxylated derivatives thereof. As indicated, the most preferred are glycityls wherein n is 4, particularly -CH 2 - (CHOH) 4 -CH 2 OH. The most preferred polyhydroxy fatty acid amide has the formula R8 (CO) N (CH3) CH2 (CHOH) 4CH2OH wherein R8 is a C6-C19 straight-chain alkyl or alkenyl group. In the compounds of the above formula, R8-CO-N < it can be, for example, cocoamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmiamide, ceboamide, etc. The oil-derived nonionic surfactants suitable for use herein include emollients derived from plants and animals, soluble in water, such as triglycerides with an inserted polyethylene glycol chain; mono- and diglycerides ethoxylates, polyethoxylated lanolins and ethoxylated butter derivatives. A preferred class of nonionic surfactants P922 oil derivatives for use herein has the following general formula: 0 H RCOCH, (OH) CH2 (OCH2CH2) nOH 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 comprises an aliphatic radical having on average from about 5 to 20 carbon atoms , preferably from about 7 to 18 carbon atoms. Suitable oils and ethoxylated fats of this class include polyethylene glycol derivatives of glyceryl cocoate, glyceryl caproate, glyceryl caprylate, glyceryl ceboate, glyceryl palmate, glyceryl stearate, glyceryl laurate, oleate. of glyceryl, glyceryl ricinoleate and the glyceryl esters derived from triglycerides, such as palm oil, almond oil and corn oil, preferably glyceryl ceboate and glyceryl cocoate. present are polyethylene glycol polyethylene glycol-based non-ionic C9-C15 fatty alcohol surfactants, which contain P922 averages from about 5 of about 50 ethyleneoxy entities per mole of surfactant. Polyethylene glycol polyetheylene glycol C9-C15 fatty alcohols suitable for use herein include Pareth-3 C8-C4, Pareth-4 C9-C11, Pareth-5 C9-Cl ?; Pareth-6 C9-C11 # Pareth-7 C9-Cu, Pareth-8 C9-C11 # Pareth-3 Cn-C15, Pareth-4 C ^ -C ^, Pareth-5 C? RC15, Pareth-6 Cu-C15 , Pareth-7 C ^ -C ^, Pareth-8 Cn-C15, Pareth-9 C ^ -C ^, Pareth-10 C11-C15, Pareth-11 Cn-C15, Pareth-12 Cu-Cl5, Pareth-13 C ^ -Cjj and Pareth-14 Cu-C15. PEG 40 hydrogenated castor oil is obtained commercially under the trade name Cremophor (RTM) from BASF. The glyceryl cocoate 'PEG 7 and the glyceryl laurate PEG 20 are commercially available from Henkel, under the trademarks Cetiol (RTM) HE_ and Lamacit (RTM) GML 20, respectively. Pareth-8 C8-C ^, is available commercially from Shell Ltd under the trademark Dobanol (RTM) 91-8. Particularly preferred for use herein are the polyethylene glycol ethers of the ceteryl alcohol, such as Cetearet 25, which is available from BASF, under the trademark Cremaphor A25. Nonoxynol surfactants can also be used. Also suitable for use herein are nonionic surfactants derived from fats P922 compound vegetables extracted from the fruit of the tree of Shea (Butyrospermum Karkii Kotschy) and the derivatives thereof. In a similar wayIn the compositions according to the invention, the ethoxylated mango, cocoa and butter derivatives of Illipe can be used. Although these are classified as ethoxylated nonionic surfactants, it is understood that a certain proportion can remain as non-ethoxylated vegetable fat or oil. Other suitable nonionic oil-derived surfactants include ethoxylated derivatives of almond oil, peanut oil, rice bran oil, wheat germ oil, linseed oil, jojoba oil, oil of the peach pit, nuts, palm nuts, pistachio nuts, sesame seeds, rapeseed, juniper oil, corn oil, peach kernel oil, poppy seed oil, pine oil, castor oil, soybean oil, avocado oil, safflower oil, coconut oil, hazelnut oil, olive oil, grape seed oil and sunflower seed oil. (iii) Amphoteric surfactants Amphoteric surfactants suitable for use in the compositions of the invention include: (a) imidazolinium surfactants of formula P922 (1) wherein R1 is alkyl or alkenyl Cj-C, .., R2 is hydrogen or CH2Z, each Z is independently C02M or CH2C02M, and M is H, an alkali metal, an alkaline earth metal, ammonium or alkanolammonium; and / or ammonium derivatives of formula (2) RxCONH (CH2) wherein R1, R2 and Z are as defined above; (b) aminoalkanoates of formula (3) R1NH. { CH2) nCO, M iminodialkanoates of formula (4) RN [(CH,) BCO, M32 and iminopolyalkanoates of formula (5) R ljKCH ^ p J qN l CHzCOaMl a CH2C02M where n, m, p, and q are numbers from 1 to 4, and R1 and M are P922 selects independently of the groups specified above and (c) mixtures thereof. Suitable amphoteric surfactants of type (a) are marketed under the trademark Miranol and Empigen and are understood to comprise a complex mixture of species. In practice, there is likely to be a complex mix of cyclical and non-cyclical species and both definitions are provided here for reasons of totality. However, non-cyclic species are preferred for use herein. Examples of suitable amphoteric surfactants of type (a) include compounds of formula (1) and / or (2) in which R1 is C8H17 (especially isocapyl), alkyl CgH19 and C11H, 3. Especially preferred are compounds wherein R1 is CgH-g, Z is C02M and R2 is H; the compounds wherein R1 is C1: LH23, Z is C02M and R2 is CH2C02M; and the compounds wherein R1 is C ^ H ^, Z is C02M and R2 is H. In the CTFA nomenclature, materials suitable for use in the present invention include cocoanfocarboxipropionate, cocoanfocarboxipropionic acid and, especially cocoanfoacetate and cocoamphodiacetate (referred to otherwise as cocoanfocarboxiglycinate).

Specific commercial products include those sold under the trademarks of Ampholak 7TX P922 (carboxy methyl bait sodium polypropyl amine), Empigen CDL60 and CDR 60 (Albright &Wilson), Miranol H2M Conc. Miranol C2M Conc. NP, Miranol C2M Conc. OP, Miranol C2M SF, Miranol CM Special (Rhonoe-Poulenc ); Alkateric 2CIB (Alkaril Chemicals); Amphoterge W-2 (Lonza, Inc.); Monateric CDX-38, Monateric CSH-32 (Mona Industries); Re oteric AM-2C (Rewo Chemical Group); and Schercotic MS-2 (Scher Chemicals). Additional examples of amphoteric surfactants suitable for use in the present invention include Octoxynol-1 (RTM), polyoxethylene (1) octylphenyl ether; Nonoxynol-4 (RTM), polyoxyethylene (4) nonylphenyl ether and Nonoxynol-9, polyoxyethylene (9) nonylphenyl ether. • It will be understood that various amphoteric surfactants of this type which are commercially available, are manufactured and sold in the form of electroneutral complexes with, for example, hydroxide counterions or with anionic sulfate or sulfonate surfactants, especially those of the C8 alcohol types -C18, sulfates, C8-C18 alcohol ethoxylates or C8-C18 acyl glyceride. Note also that the concentrations and proportions by weight of the amphoteric surfactants are based herein on the non-complexed forms of the surfactants, any counterions of the anionic surfactant will be considered as part of the total content of the anionic surfactant component.

P922 Examples of preferred amphoteric surfactants of type (b) include N-alkyl polytrimethylene polycarboxymethylamines, which are sold under the trademarks Ampholak X07 and Ampholak 7CX from Berol Nobel and also the salts, especially the salts of triethanolammonium and the salts of the acid N-lauryl-beta-amino propionic and. of N-lauryl-imino-dipropionic acid. These materials are sold under the trademark Deriphat of Henkel and Mirataine of Rhône-Poulenc. (iv) Zwitterionic surfactants The auxiliary water-soluble zwitterionic surfactants for inclusion in the compositions of the present invention include alkyl betaines of the formula R5R6R7N + (CH2) nC02M and amido betaines of the following formula (6): wherein R5 is C11-C22 alkyl or alkenyl, Rd and R7 are independently Cj-C alkyl, M is H, an alkali metal, an alkaline earth metal, ammonium or alkanolammonium, and n, m are each numbers from 1 to 4 The preferred betaines P922 include cocoamidopropyl dimethylcarboxymethyl betaine, laurylamidopropyl dimethylcarboxymethyl betaine and Tego betaine (RTM). The water-soluble sultaine auxiliary surfactants suitable for inclusion in the compositions of the present invention include alkyl sultaines of the following formula (7): R '' R 11CON (CH2) I + pN '(CH2) nCH (OH) CH2S? 3M R3 wherein R1 is C7 to C22 alkyl or alkenyl, R2 and R3 are independently Cx to C3 alkyl, M is H, alkali metal, alkaline earth metal, ammonium or alkanolammonium and m and n are numbers from 1 to 4. For use herein it is preferred to cocoamidopropylhydroxysultaine. The water-soluble amine oxide auxiliary surfactants, suitable for use in the compositions of the present invention, include alkyl amine oxide of R5R6R7NO and amido amine oxides of the following formula (8): where Rs is alkyl or alkeni from Cxl to C22, R6 and R7 are independently C to C3 alkyl, M is H, alkali metal, alkaline earth metal, ammonium or alkanolammonium and m and n are numbers from 1 to 4. The oxides of Preferred amine include cocoamidopropylamine oxide, lauryl dimethyl amine oxide and myristyl dimethyl amine oxide.

Additional Optional Materials Various additional optional materials, each at a level of from about 0.001% to about 5%, preferably from about 0.01% to about 3%, can be added to the presently described colorant compositions. of about 0.05% of about 2% by weight of the composition. These materials include proteins and polypeptides and derivatives thereof; soluble or solubilizable preservatives; natural preservatives, such as benzyl alcohol, potassium sorbate and bisabalol, benzoic acid, sodium benzoate and 2-phenoxyethanol; dye removers, such as oxalic acid, sulphated castor oil, salicylic acid and sodium thiosulfate; H202 stabilizers; moisturizing agents, such as hyaluronic acid, chitin and sodium polyacrylates grafted with starch, such as Sanwet (RTM) IM-1000, IM-1500 and IM-2500 available from Celanese Superabsorbent Materials, Portsmit, VA, USA and P922 described in US-A-4, 076, 663 as well as methyl cellulose, starch, higher fatty alcohols, paraffin oils, fatty acids and the like; solvents; antibacterial agents, such as Oxeco (phenoxy isopropanol); low temperature phase modifiers, such as ammonium ion sources (for example NH 4 Cl); agents for viscosity control, such as magnesium sulfate and other electrolyte; quaternary amine compounds, such as distearyl-, dilauryl-, hydrogenated di-bait, dimethyl ammonium chloride, dicetyldiethyl ammonium-ethyl sulfate, di-dimethyl-ammonium-methylisulfate, disodium dimethyl-ammonium chloride, and dicoco-dimethyl-ammonium chloride; hair conditioning agents, such as silicones, higher alcohols, cationic polymers and the like; enzyme stabilizers, such as water soluble sources of calcium or borate species; coloring agents; Ti02 and mica coated with Ti02; perfumes and perfume solubilizers; and zeolites such as Valfour BV400 and derivatives thereof and Ca2 + / Mg2 + sequestrants such as polycarboxylates, amino polycarboxylates, polyphosphonates, amino polyphosphonates etc. and water softening agents, such as sodium citrate. Other optional materials include anticaepa assets such as ZPT, and perfumes.

P922 Examples The invention will now be illustrated by the following examples. In these examples, several standard tests are used as follows.

I. evaluation of the initial color and of the color change (measurement of? E) The equipment used to measure both the initial color and the change of color of the substrates (hair / skin), stained with the low pH coloring compositions of the present invention was a Hunter Colourquest spectrophotometer. The value used to express the degree of color change in any particular substrate is Delta E (? E). Delta E, as defined herein, is represented by the actual sum of the values L, a, and b, such that: ? E = (? L2 +? A2 +? B2) 1/2 and L is a measure of clarity and darkness (intensity of color) where L = 100 is equivalent to white and L = 0 is equivalent to black. In addition, "a" is a measure of the red and green ratios (color tones), so that the positive is equal to the red and the negative to the green and "b" is a measure of the yellow and blue ratios (tones of the color), so that the positive is equal to P922 yellow and the negative is equal to blue. Measurements with the Hunter Colourquest can be performed on the Hunter Labscan Colorimeter, which is a full-spectrum spectrocolorimeter with a wavelength of 400-700 nanometers that records the color of hairpieces (test braids), in terms of the values " _L "," a "and" b ". the machine adjusts or calibrates in: mode - 0/45; Port size - 1 inch; vision size - 1 inch; light - D65; field of view - 10 °; UV lamp / filter-none. The hair is placed in a sample holder designed to keep the hair in a uniform orientation by measuring. > Equivalent colorimeters can be used but, it must be ensured that the hair does not move during the measurement. The hair should be extended to cover the 1-inch port during the color measurement. In the carrier of dots, dots are placed to guide the placement of the carrier in the port. The points are aligned with a mark on the port and the readings are taken in each zone. Eight measurements are taken per hairpiece, 4 on each side and three hairpieces are processed.

Standard Hair Hairpiece The compositions according to the present invention can be used to color hair of all P922 colors types and conditions. For illustrative purposes, several test hairpieces can be tested here. Two of these standard hairpieces can be measured in terms of their approximate values L, a, b. ___ ___ __í light chestnut (with approx 60 approx 9 approx 32 wavy permanent and discolored) 40% dark brown 35-37 4.5-5.5 11.5-12.7 gray Yak hair (virgin or with permanent wavy and / or discolored) can also be used. This has values of: L = from approximately 82 to 83, a = from approximately -0.5 to 0.7, b = from approximately 11 to 12.

III. Method for coloring a hairpiece To color the hair, a hairpiece of 4 grams and approximately 8 inches long (or a 2-inch and 4-inch-long hair insert) was hung on top of a suitable container. The test dye product was then prepared (i.e., when applicable, the components in separate bottles were mixed) and about 2 grams of product per gram of hair were directly applied to the test hair plug. The dye was distributed by massage through the hair piece for up to approximately 1 P922 minute and then left on the hairpiece for up to about 30 minutes. After it was rinsed with running water for about 1 or 2 minutes, then the colored hair insert was cleaned (in accordance with the shampoo protocol IV below) and dried. The drying can be carried out either naturally (ie without the aid of heat) or by using a dryer. The color development (initial color) of the colored, cleaned and dried test hair can then be evaluated using the Hunter Colourquest spectrophotometer. For the supply of a red hue (tone) to a light brown hair with previous permanent waving and previous discoloration (which has values L, a, and b of approximately 60, 9 and 32) the preferred initial shade of the painted hair will have a "value of pitch (tangent angle of (b / a)), in the range of from about 25 to about 70, more preferably, from about 30 to about 65, most preferably, from about 35 to about 60 and where , 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.

P922 To provide a brown or black (tone) shade to light brown hair with previous permanent waving and pre-bleaching (having L, a, b values of approximately 60, 9 and 32) the preferred initial shade of colored hair will have a value of pitch (tangent angle of (b / a)) 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. For the supply of a light brown shade (tone) to light brown hair with wavy forethought and previous discoloration (having values L, a, b of approximately 60, 9 and 32) the preferred initial shade of the colored hair will have a tone value (tangent angle of (b / a)) in the range of from about 70 to about 110 and wherein 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. A significant color change, as provided by the dyeing compositions according to the present invention, often means a color change on hair with permanent waving and discoloration, in terms of Delta E, P922 which is preferably greater than about 5 or 8, preferably, greater than about 10, more preferably, greater than about 12, and more preferably, greater than about 15 and especially, greater than about 20.

IV Method of cleaning the hairpiece Hairpieces with colored hair undergo a repeated cleaning cycle, where the following process is repeated. A 4-inch, 8-inch test insert (or a 2-gram, 4-inch test) of colored hair was attached to a suitable container and rinsed thoroughly for approximately 10 seconds using hot water (approximately 100 ° F). at a pressure of approximately 1.5 gallons / minute). Then, to the wet test hairpiece, using a syringe, the shampoo was applied directly (approximately 0.1 ml of nonconditioning shampoo per gram of hair). After the foaming of the hair for about 30 seconds, the hair was rinsed under running water for about 30 seconds. The process of applying the shampoo and contacting the foam was then repeated with a final rinse of 60 seconds. The excess of water can be removed from the test sample P922 ~ - = "squeezed out" using the fingers The test hair is then dried either naturally or using a dryer box preheated to approximately 140 ° F (for about 30 minutes). and dry can then undergo color evaluation (Delta E discoloration) During any individual test cycle, each different hair piece that will be evaluated must be tested in water at a temperature, pressure level and equivalent hardness level. Delta E discoloration for light brown hair with permanent wavy • previous, pre-bleached (having L, a, b values of approximately 60, 9 and 32) that has been dyed with a red hue (with a tone value in the range of from about 25 to about 70) is preferably less than about 5.0, preferably, less than about 4.5, more preferably, less than about 4.0, particularly preferably less than about 3.0 or 2.0 and, where the change in hair color,% delta E, after up to 20 washes, is less than about 20%, and preferably, less than about 15%, with more preferably less than about 10%. The results of the Delta E discoloration for P922 light brown hair with permanent wavy and pre-bleached (which has values L, a, b of about 60, 9 and 32) which has been colored with a brown or black hue (with a hue value of less than about 25) are preferably less than about 2.3, preferably, less than about 2.0, more than preferably, less than about 1.7 and wherein, the change in hair color,% delta E, after up to 20 washes, is less than about 5%, preferably less than about 4.5%, more preferably less of about 4%, more preferably less than about 3.5%. The results of the Delta E discoloration for light brown hair with previous permanent waving and previous discoloration (which has values L, a, b of approximately 60, 9 and 32) that has been colored with a light chestnut hue (with a tone in the range of from about 70 to about 110) are preferably less than about 2.6, preferably, less than about 2.3 and wherein the change in hair color,% delta E, after up to 20 washes, is less than about 15 %, preferably, less than about 12%, more preferably, less than about 10%, more preferably less than about 8%.

In the preferred embodiments herein, the change in color of hair dyed over time (Delta E discoloration) is less than about 15%, preferably, less than about 12%, more preferably, less than about 10. % and more preferably less than about 8%.

V Permanent Waving Protocol The following method was used to permanently rip hair that will normally be subjected to subsequent discoloration. On top of a suitable container, a hair piece of 4 grams and approximately 8 inches long was hung. The solution provided for the permanent wavy with the trade name "Zotos" was applied to the hair, to completely saturate it. The hairpieces became saturated again then. The hairpieces were then placed on a plastic tray for 20 minutes and then rinsed for 1 1/2 to 2 minutes with tap water at 37 ° C. The hairpieces were dried by squeezing and toweling. The hairpieces were then hung back on top of the container and the neutralizer "Zotos" available commercially was applied to saturate them. These were then placed in the plastic tray for 5 minutes and subsequently rinsed for 1 1/2 to 2 minutes.

P922 tap water at 37 ° C. The hairpieces were shampooed twice and allowed to dry.

VI Discoloration protocol The permanent wavy hairpieces were dried for 20 minutes and hung over the edge of the container. A maximum of 9 or 10 hairpieces were treated at the same time. The commercially available decolorizing agent of Clairol, "Born Blonde (with chamomile)" was mixed in accordance with the instructions and 10 grams of the material were applied to each insert and they received a deep massage. Each hairpiece was wrapped or rolled in a non-tight form in an adherent film and left for 30 minutes. Subsequently, they were rinsed for 2 minutes with tap water at 37 ° C. Then, shampoo was applied once more.

EXAMPLE 1 In this example, formulation 1 according to the invention was compared with a commercially available product and the color fading of the two dyeing compositions, as measured by? E, was compared. The compounds used are as follows: P922 (i) CH 3CH 2NHS02CH3 'ii) (A) pyrazolone (ii) (A) a-naphthol (ii) (B) Benzoylacetanilide Formulation 1 had the following composition: % by weight Ceteareth 25 0.84 Cetyl alcohol 1.16 Stearyl alcohol 1.16 (i) 0.87 P922 Pyrazolone (i) (C) 0.16 a-naphthol (ii) (A) 0.0046 Benzoylacetanilide (ii) (B) 1.86 Ethanol 9.3 NHOH 1.6 Peroxide Hydrogen 3.0 Sodium Sulfite 0.46 EDTA 0.46 Water ~ _ up to 100 The pH of the formulation 1 was from 9 to 10. The comparative formulation was L 'Oreal Recital "Santiago". To a 4 grams light hair hairpiece with permanent wavy and discolored 8 grams of each formulation were applied for 30 minutes, as described in the above coloring method. Permanent waving and discoloration were carried out in accordance with the protocols described above. The values of L, a and b were calculated in unstained hair and in dyed hair. The color difference between the two states was calculated to provide the initial? E, in the manner previously described for the measurement of? E. The dyed hair was then subjected to 40 washes, using the washing protocol described above. After the 40 washes, they were measured P922 again the values L, a and b and the color difference between the initial dyed hairpiece and the washed hairpiece, as described above for the? E, was calculated to provide the discoloration? E. The values of the? E initial,% discoloration and discoloration? E are given below.

These results show that the commercial formulation and formula 1 of the invention provide a similar delta and initial, wherein the formulation of the invention in fact provides a greater? E and, consequently, a greater color change with the dyeing. However, it will then be observed that the decolorization E after 40 washes is significantly less for the formula 1 of the invention than for the available product P922 in commercial form.

Example 2 This example demonstrates the manner in which the system of the invention can provide a wide range of colors, using only four compounds. Three formulations were tested using the four materials (i), (ii) (A), (ii) (B) and (ii) (C) above, as the only coloring agents. The formulations were numbered 2, 3 and 4 and are as follows: In the previous compositions, all the P922 components are provided by weight of the total composition. The light brown 4 gram hair hairpiece with permanent and bleached wavy was colored in the same manner described in Example 1. The initial color change? E and the final color are given below.

It can be seen that this set of only 4 coloring components has the ability to provide a range comprising light chestnut, reddish brown, chestnut.

Example 4 The following comparisons demonstrate the advantages of a system according to the invention, compared to a system disclosed in GB 1,025,916. The following formulations were tested.

P922 The experimentation is carried out either in yak virgin hair (not mistreated) or in yak hair with permanent wavy (mistreated). All formulas were applied to the relevant hairpiece in RT for 30 minutes at a pH of about 10. Formulas I and III contain the two different couplers in a weight ratio of 1: 1 and formulas II and IV contain the two different couplers in a molar ratio of 1: 1. Formulation IV contains ascorbic acid as antioxidants. The results were as follows.

P922 The formulations III and IV contain a coupler (B), according to the invention and, the formulations I and II contain a yellow coupler used in GB 1025916. It can be seen that the formulations according to the invention provide the best absorption values and discoloration of each type of hair the discoloration values are generally lower for virgin yak hair than for yak hair with permanent wavy hair, since the hair with permanent wavy tends to be more porous and, in general, to discolor more quickly .

P922

Claims (31)

CLAIMS i

1. A composition for hair coloring, comprising: (i) one or more developers selected from aromatic amino systems that have the ability to be oxidized and, after this, undergo a single electrophilic attack, and (ii) one or more couplers selected from: (A) (1) naphthols having an active leaving group in the para position, with respect to the OH group, or (2) phenols with formula wherein the H of para with respect to the OH group is an active leaving group and R1, R2, R3 and R4 are each independently selected from the group consisting of H, OH, methyl, ethyl, n-propyl, -propyl, t-butyl, NH2, C02H, C02R and COR, in which R is substituted or unsubstituted alkyl or alkenyl, () 1,3-diketones (1) containing the group P922 wherein the N-phenyl group has no carboxy substituents, or (2) containing the group wherein Rs contains an aryl group, and or (3) of the formula wherein R6 is selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, t-butyl and phenyl and R7 and R8 are each independently selected from the group consisting of methyl, ethyl, n-propyl , hydroxymethyl and hydroxypropyl, or (4) of the formula P922 t where R37 is C4 alkyl, and in all of these, Z is an active leaving group, (C) compounds of the formula wherein X is a non-salient substituent and wherein Z is an active leaving group and wherein A is H or methyl, such that in the presence of an oxidizing agent the developer or each developer reacts with the coupler or with each coupler practically only in the position that has the active leaving group and as long as the composition includes at least one coupler (B) or (C).

2. A composition according to claim 1, wherein one or more developers (i) is selected from N, N-disubstituted phenylenediamines.

3. A composition according to claim 1 or P922 2, wherein the coupler (A) is selected from (1) naphthols having an active leaving group in the para position, with respect to the OH group, and the coupler (B) is selected from 1,3-diketones (1) that contain the group wherein the N-phenyl group has no carboxy substituents, or (2) of formula wherein R5 contains an aryl group.

4. A composition according to any of the preceding claims, wherein the coupler (B) is of formula IV: wherein R is selected from alkyl, alkenyl, alkaryl, P922 aryl, and aralkyl, preferably phenyl and C1.3alkyl.

5. A composition according to any of the preceding claims, wherein at least one coupler (A) is α-naphthol.

6. A composition according to any of the preceding claims, wherein at least one coupler (B) is acetoacetanilide or benzoylacetanilide.

7. A composition according to any of the preceding claims, wherein one or more developers (i) are selected from the compounds of the formula and compounds of the formula wherein Y is selected from -N02, -C02H, -C02R, -COR and OH and R13, R14, R15 and R16 are independently selected from H, methyl, ethyl, n-propyl, i-propyl, F, Cl, OH, N02, -C02H, P922 -C02R and -COR.

8. A composition according to any of the preceding claims, wherein at least one coupler (A) is 3-aminophenol.

9. A "composition according to any of the preceding claims, wherein at least one coupler (B) is N, N-diethyl acetoacetamide or N, N-dimethyl acetoacetamide

10. A composition according to any one of the preceding claims, in which that at least one coupler (C) is selected from the compounds of the formula wherein R10 is selected from the group consisting of H, methyl and phenyl and R11 is H or methyl.

11. A composition according to any of the preceding claims, wherein at least one developer (i) is selected from the group consisting of 2,6-dichloro-p-aminophenol, 2-chloro-p-aminophenol, 3-chloro- p-aminophenol, 2,3-dichloro-p-aminophenol and 3,5-methyl-p-aminophenol.

12. A composition according to any of the preceding claims, which includes not more than two P922 couplers of each of the types (A), (B) and (C).

13. A composition according to any of the preceding claims, which includes only a developer compound (i). A composition according to any of the preceding claims, which does not contain more than 0.1% by weight of oxidative coloring agents, which are not of types (i), (A), (B) and (C) of the formulas X to XIII, provided herein. 15. "A composition according to any of the preceding claims, which does not contain more than 0.1% by weight of oxidative coloring agents, which have the ability to react more than once to the conditions of hair coloring. according to any one of the preceding claims, which does not contain more than 0.1% by weight of any oxidative coloring agent, which can react with itself to the conditions of the coloring of the hair 17. A composition according to any of the preceding claims, in the that practically all the developer molecules (i) do not react with practically other developer molecules, under the conditions of hair coloring 18. A composition according to any of the P922 preceding claims, having a pH of at least 6.1, preferably, at least 6.5. 19. A composition according to any of the preceding claims, which contains ammonia or ammonium hydroxide in an amount of at least 0.01% by weight. 20. A kit or kit for coloring the hair, comprising as hair coloring components: (i) one or more developers, as defined in claim 1, and (ii) one or more couplers (A) and / or one or more couplers (B) and / or one or more couplers (C), 'as defined in claim 1, provided that they comprise at least one coupler (B) or (C). 21. A method for coloring the hair, comprising, providing: (i) one or more developers, as defined in claim 1, and (ii) one or more couplers (A) and / or one or more couplers (B) ) and / or one or more couplers (C), as defined in claim 1, provided that they comprise at least one coupler (B) or (C), and (iii) an oxidizing agent, and apply (i), (ü) and (iii) the hair to be colored. P922 22. A method according to claim 21, wherein the hair is practically not mistreated. 23. A method according to claim 21, wherein the hair has previously been discolored, permanently curled and / or pre-colored. 24. A method according to claim 21, wherein part of the hair is practically untreated and part of the hair has previously been discolored, subjected to permanent waving and / or pre-colored. 25. A hair coloring system comprising: • (i) one or more developers as defined in claim 1, and (ii) one or more couplers (A) and / or one or more couplers (B) and / or one or more couplers (C) and, optionally, one or more compounds of formulas XI to XIII hereof, which do not comprise other oxidative coloring agents and the system has the ability to provide a broad spectrum of shades of colors without using agents additional dyes. 26. A system according to claim 25, wherein the couplers include only the couplers (A) and / or (B) and / or (C). 27. A system according to claim 25, which P922 comprises couplers (A) and (B), optionally, together with couplers of the formula wherein R10 and R11 are selected from alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl, aralkyl, R'NHCOR, R 'CONHR, S02R, S02NHR, R'S02R and R'S02NHR. 28. A set or method, method or system according to any of claims 20 to 27, having any of the additional features set forth in claims 2 to 19. 29. A composition, kit, method or system according to any of the preceding claims , wherein the developer (i) is selected from the compounds containing a single primary amine group and which react substantially only in the primary amine group under the conditions of hair coloring. 30. A composition for coloring the hair, comprising N, N-dimethyl acetoacetamide and / or N, N-diethyl acetoacetamide. 31. A composition for hair coloring, comprising a compound of the formula P922 wherein R is H, alkyl or phenyl Cl-4 P922