CZ398699A3 - Preparations for dyeing the hair and method of their use - Google Patents

Abstract

The present invention relates to hair coloring compositions which are characterized limiting harmful effects on skin and hair. These the means comprise: (i) one or more generators selected from of aminoaromatic systems capable of oxidation and subsequent undergoing one electrophilic impact, and (ii) one or more Multiple coupling (binding) substances selected from (A) phenols and naphthols that have reactive a (cleavage) group at the para position to the hydroxyl group; (B) 1,3-diketone derivatives which are also active a leaving group, or (C) pyrazolone derivatives also containing a leaving group; přiza the presence of an oxidizing agent, each generator reacts with everycoupler in only active split groups; and (iii) an inorganic peroxide oxidant in from 0.0001 to 0.05 moles per 100 grams of composition. Alternative compositions may also contain larger amounts of an oxidizing agent, of course, assuming their value The pH will be below 6.

Description

Hair dye products and their use ·· ·· • 0 0 0 0 0 0 0 0 0 «0 · 000 000 • 0 0 0000 00 00

Technical field

The present invention relates to novel hair dye compositions and methods for their use in the hair dye process.

BACKGROUND OF THE INVENTION

Means for coloring hair to different colors, either to change the natural color of the hair or to cover gray hair, are well known. These compositions contain various aromatic compounds, commonly referred to as developers (also known as precursors or

primary intermediates), together with other aromatic compounds commonly known as coupling compounds (copulators). These are referred to as oxidative hair coloring agents because they require an oxidizing agent to produce a color.

Generally, 1,4-disubstituted benzene compounds, most commonly 1,4-diaminobenzene compounds, are developed, and the disubstituted benzene compounds such as 1,3-disubstituted benzene compounds may also be copolymers. The range of copulator structures is much more diverse than developers.

During use, these compounds are subjected to oxidizing conditions under which the generators and the copulators interact to form a color. This is generally believed to occur in sequential sequences in which the generator molecules are activated by oxidation and react with the couplers to form reactive dimers. These then continue to produce color trimmers that no longer react. It is believed that monomeric developers and copulators, and to a lesser extent dimers, diffuse into the hair shaft during a reaction that is sufficiently slow. Inside the hair, the dimers react further to trimers that are too large to diffuse outwardly, thus being trapped therein, coloring the hair.

Standard products normally contain several different generators and several different copulators, e.g. 5 generators and 5 or more copulators. In general, it is believed that 10 to 12 different compounds are required to achieve the full range of colors.

The desired oxidation conditions are usually formed by treating the hair with oxidative coloring agents and an oxidizing agent. The most commonly used oxidizing agent is hydrogen peroxide.

Hair coloring compositions containing conventional oxidative coloring agents are generally formulated for high pH, often from pH 9 to pH 12. This high pH value is typically a " high "

• Creates using ammonium sources. Ammonia has the additional function of acting as a hair swelling agent (HSA). This agent promotes (accelerates) the oxidation and dyeing process by swelling the hair fibers. This facilitates the diffusion of both the oxidizing agent and the oxidative coloring agent into the hair, thereby faster and more thorough oxidation of the coloring agent and faster coloring of the hair.

Although this system is effective and commercially successful, it unfortunately has various disadvantages. First, the generators can react with each other as well as with the copulators, and the reactive dimers can react with both the generators and the copulators. Thus, the reaction chemistry is undefined, and it is not possible to predict with any precision the compounds that will be present in the hair at the end of the color forming reaction. The exact composition of the colored molecules present in the hair may vary from process to process, depending on the prevailing conditions. The colors obtained may therefore vary with different applications.

Another disadvantage is the color fading after a certain time. The lack of fastness in wash (washability) contributes to fading. The resulting trimeric colored molecules tend to dissolve in water and other solvents and thus eliminate from the hair after repeated washing, or after using, for example, hair spray or other hair care compositions. This leads to gradual fading or a change in the color tone used. Color is also affected by factors such as UV light, combing or sweating.

The use of large amounts of hydrogen peroxide also has disadvantages. In addition to reaction with oxidative dye components, hydrogen peroxide can also oxidize disulfide bonds in the hair. This can lead to adverse effects on the hair, such as embrittlement and hair damage. This problem arises at least in part because relatively high concentrations of the oxidizing solution need to be used in order to achieve efficient oxidation of standard oxidative hair coloring agents (hair dyes). This concentration of the oxidizing solution is usually such that it is 20 to 40% by volume of oxygen, i.e. 6 to 12 weight percent, based on the concentration in the component supplied to the consumer and containing the oxidizing agent. Another problem arises from the fact that the oxidation reaction takes place in two stages.

Accordingly, there must be sufficient oxidizing agent in the hair coloring composition if both oxidation steps are to be induced. When hydrogen peroxide is used, it is often at a concentration of 3% by weight in the solution applied to the hair. The normal hair dyeing process requires longer dye times (10 to 60 minutes). Under these harsh conditions of a strongly oxidizing agent, hair damage can occur, for example, by oxidizing disulfide bonds in the hair.

.1 · φ * · · · · · ·

The use of large amounts of ammonia or other bases can also lead to skin irritation and hair damage. Ammonia and other bases lead to swelling of the skin and hair, thus promoting stains on the skin as well as stained hair. Furthermore, ammonia has an undesirable odor and can lead to the tear effect.

High pH conditions may also lead to hair damage, but this is normally required when standard oxidative dye materials are used.

These problems with commercial products have persisted for many years and have not yet been resolved.

GB 1,025,916 discloses certain generators and copulators of various types. This document discloses generators that are derivatives of Ν, Ν-disubstituted phenylenediamine. Three classes of copulators are described below. Phenol-based copolymers give a blue color, some R-CO-CH2-COR derivatives give a yellow color, and some pyrazolone derivatives give a red color.

These combinations have the advantage that the generators do not react with each other and can only react with each copolymer in one way, so that the final chemical composition of the dye obtained can be well defined and predicted.

GB 1,025,916 describes the mixing of pairs of copulators, such as red with blue, blue with yellow, etc., in order to obtain shades of color which are achieved by using each of the copulators individually. Various examples of hair dyeing using proposed developers and copulators are described. In some examples, the developer applied to the hair is allowed to act for some time, then a copolymer is applied, which is also allowed to act for some time, followed by the use of an oxidizing agent.

In most examples, the developer, copolymer, and hydrogen peroxide as an oxidizing agent are mixed, and the composition is applied to the hair, which is allowed to act for some time (normally 20 minutes), and the hair is washed. This method is a standard method of using conventional commercial hair dyes containing oxidative hair coloring agents. These are commonly supplied in containers containing two vials. In one, there are generators and copulators, and the other contains an oxidizing agent. The contents were mixed prior to use and applied to the hair.

In all the examples described in GB 1,025,916, high pH (at least pH 10 in all cases), high ammonia or sodium hydroxide content, and high oxidant content (about 3% by weight hydrogen peroxide in the applied solution) are maintained for standard oxidative hair dye.

000 000 000 000

Thus, the methods described in GB 1,025,916 still suffer from the problems of embrittlement and hair damage, skin irritation and staining, which occur using standard oxidative staining systems.

It is therefore desirable to provide a hair dyeing system in which the final color can be predicted and controlled, but also to reduce embrittlement and damage to the hair, skin irritation, and skin staining.

SUMMARY OF THE INVENTION

According to a first aspect of the invention, we propose a hair coloring composition which consists

(i) one or more generators selected from amino-aromatic systems capable of oxidizing and undergoing a single electrophilic shock; and (ii) one or more copolymers selected from:

AJ from phenols and naphthols having an active leaving group in the para position to the hydroxyl group,

B / from 1,3-diketones containing a group

wherein Z is an active leaving group, and C / z compounds containing a group

O

wherein Z is an active leaving group and X is an active leaving group or a non-leaving substituent, such that in the presence of an oxidizing agent (each) the developer reacts with the copolymer essentially only at the position at which the active groups Z and X are active; and (iii) from an inorganic peroxide oxidizing agent in an amount of 0.0001 to 0.05 moles per 100 g of the composition.

• * 9 9 99

DETAILED DESCRIPTION OF THE INVENTION

According to the invention, the generator is an amino-aromatic compound having a structure that is capable of being oxidized by an oxidizing agent. Thus, the structure is such that the oxidized generator is capable of undergoing the electrophilic impact of one other molecule. In other words, the structure of the generator is such that it reacts substantially only in the position that normally is in the amine. Suitable generators of this type are amino-aromatic systems in which there is only one primary amino group to be reacted, while other amino groups and other reactive groups are protected by blocking substituents.

The three defined types of copolymers are selected so that in the presence of the oxidizing agent a major part of the copolymer is coupled to the generator in only one position, thereby producing only one resulting color dimer. Some type C / couplers with another active cleavage group X also react at the X position to provide one resulting color trimmer.

In this case, only one type of final color molecule is also formed from this copulator. The defined generator also reacts in only one position.

We assume that color is formed by reacting one or two developer molecules with one copolymer molecule to form a color dimer or trimer. Dimers and trimers are not reactive, so no further reaction occurs. As a result, color formation is most effective. In addition, the colored molecules produced are very pure. Knowing the developer and copolymer molecules present in the reaction system, we can accurately predict the final combination of color molecules that will be produced. This is a significant advantage over standard oxidative color systems.

Furthermore, the hair colored molecules have a markedly limited solubility in water when compared to trimers formed in standard oxidative dye systems, which helps to achieve greater wash stability.

We have also found that the reaction between a defined generator and defined couplers is very fast and efficient. This allows these hair dyeing systems not to require as long a period of action as has been common to this day if the dyeing was to be permanent and deep.

Furthermore, we have surprisingly found that using the described developers and copulators, dye compositions are obtained which, even with a very low content of inorganic peroxide oxidizing agent, provide an effective and fast coloring of the hair. The result is less hair damage.

We have also found that the use of this low oxidant content remains open to the use of these systems at low pH. This offers a further possibility of limiting the amount of ammonia and thus the amount of ammonia removed; the result is • • 44 *

·· · *

reduction of unwanted odor, tearing effects, skin irritation and skin spots, and hair damage.

A further advantage of the composition according to the invention is that reducing the amount of oxidizing agent leads to more economical production.

Some suitable copolymer molecules A (B), and C (C) are known in the art, where they are used as suitable developers. Upon reaction with the developer molecule, the A / C coupler gives a blue-green color (cyan), the B / yellow coupler and the C / magenta coupler (fuchsin).

Each copolymer comprises a group with a specific formula such that the active leaving group is at a particular (defined) location. By "active cleavage group" we mean any group that can be removed (under the conditions prevailing in the hair dyeing process) so that the developer reacts at this position with the copolymer molecules. Thus, the bond between the molecule. The coupler and generator are formed at the site where the leaving group was active. Examples of active leaving groups are hydrogen H, PhO, Cl, Br, alkoxy (RO) such as phenoxy PhO, and R5 in which R is alkyl or aryl, but any leaving group that is liberated during the reaction to allow coupling (coupling) of the generator and the copulator.

If X is an active leaving group, then it is any of the groups listed above for Z.

The A / couplers give a cyan color. The respective shade or color intensity can be varied by changing the substituents in the phenol or naphthol molecule. It has an active leaving group in the para position relative to the OH group. It may be an active proton, i.e., the aromatic ring is not substituted at the para position and the other substituents on the ring are not such as to limit reactivity at that position.

Generally, the A / copolymers have the formula I:

wherein Z is H or another active leaving group. Preferred Z is hydrogen H.

R ¹ , R ² , R ³ and R ⁴ are independently of one another: H, OH, -CO ₂ H, -CO ₂ R, F, Cl, Br, -CN, -NO ₂ -,

CF 3, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl, aralkyl, -NH ₂ , NHR, -NHCOR, -NR ₂ , NHCOR, -R'NHCOR, -CONHR, -R CONHR, -ROH, -SO ₂ R, - SO ₂ NHR, -R'SO ₂ NHR, SO 3 H, -OR, -ROR or -COR, wherein R is H, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl or aralkyl, and R 'is alkylene, alkenylene, cycloalkylene, cycloalkenylene, arylene, · ♦ · · · · · · · · · · ry ry · ry ry ry · * ry ry

1 alkarylene or aralkylene, or substituted versions thereof. In addition, R and R may together form a substituted or unsubstituted cycloalkyl, cycloalkenyl or aryl group, wherein the substituent groups are OH, -OR, Cl, Br, DF, -COOH, -COOR, NH ₂ and -COR.

Unless otherwise stated, in this specification alkyl and alkenyl are usually C 1-8, often C 1-4, cycloalkyl and cycloalkenyl are usually C 5-8, often C 1-4, aryl or ar- are usually phenyl and / or naphthyl, and the alk group in alkaryl is usually Cm, often Cm ·

In the case of copolymer A / and when R ¹ , R ² , R ³ or R ^{4 are} alkyl, it is preferred that the alkyl is methyl, ethyl, n-propyl, isopropyl and t-butyl. When R is alkyl, it is preferred that it is one of said groups, and when R 'is alkylene, it is preferred that it is derived from one of said groups.

The substituents R ^1, R ² may form a second benzene ring, so kopulátorem A / naphthol derivative of formula II:

In this case, it is preferable that R ³ and R ⁴ are H, and the inflator is alpha-naphthol. In another suitable A / o copolymer of formula II, R ⁴ is H and R ³ is:

Z (ΠΙ)

Z (IV) · * * *

999 999

9 · · ♦

The A / coupler may be a naphthol having no solvent substituents (other than Z), especially not -COOH or -OH. It is preferred that the naphthols be unsubstituted.

We found that kopulátory with the following formula II (in particular where R ³ and R ⁴ is hydrogen, and especially when Z is hydrogen) have a particularly advantageous combination of properties for improving stability during washing and during rapid staining even when colored hair were damaged eg, by persistent or discolouration. This is believed to be due to the structure of their molecules: as monomers they are small enough to diffuse easily into the hair shaft (which is quite porous after damage), but as dimers are trapped in the hair shaft. In addition, their solubility in water is low enough so that they do not wash away easily during further work with the hair.

Preferred copolymers of the formula I are independently OH, H, methyl, ethyl, n-propyl, i-propyl, t-butyl, -NH ₂ , -COOH and independently selected as R ¹ , R ² , R ³ and R ^4. -COR. In these preferred A / Z-Z couplers hydrogen H is selected.

A preferred copolymer of this preferred type is 3-aminophenol.

We have found that these preferred copulators exhibit particularly good performance on damaged hair. They are an example of good color formation and washing stability.

In all of the above formulas, Z is an active leaving group. Suitable examples of Z are H, PhO, Cl and Br, but any other group that reacts similarly (under hair dye reaction conditions) may be used. If Z is PhO, Co, or Br, then the reactivity of the copolymer tends to increase compared to those in which Z is hydrogen H.

In any of the above formulas, the defined groups may include, unless otherwise indicated, non-interfering (non-interfering) substituents, i.e., any group that does not hinder the coupling reaction between the generator and the coupler. The substituent may in particular be a phenyl or naphthyl group. Suitable non-interfering substituents are COOH, CH 3, SO ₂ , NHCH 3, SO ₃ H, C 1-6 -alkyl such as ethyl or propyl, and CONHR, wherein preferred R is C 1-3 -alkyl. The alkyl and CONHR substituents have the advantage that the solubility of the final color molecule is limited. The phenyl groups may contain one or more substituents which may be the same or different. If the substituents are phenyl, monosubstitution is preferred. It is preferred that these groups are not substituted unless otherwise stated.

The yellow copolymers B / contain a group of 1,3-diketone

(V) ι 9 · t 9 99 9 · ·

wherein R ⁵ and R ⁶ independently of one another are H, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl, aralkyl, -R'NHCOR, -R'CONHR, -ROH, R'SO ₂ R, -R'COONHR , -NHCOR, -NR ₂ , NHR, -NH ₂ , -ROR, and -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. These can also be substituted versions. Suitable substituents are OH, -OR, Cl, Br, F, -COOH, -COOR, -NH _2, and COR.

In preferred formulations, at least one of R ⁵ and R ⁶ comprises an aryl group. Some of the B / copulators have the formula VI:

In this formula, R ^{5 can} be, for example, methyl, phenyl, t-butyl or N (CH 3) ₂ CH ₂ CH ₂ OH. When R ^{5 is} tertiary butyl, the advantage arises from the fact that the colored dimer produced has a particularly good light-decomposition resistance. R ⁵ can also be phenyl. It is also preferred that N-phenyl in Formula VI does not contain solvent substituents. It is particularly preferred that it does not contain -COOH or -OH substituents. It is preferred that N-phenyl is not substituted. In formulations in which R ⁵ phenyl has no solvent substituents, especially -COOH and -OH. Most preferably, it is completely unsubstituted.

We have found that the copolymers of formula VI have a particularly advantageous combination of properties for improving wash stability, even while maintaining the dyeing rate, particularly in damaged hair. It is believed that this is due to the structure of their molecules: as monomers they are small enough to diffuse easily into the porous damaged hair shaft, but as dimers they are trapped in the hair shaft. In addition, their solubility in water is low enough so that they do not wash away easily during further work with the hair.

In other preferred type B / R ⁵ couplers, methyl, ethyl, n-propyl, i-propyl, t-butyl or phenyl (particularly methyl), and R ⁶ is NR ₂ , wherein the R groups are the same or different, and are to ···· · · · · * 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 The R groups mentioned above, in particular methyl, ethyl, n-propyl, i-propyl, t-butyl or phenyl (in particular ethyl).

In other suitable kopulátorech B / R ⁵ and R ⁶ independently are short chain alkyl (CM), such as methyl, ethyl, i-propyl, n-propyl or t-butyl, or short-chain alkoxy (C1-4 ) such as methoxy or ethoxy. R ⁵ is especially C 1-4 alkyl (especially methyl) and R ⁶ is C 1-4 alkoxy (especially methoxy).

In these formulations, it is preferred that the alkyl groups be hydroxylated to provide, for example, hydroxymethyl (usually 2-hydroxymethyl), hydroxyethyl, hydroxypropyl or hydroxybutyl.

Couplers B / these latter types are particularly useful for dyeing undamaged and damaged hair. In the case of undamaged hair, they show a rapid dye uptake without loss of washing stability. In the case of damaged hair also show good washing stability.

In formulas V and VI, such as Z may be any of the leaving groups listed for Z in the copolymers A above. Preferred Z is H.

In some of the above formulations, unless otherwise stated, the groups defined therein may also contain a non-interfering (non-interfering) substituent, ie, a group that does not prevent the coupling between the generator and the coupler. In particular, they may substituted phenyl and naphthyl groups. Suitable non-interfering groups are COOH, CH 3, SO 2, HNCH ₃ , SO ₃ H, alkyl such as ethyl or propyl, and CONHR, wherein R preferably is C 1-3 -alkyl. The alkyl and CONHR substituents have the advantage that the solubility of the final color molecule is limited. Phenyl groups may contain one or more substituents, the same or different substituents. When phenyl groups are substituted, mono-substitution is preferred. It is preferred that these groups are without a substituent (unless stated otherwise).

C-type copolymers are pyrazolone derivatives, i.e. contain a group

O

wherein Z is an active leaving group and X is an active leaving group or a non-leaving substituent.

Normally X is a non-cleavable substituent, and the couplers have the formula VII:

wherein R ⁷ is H, -OH, -COOH, -COOR, F, Cl, Br, -CN, -NO ₂ , CF ₃ , alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl, aralkyl, -NH ₂ , - NHR, -NR ₂ , NHCOR, -R'NHCOR, -SO ₃ H, -OR, ROR, or -COR. R ⁸ is H, alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkaryl, aralkyl, RNHOR, -RCONHR, -ROH, -R'SOONHR or -ROR. R is H, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl, aralkyl, -R'NHOR, -R'CONHR, -ROH, -R'SOONHR or ROR. R is H, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl or aralkyl, and R is alkylene, cycloalkylene, alkenylene, cycloalkenylene, arylene, alkarylene or aralkylene (or a substituted version of any of them). Suitable substituent groups are OH, -OR, Cl, Br,

F, -COOH, -COOR, -NH _3, and -COR.

For example, R ⁷ is H or methyl. Alternatively, it may be -NHR or -NHCOR wherein R is alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl or aralkyl.

Preferred R ⁷ is H, lower (C 1 -C 6 alkyl such as methyl, ethyl, n-propyl, i-propyl or t-butyl, or substituted or unsubstituted phenyl, especially H, methyl or methylphenyl.

Preferred R ⁸ is H, lower (C 1-4) alkyl such as methyl, ethyl, n-propyl, i-propyl, t-butyl, or is substituted or unsubstituted phenyl. When it is phenyl, it is preferred that it is free of solvent substituents, especially -COOH and -OH. M-SO ₃ H and pSO ₃ H may be used. When R ^{8 is} phenyl, it is preferred that it is unsubstituted. R ⁸ is also preferably H, phenyl or methyl.

We have found that the copolymers of the last (above) formulations have a particularly advantageous combination of properties for improving wash stability, even while maintaining the dyeing rate, especially in the case of damaged hair. It is believed that this is due to the structure of their molecules: as monomers they are small enough to diffuse easily into the porous damaged hair shaft, but as dimers they are trapped in the hair shaft. In addition, their solubility in water is low enough so that they do not wash away easily during further hair care.

Suitable type C / copolymers have the formula VIII:

In formulas VII and VIII, Z may be any cleavage group mentioned for Z in the case of the A / and B / copolymers above.

In any of the above formulations, unless otherwise noted, the listed groups may also contain a non-interfering substituent, ie, a group that does not prevent the coupling reaction between the developer and the coupling. In particular, phenyl and naphthyl groups may have substituents. Suitable non-interfering groups are COOH, CH 3, SO ₂ , NHCH 3, SO ₃ H, C 1-3 -alkyl such as ethyl or propyl, and CONHR, wherein R is preferably C 1-3 -alkyl. The alkyl and CONHR substituents have the advantage that the solubility of the final color molecule is limited. Phenyl groups may contain one or more substituents, the same or different substituents. When phenyl groups are substituted, mono-substitution is preferred. It is preferred that these groups are free of other substituents (unless otherwise indicated).

Specific examples of type A / couplers are alpha-naphthol, 3-aminophenol and compounds with the following structural formulas:

Specific examples of type B / couplers are benzoylacetanilide, acetoacetanilide, Ν, Ν-diethyl- and Ν, Ν-dimethyl acetoacetamide, and compounds of the following formulas:

····

I 9 9

Specific examples of type C / copolymers are: pyrazolone with the structural formula:

and compounds of the same formula except that phenyl is replaced by hydrogen H or methyl, and / or Me is replaced by H, and further compounds with the following structural formulas:

NO ₂

Cl

4444 4 4 ·· 44 44 ·· ·

Each of the above couplers may also be used in the form of a salt such as sulfate, phosphate and hydrochloride, most preferably sulfate and hydrochloride.

Compounds containing free amino groups are more preferably used in the form of a salt. The salt form of these compounds forms a powder which is often more stable than the free base form.

The solubility of the copolymers and their structures should be chosen so that they are sufficiently soluble for formulations suitable for application using water, and that the solubility and size allow for a sufficiently rapid diffusion into the hair shaft. We found a general rule that copolymers with low solubility and large molecule diffuse into the damaged hair fast enough. We have also found that smaller and more soluble molecules are particularly suitable for undamaged hair.

In addition, the final color molecule produced must be of such size and solubility that it does not easily wash out of the hair. Again, we have found that larger, more insoluble colored molecules provide greater washout resistance in damaged hair, and smaller, more soluble molecules provide good washout stability on intact hair.

The composition of the invention comprises one or more of A (A), B (A), and C (A), in combination with the described developer and antioxidant. A particular advantage of using these copulators is that it is possible to obtain a full palette of colors using three specific types of copulators and one type of developer. Preferably, the composition comprises at least two of the three types of copulators. In particular, it should comprise at least one of the couplers B (or C). It is more preferred that it comprises at least one of each type of A /, B /, and C / type copulators. In the most preferred compositions there are at most two or even only one compound of one or all of the types A (, B) and (C).

This allows the copulators to be supplied in the form of a mixture with the desired amount of each type of copolymer, so that any desired color can be achieved. Alternatively, the copolymer materials may be packaged separately, and the consumer will select the desired color by mixing the correct amounts of each copolymer, and form the colorant itself.

The total content of the copolymer is usually 0.001 to 5 or 10% by weight of the total composition applied to the hair. The preferred total amount of the copolymer is at least 0.01 wt. %, often at least 0.1 to 1 wt. %. However, it is also preferred that this amount is not more than 6 wt. and, for some formulations, at most 3%, such as at most 2.5% by weight.

Type A (and C) couplers can be used in particularly small amounts. For example, type A / couplers are used in an amount (calculated on the total weight of the hair composition) of 0.001 to 1%, more preferably 0.004 to 0.5%, for example at most 0.05%. Type C / couplers are used from 0.01 to 2 or 4%, preferably 0.03% to 3%, and in some preferred compositions at most 1% or 0.5%. Type B) copolymers are often used in larger amounts, for example 0.05 to 3 or 4 wt. %, or e.g. 0.1 to 2 or 3% by weight.

The generator is an amino-aromatic compound capable of being oxidized and subjected to a single electrophilic shock in an oxidized state. It can be, for example, an aromatic system with a single substituent - a primary amine.

The generator is of a type that reacts substantially only at one position (normally the position at which the amine is). In some instances, the developer structure is such that it allows it to react with other developer molecules, but the developer preferably reacts with the copolymer molecules. A preferred generator structure is one in which it does not substantially react with the molecules of the other generator.

Suitable developing agents are o-nitro- and p-nitro-alpha-naphthylamines having the following formulas:

NH

NO ₂

Other suitable generators are the ω- and p-nitrophenylamines of IUN-Ph-NCh, N, N-disubstituted o-phenylenediamines and Ν, Ν-disubstituted p-phenylenediamines.

The generator may be Ν, Ν-disubstituted p-phenylenediamine. These generators have a disubstituted amino group and react only at the primary amine site. In this case, they normally have formula IX:

► · 9 • 9%

9 9 9 9 · 9 «99« ^r1 ° \ .R ⁿ N

NH ₂ (IX) wherein R ¹⁰ and R ¹¹ independently of one another are H, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl, aralkyl, -R'NHCOR, -R'CONHR, -ROH, R'SOOR, -R SOONHR, or -ROR wherein R is alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl, aralkyl, and R 'is alkylene, cycloalkylene, alkenylene, cycloalkenylene, arylene, alkarylene or aralkylene, or substituted versions thereof. Suitable substituents are OH, -OR, Cl, Br, F, -COOH, -COOR, -OR and -COR. Another alternative is that R ¹⁰ and R ¹¹ may together form a substituted or unsubstituted cycloalkyl, cycloalkenyl or aryl ring.

Preferred R ¹⁰ and R ¹¹ are (independently of each other) C 1-6 -alkyl, preferably methyl, ethyl or ipropyl; C 18 -hydroxyalkyl, preferably -CH 2 CH 2 OH; alkylene-alkoxy, preferably ethylmethoxy (CH 2 CH 2 OCH 2); or R ¹² or R ¹² SO2NHR ^I2 NHSO 2 R ¹² wherein R ¹² is C. _3- alkyl, e.g. CH 2 CH 2 NHSOOCH 3.

Particularly preferred generator of the above formula III are those in which R ¹⁰ and R ¹¹ are both CH2CH3, or ^R10 is ethyl and ^R11 is CH2CH2NHSOOCH3. We assume that the last R ¹¹ contributes to dermatological compatibility. In other suitable generators, R ¹⁰ is ethyl and R ¹¹ is hydroxyethyl; or R ¹⁰ is ethyl and R ¹¹ is -CH 2 CH 2 OCH 3 (methoxyethyl); or R ¹⁰ is selected from H, methyl, ethyl or propyl and R ¹¹ is selected from methyl, ethyl or propyl.

Generally, we can choose compounds with the general formula X:

(X)

Group Y is a blocking group that ensures (under hair dyeing conditions) that the reaction takes place only at the primary amine site. The group Y may be, for example, -NR ¹⁰ R ' ¹ (as in formula IX above). Another suitable Y group is -NO ₂ , -COOH, -COR and OH. R is as defined above for Formula IV.

In an alternative generator formula, the blocking group Y is ortho to the amino group, resulting in the following formula XI:

Therefore, the Y group is positioned such that the generator undergoes only one reaction, on the primary amine group and under the given reaction conditions.

As R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ , (each independently) can be any of the groups listed for R ¹ to R ⁴ above. R ¹³ and R ¹⁴ together and / or R ¹⁵ and R ¹⁶ together may form a substituted or unsubstituted cycloalkyl, cycloalkenyl or aryl ring.

Preferred R ¹³ to R ¹⁶ are independently H, methyl, ethyl, n-propyl, i-propyl, F, CL, OH, -COOH, -COOR or -COR.

In all of the above formulas, unless otherwise stated, there may also be some non-interfering substituent, ie, a group that does not interfere with the reaction between the generator and the coupler. The substituents may in particular be phenyl and naphthyl groups. Suitable non-interfering substituents are COOH, CH 3, SO ₂ , NHCH 3, SO ₃ H, C 1-3 -alkyl such as ethyl or propyl, CONHR, wherein R is preferably C 1-3 -alkyl. The alkyl and CONHR substituents have the advantage that the solubility of the final color molecule is limited. The phenyl groups may contain one or more substituents which may be the same or different. When phenyl groups are substituted, monosubstitution is preferred. More preferably, these groups are not substituted (unless otherwise indicated).

Another preferred generator has the following formula XII:

Specific examples of generators according to the invention are generators having the following structural formula:

Β Β Β ΒΒΒ ΒΒΒ ft ΒΒΒ

ΒΒΒ

These are particularly suitable for coloring damaged hair. Other generators according to the invention are:

HOCH ₂ CH _{2 x} CH ₂ CH ₂ OH

nh ₂ which tends to fade color faster than some other developers, and

Me _xx Me N

NH ₂ which is highly reactive.

Examples of other preferred colorants suitable especially for dyeing undamaged hair are: 2,6-dichloro-p-aminophenol, 3.chloro-p-aminophenol, 2-chloro-p-aminophenol, 2,3-dichloro-p-aminophenol and 3,5- methyl-p-aminophenol.

The above derivatives contain salts such as sulphates, phosphates and hydrochloride, with sulphate or hydrochloride being more preferred. Salts commonly bind with an amino group. The preferred generator in which ^R10 is ethyl and ^R11 is CH2CH2NHSO2CH3, is conveniently prepared in salt form as a stable powder (more stable than the free base form). We have found that the salt is formed to contain 3 moles of salt per 2 moles of free base. Another useful salt is the hydrochloride salt of the developer, such as 2,6-dichloro-p-aminophenol.

The content of the developer in the composition is 0.01 to 5 or 7% by weight of the total hair composition. A preferred amount is from 0.3 to 2 or 4%, most preferably from 0.4 to 2%

1.5 or 3% by weight.

We have found that with sufficient solubility of the developer and copolymer compounds in the composition and under the conditions of application of the composition to the hair, they will diffuse into the hair shaft sufficiently quickly. However, the colored molecules must have a sufficiently low solubility to withstand hair wash.

Solubility can be important for both developers and copulators. The developer and copolymer compounds themselves must be of such solubility that they can be formulated at appropriate concentrations. For high pH application, the solubility must be at least 10, more preferably at least 15, and most preferably at least 20 g / 100 mL of deionized water at pH 10 and 25 ° C. They may have a solubility of at least 25 g / 100 ml, or even up to 50 or 80 g / 100 ml, but normally do not exceed 30 g / 100 ml.

Generally, the developer and copolymer compounds must have low solubility of the final color dimer (or trimers, if produced) under normal hair conditions, and in particular washing conditions. Thus, the solubility (at pH 8) of the final color molecule is preferably below 5 g / 100 ml, and most preferably below 0.5 g / 100 ml deionized water at 25 ° C, or even below 0.2 g / 100 ml.

In the case of compositions to be used at high pH (e.g., above pH 10), the solubility indicator can be given based on pKa. Thus, if one or more generators and copulators (especially generators) have an ionized moiety that is substantially ionized at a pH above 9, more preferably above 10, then this is an indicator of solubility at pH 10. However, in the final color molecule and at pH at the hair shaft (which is usually 5.5 to 6) becomes a non-ionized group. This suggests that it has limited solubility under normal conditions. This can often be accomplished by supplying at least one group having a pKa of 8 to 12 (and therefore ionized above that pH) in the developer or copolymer molecule, and which, when reacted to the final color molecule, also has a pKa of 8 to 12 (and therefore not ionized below this pH). Solubility can be influenced by various factors, but pKa may in some cases be a good indicator of likely solubility.

· • ♦ · · · · · · · · · · · · · · · · · ·

We have found that the advantage of the coloring compounds of the present invention is that they provide uniform coloring and resistance to fading in both damaged, flowing and undamaged hair. This is particularly advantageous in cases where the hair has been dyed once and then allowed to grow, resulting in unstained and undamaged hair. Upon re-dyeing, undamaged and previously colored, faded and damaged hair must be colored and show the same fade resistance. It is very important to impart color and, at the same time, wash and fade resistance to damaged hair (damaged, for example, when bleaching and / or performing permanent waving and / or previous dyeing). The advantage of the composition according to the invention over standard oxidative dye systems is that it is possible to achieve a full range of colors using a very small number of compounds. Preferably only one or two (most preferably only one) developer compound is used. This is further preferably used in combination with at most three, more preferably only one or two compounds of any of types A /, B /, or C /.

All of these copolymers and generators can be termed "oxidative" coloring agents (dyes) because they require an oxidizing agent to initiate the reaction. Only those oxidative dyes contained in the composition in which it may be below 0.1 wt. %, more preferably below 0.08 wt. % or below 0.05 wt. %, or substantially no oxidative dyes of type (i) and A (B) and (C), or according to the preferred formulas above.

It is preferred that the composition according to the invention contains at most 0.1 wt. %, more preferably at most 0.08 wt. %, and most preferably at most 0.05 wt. %, or substantially no non-oxidative dye material that would be able to undergo the reaction more than once (under oxidation conditions in the dyeing reaction).

It is preferred that the composition according to the invention contains at most 0.1 wt. %, more preferably at most 0.08 wt. %, and most preferably at most 0.05 wt. %, or substantially no material that could react within the molecule itself. It is preferred that the total amount of such materials does not exceed the above values.

Other coloring agents, such as, for example, vegetable dyes, may be used, but it is preferable that no non-oxidative dye is included. However, it is most preferred that no coloring component other than the developer (i) and copolymers (A), (B) and (C) defined in the invention is included. That is, in the hair coloring composition, the coloring components are essentially the developer (s) and copolymers A /, B / and / or C /. However, minute amounts of other coloring components may be added, provided that they do not substantially affect the final color.

♦ ♦ · • • • <»» »» <<<<<<<<

In particular, the compositions according to the invention excel in good dye uptake and fade resistance when used to dye hair which has been damaged by, for example, discoloration, prior dyeing or, above all, permanent preparation.

The advantage of the composition according to the invention over standard oxidative dye systems is that it is possible to achieve a full range of colors using a very small number of compounds. Preferably only one or two (most preferably only one) developer compound is used. This is further preferably used in combination with at most three, more preferably only one or two compounds of any of types A (B) and (C).

The inorganic peroxide oxidizing agent is present in the composition in an amount of 0.0001 to 0.05 moles per 100 g of the composition.

An amount of 0.05 moles per 100 grams of composition or less is sufficiently small so that the effect of damaging the hair with a larger amount of an inorganic peroxide oxidizing agent such as hydrogen peroxide is limited. Here, an amount of 0.0001 moles per 100 grams of the composition or more provides a sufficient oxidizing effect on the dyes to form molecules of the desired color.

The preferred amount (oxidizing agent) is at most 0.04, more preferably at most 0.03 moles per 100 grams of composition. The most preferred amount is 0.03 moles per 100 g of composition. Often the amount of inorganic peroxide oxidizing agent is at least 0.003 moles per 100 grams of the composition, more preferably at least 0.002 moles.

Preferred compositions according to the invention comprise an inorganic peroxide oxidizing agent in an amount of 0.003 to 1.5 wt. %, more preferably at most 1.2 wt. %, and most preferably at most 1.0 wt. %. Preferred compositions often contain an inorganic peroxide oxidizing agent in an amount of 1 wt. %. The preferred amount of inorganic peroxide oxidizing agent is at least 0.005 wt. %, more preferably at least 0.01 wt. %.

Preferred oxidizing agents of all types include those that are water soluble. The water-soluble oxidizing agents defined herein have a solubility in the range of 10 g in 1,000 ml of deionized water at 25 ° C ("Chemistry", C.E.Mortimer, 5th Ed. P. 277).

Suitable inorganic oxidizing agents are hydrogen peroxide, sodium periodate, sodium perborate and sodium peroxide, as well as inorganic perhydrate salts of oxidizing compounds such as alkali metal salts of perborates, percarbonates, perphosphates, persilicates, and persulfates. Inorganic perhydrate salts may be used as monohydrates, tetrahydrates, etc. Mixtures of two or more of these inorganic peroxide oxidizing agents may also be used. Alkali metal bromates and iodates are suitable, with bromates being more preferred.

Hydrogen peroxide is most preferred for use herein. We have found that the process of the invention has great advantages when the oxidizing agent is hydrogen peroxide, since this is a very effective oxidizing agent, but may lead to greater problems associated with hair damage than other oxidizing agents. Therefore, limiting its content brings great benefits.

It is preferred that the total amount of oxidizing agents in the composition consists essentially of inorganic oxidizing agents only. However, the total amount of oxidizing agents may include other oxidizing agents, including preformed organic peroxyacid oxidizing agents and other organic peroxides such as urea peroxide, melamine peroxide, and mixtures thereof.

Suitable preformed organic peroxyacid oxidants have the general formula R ³⁰ C (O) OOHH wherein R ³⁰ is selected from saturated and unsaturated, substituted and unsubstituted, straight or branched alkyl, aryl or alkaryl groups of 1 to 14 carbon atoms .

One class of organic peroxyacid compounds suitable for use in the present invention are amide substituted compounds having the following general formulas (XII) and (XIV):

wherein R ³⁰ is a saturated or unsaturated alkyl or alkaryl group or an aryl group having 1 to 14 carbon atoms, R ³² is a saturated or unsaturated alkyl or aralkyl group or an aryl group having 1 to 14 carbon atoms, and R ³¹ is H or a saturated or unsaturated alkyl or aralkyl group or an aryl group having 1 to 10 carbon atoms. Amide substituted organic peroxyacid compounds of this type are described in EPA-170.386.

Other suitable organic peroxyacid oxidizing agents are: peracetic acid, pemonoyl acid, nonylamidoperoxycaproic acid (NAPCA),

0000 0 0

00 0 0 1 perbenzoic, m-chloro-perbenzoic, di-peroxy-isophthalic, mono-peroxyphthalic, peroxylauric, hexanesulfonyl-peroxypropionic, N, N-phthaloylamino-peroxycaproic, monoperoxysuccinic, nonanoyl-oxybenzoic acid, peroxy-nano-piperidipanoic acid , diacyl and tetraacyl peroxides, in particular diperoxy dodecanedioic acid, diperoxy tetradecane diacid and diperoxy hexadecane diacid, and derivatives thereof. Mono- and di-perazelaic acid, mono- and di-perbrassylic acid, N-phthaloylamino-peroxycaproic acid, and derivatives thereof, are also suitable for use herein.

Preferred peroxyacid material is peracetic acid and pernonoyl acid, and mixtures thereof.

When organic oxidizing agents in the form of preformed organic peroxyacids are added, this is in an amount of 0.0001 to 0.1 moles per 100 g of composition, preferably 0.001 to 0.05 moles, more preferably 0.003 to 0.04 moles, and most preferably 0.004 up to 0.03 mol per 100 g of composition.

Preferred preformed peroxyacid oxidizing agents, when used, are 0.01 to 8%, more preferably 0.1 to 6%, even more preferably 0.2 to 4%, and most preferably 0.3 to 3% by weight of the dye composition. hair.

When both inorganic oxidizing agents and preformed organic peroxyacid oxidizing agents are used, the weight ratio of inorganic peroxide oxidizing agents to preformed organic peroxyacid reagents is 0.0125:

up to 500: 1, more preferably 0.0125: 1 to 50: 1.

If still other organic peroxides are used, their suitable amount is 0.01 to 3%, more preferably 0.01 to 2%, more preferably 0.1 to 1.5%, and most preferably 0.2 and% to 1% by weight of the composition.

The compositions of the invention may be formulated so that their pH is high, ie above pH 6.1 or 6.5, and in particular above pH 7 or 8, and most preferably at a pH of 9 to 12. These compositions may contain ammonia (or other base) such as a hair swelling agent, especially when formulated at high pH. If used, the ammonia (or other base) is added to the composition in an amount of at least 0.01 wt. %, more preferably at least 0.05 wt. %, and most preferably 0.1 to 3% by weight of the total composition, such as from 0.2 or 0.4 to 1 or 2% by weight.

These hair dyeing systems are particularly effective when the task is to dye gray hair. Low oxidant content means that colored hair will not be 9 9 9 9 9 9 9

9 9 ·

9 · 9,999

999 9 • 9 99 but the presence of ammonia promotes swelling of gray hair (which is believed to stain more difficult than colored hair), thus facilitating the diffusion of coloring materials and oxidizing agents into gray hair.

These systems are also effective for coloring light or blond undamaged hair with dark colors. They do not require discoloration (which is carried out by known systems often with a high oxidant content); they use the effect of swelling of undamaged hair with ammonia; while undamaged hair is known to dye more difficult than damaged.

However, the composition of the invention is also particularly suitable for low pH formulations. Thus, a preferred composition comprising the generators (i), A /, B / and / or C / copolymers and an oxidizing agent has a pH in the range of 1 to 6. Preferably, these compositions have a low content (e.g. below 0.5 or 0, 3% by weight) of ammonia or other base, and are most preferably substantially free of ammonia or other base.

We have found that low pH formulations are far milder against hair and skin than standard high pH formulations. Spots and skin irritation, even odor and tear effect are limited. Surprisingly, they also achieve effective oxidation of coloring agents and effective hair coloring.

Low pH hair coloring systems containing standard oxidative coloring agents are described in our application Serial No. 9626713.3.

In the low pH compositions (according to the invention) the preferred pH is 1.5 to 5.8, more preferably 1.8 to 5.5, even more preferably 2 to 5, and most preferably 3.5 to 4.5.

It is also preferred that the composition comprising only the developer (i) and the A /, B / and / or C / copolymers have a pH in the range of 1 to 6, preferably 1.5 to 5.8, more preferably 1.8 to 5.5, even more preferably 2 to 5, and most preferably 3.5 to 4.5. We have found that at this low pH, the developers and copolymers of the invention have greater storage stability.

The compositions of the invention may also contain one or more buffering agents. Various pH modifiers may be used to adjust the pH of the final composition or any portion thereof.

Acidifying agents well known in the art of treating keratin fibers, and in particular human hair, may be used to adjust the pH and achieve a low pH; they are inorganic and organic acids such as hydrochloric, tartaric, citric, succinic, phosphoric, and carbonic and sulfonic acids such as ascorbic, acetic, lactic, sulfuric, formic, ammonium sulfate and sodium (primary) dihydrogen phosphate / acid · Phosphoric, (secondary) disodium hydrogen phosphate / phosphoric acid, chloride potassium / hydrochloric acid, dihydrogen phthalate / hydrochloric acid, sodium citrate / hydrochloric acid, potassium dihydrogen citrate / citric acid, potassium dihydrogen citrate / citric acid, sodium citrate / citric acid, sodium tartrate / acetic acid, sodium citrate / citric acid, sodium tartrate / acid tartaric acid, sodium lactate / lactic acid, sodium acetate / citric acid and sodium chloride / glycine / hydrochloric acid, succinic acid, and mixtures thereof ěsi.

Examples of alkaline buffers for high pH adjustments are ammonium hydroxide, ethylamine, dipropylamine triethylamine and alkanediamines such as 1,3-diamine-propane, anhydrous alkaline alkanolamines such as mono- or di-ethanolamine, with those fully substituted on the amine group preferred. such as dimethylaminoethanol, polyalkylene polyamines such as diethylenetriamine, or a heterocyclic amine such as morpholine, and also alkali metal hydroxides such as sodium and potassium hydroxides, alkaline earth metal hydroxides such as magnesium and calcium hydroxides, and basic amino acids such as L arginine, lysine, alanine, and leucine, iso-leucine, oxylysine and histidine, and alkanolamines such as dimethylaminoethanol and aminoalkyl propanediol, and mixtures thereof. Also suitable for use in the present invention are compounds which, upon dissociation in water, form HCO3 (hereinafter referred to as &quot; ion-forming compounds &quot;). Examples of suitable such compounds are Na ₂ CO 3, NaHCl 3, K ₂ CC 3, (NFL 4 CCb, NH 4 HCO 3, CaCO 3 and Ca (HCO 3) ₂ , and mixtures thereof.

Preferred buffers for use herein are organic and inorganic acids having a first pK a below pH 6, and then also their conjugate bases. As defined in the invention, the first pKa refers to the negative logarithm (based on 10) of the equilibrium constant K, where K is the acid dissociation constant. Suitable organic and inorganic acids for use herein are: aspartic, maleic, tartaric, glutamic, glycolic, acetic, succinic, salycilic, formic, benzoic, malic, lactic, malonic, oxalic, citric, phosphoric acid, and mixtures thereof.

It is also preferred that the composition containing the oxidizing agent in an amount of 0.0001 to 0.5 moles per 100 g of said composition also has a pH in the range of 1 to 6, preferably 1.5 to 5.8, more preferably 1.8 to 5.5, even more preferably 2 to 5, and most preferably 3.5 to 4.5.

There are various ways in which the composition of the invention can be delivered. It is normally supplied as a set of hair dye components in two or more separate hair dyes. • · · · · · · · · · · · · · · · · · · · · · · · · · · · · Packaging. The consumer mixes the components as instructed to form a composition to use to color the hair.

We have found, as one of the advantages of the invention, that a composition with a small amount of oxidizing agent and a low pH value can be supplied in a single phase form, ie that the composition comprising developers (i), A /, B / and / or C / and / or inorganic peroxide the oxidizing agent is stable at low pH during storage.

Thus, the composition of the invention may be delivered as a single-phase composition even when used in a low pH composition of the invention.

There is substantially no reaction between the coloring materials and the oxidizing agent in the composition, especially when maintained at room temperature. However, when applied to the hair, the coloring components react.

Another advantage of the low pH compositions of the invention when delivered in the form of a kit of components of the hair coloring composition (wherein the components are in two or more separate containers) is the stability of the components after mixing (when the composition is low pH). Low pH formulations have the advantage that they remain stable for longer periods after mixing than high pH formulations. Thus, low pH formulations may be mixed and remain useful, for example, for half or one hour. This gives the consumer additional time to apply the blended composition: for example, he can perform the first application, and then make "repairs" using the same hair dye package.

Generators, copulators, antioxidants and oxidizing agents, and other materials applied to hair as components of the composition of the invention must be in a suitable physical form. A preferred form is a liquid. The liquid must have a low viscosity, such as water, or it can have a higher viscosity. The material may be suspended in a gel (jelly). The gel may be stiff or of low viscosity.

Hair coloring materials are often formulated so that, after mixing to form the hair coloring composition of the invention, they have a creamy consistency that is suitable for application to the hair. The final composition applied to the hair often takes the form of an emulsion.

Each individual material must be supplied in such a form that the composition containing it has a pH above or below 7. e.g. it may have a pH of from 1 to 11. To promote the solubility of various components, especially generators and copulators, in water based carriers, the carrier must have a pH above 6.1 or 6.5 or 7, such as pH 8 or 9 to pH 10 or 11. A pH of from 1 to 6 helps improve the stability of the components.

The materials must be adjusted so that the pH of the final formulation after mixing for application to the hair has a pH below 7, although any component used has a pH above 7. Alcohol such as alcohols such as e.g. ethanol, in an amount of, for example, from 5 to 10 or 25%.

The composition of the invention may also contain an antioxydant as described in our dependent application number 9710754.4. Suitable antioxidants are sulfites, such as sodium sulfite, and chelants. A suitable amount of antioxydant is 0.01 to 4 wt. %, e.g. 0.1 to 1.5 wt. %.

According to a second aspect of the invention, a hair coloring kit is provided comprising:

(1) a separately packaged coloring component comprising (i) one or more of the generators defined above, and (ii) one or more copolymers selected from the types A /, B / and C / as defined above, and (2) a separately packaged oxidizing component; wherein the separately packaged oxidizing component comprises an inorganic peroxide oxidizing agent in such a molar amount and the whole kit is prepared such that after mixing the coloring component and the oxidizing component the combined composition comprises an inorganic peroxide oxidizing agent in an amount of 0.0001 mol to 0.05 mol per 100 g of the composition.

In this aspect of the invention, it is important that the entire kit composition produced provides a ready-made finished composition with the desired amount of oxidizing agent. This can be done, for example, by delivering a complete kit such that it is sufficient to mix the separately packaged components to prepare the composition with the correct amount. A second possibility is to supply this kit with instructions to the consumer, in which ratio the separately packaged coloring component is mixed with the separately packaged oxidizing component to achieve the desired final amount of oxidizing agent.

The separately packaged dye component must be supplied as separate components. For example, it may comprise a separately packaged developer component comprising one or more developer compounds i), and a separately packaged component of a copolymer comprising components A (B) and (C). Alternatively, the copulators can be supplied separately packaged so that the A / copulators are supplied as a blue-green component,

· B / as yellow component and C / as magenta (fuchsin) component together with consumer instructions how to mix different colors.

The components of the hair coloring set according to the second aspect of the invention must meet the characteristics (properties) of the composition of the invention described above.

As a third aspect of the invention we provide a hair dyeing method consisting of preparation

(i) one or more generators as defined above; (ii) one or more copolymers selected from types A /, B / and C / as defined above; and (iii) an inorganic peroxide reagent; and (i), (ii) and (iii) for hair having The amount of inorganic peroxide oxidizing agent used is from 0.0001 mol to 0.05 mol per 100 g of applied total composition.

It is preferred that all components are applied substantially simultaneously. It is particularly preferred that they are mixed in a single composition and then applied to the hair together. However, the term "substantially simultaneously" also includes the application of one or more hair components followed by the application of the remaining components for up to 5 minutes.

The application of the components substantially simultaneously, especially mixing and application, is particularly advantageous for the user in view of better mastering the entire process.

The reaction conditions are those commonly used in hair dyeing. The temperature is usually from 10 to 45 ° C, often 20 to 35 ° C. The pH may be high (e.g. above 6.1 or 6.5, often above pH 8 or 9, or even above 10), but often low (e.g. below pH 7 or 6).

In the specification of the invention in the section on cleavage groups as well as in the section on compounds reacting only in one position or only with a certain other compound, the reaction conditions are those in which the dye compounds are applied to the hair.

Any component having the properties of the composition described above may be used in the method of the invention.

According to a fourth aspect of the invention, we provide a hair dyeing system comprising:

(i) one or more generators as defined above; (ii) one or more copolymers selected from the types A /, B / and C / as defined above; and iii) an inorganic peroxide oxidizing agent in an amount of 0.0001 to 0.05 moles per 100 g of composition; which does not contain any other oxidative coloring agents

It is capable of producing a wide range of color shades without the use of an additional coloring agent.

In this system according to the fourth aspect of the invention, the amounts and types of developer and copulator are chosen to obtain the appropriate color required for any application, since the choice of any (different) colors is achieved using the same set of generators and copulators. The system may preferably provide at least one light brown shade, at least one red shade and at least one dark brown shade, and even more preferably it may provide at least one light (blond) shade and at least one black shade.

This system preferably contains only one to four, more preferably one to three, and most preferably even only one or two compounds of each type i), A (, B) and (C). Thus, in this preferred embodiment of the system of the invention, a wide variety of colors is obtained using only a few, or even only four, coloring components.

This system shall also include instructions for selecting the quantities and types of components (i), (ii) and (iii), and to achieve the full color register and color fastness grades.

The system must be supplied to consumers (eg those who dye their hair themselves or hairdressing salons) together with instructions for selecting appropriate quantities of each coloring component and for choosing different colors and degrees of color fastness. The system can also be used by manufacturers of hair dye products. The manufacturer produces four different types of coloring components and chooses the quantities and types needed for each individual color he wants to sell.

Any of the materials described above in the context of the composition of the invention may be used in the system of the invention.

The invention also has a further aspect, according to which a hair coloring composition comprising:

(i) one or more generators selected from amino-aromatic systems capable of oxidation and then undergoing a single electrophilic shock; and (ii) one or more copolymers selected from:

A / phenols and naphthols with an active leaving group in the para position relative to the hydroxyl group,

B / 1,3-diketones containing a group

In which Z is an active leaving group:

C / compounds containing group:

O

wherein Z is an active leaving group and X is an active leaving group or a non-leaving substituent, such that in the presence of an oxidizing agent (each) the developer reacts with the (each) copolymer essentially only in the position at which the active group Z is active; X (when X is an active leaving group), and iii) an inorganic peroxide oxidizing agent, wherein the composition has a pH of from 1 to 6.

According to this aspect of the invention, the composition may contain conventional amounts of oxidizing agent provided that its pH is below 6, providing the low pH benefits discussed above. According to this aspect of the invention, any feature resulting from the foregoing aspects of the invention may be used wherever it is relevant. The set of components, method and system of the first to fourth aspects of the invention can also be used at low pH only with a conventional amount of oxidizing agent, as follows from this further aspect of the invention.

Other conventional components of hair dye compositions, such as those described in our dependent application no. 96026713.3.

Each of these compositions may also contain the following various optional ingredients.

Oxidative dye precursors

Preferred purely oxidative dyes in the composition of the invention are materials i) and ii) described above. However, the compositions may optionally also contain other oxidative coloring materials in minor amounts. These may be the materials described in our copending application PCT / US97 / 22719, Reg.

· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

Generally speaking, oxidative primary dye intermediates are those monomeric materials that upon oxidation form oligomers or polymers having longer conjugated electron systems in the structure of the molecule. The resulting oligomers and polymers, due to the new electron structure, show some shift in the spectrum towards the visible region and appear colored. Oxidative primary intermediates capable of forming color polymers include, for example, aniline having a single functional group, which upon oxidation forms a series of conjugated imines and quinoid dimers, trimers, etc., in a range of colors from green to black. Compounds, such as p-phenylenediamine with two functional groups, can oxidatively polymerize and produce higher molecular weight colored materials with longer conjugated electron systems. A representative list of primary intermediates and secondary copolymers suitable for use in the present invention is found in Sagarin: "Cosmetic Science and Technology", Interscience, spec. Edition, Vol. 2, pp. 308-310.

Non-oxidative and other dyes

The hair dye compositions used in the present invention, in addition to the major oxidative hair dye agents i) and ii) and optional oxidative dyes may also optionally include non-oxidative and other dye materials. Optional non-oxidative and other dyes suitable for use in the hair coloring compositions and methods of the present invention are semi-permanent (semi-permanent), transient and other dyes. The non-oxidative dyes mentioned herein are so-called "direct-acting dyes", metal-based dyes, metal chelates as dyes, fiber-reactive dyes, and other synthetic and natural dyes. Various types of oxidative dyes are described in detail in: C. Robbins, "Chemical and Physical Behavior of Human Hair", 3rd Ed., Pp. 250-259; "The Chemistry and Manufacture of Cosmetics", Vol. IV, 2nd ed., Chap. 45 (G.S. Kas, pp. 841-920); "Cosmetics: Science and Technology, Vol. II, 2nd ed., Balsam Sagarin, chap. 23 (F.E.Wall, pp. 279-343); The Science of Hair Care, edited by C. Zviak, Chap. 7, pp. 235-261; and "Hair Dyes", J.C. Johnson, Noyes Data Corp., Park Ridge USA (1973), pp. 2-91 and 113-139.

Non-oxidizing direct dyes are also referred to as tinting agents and have long been known in the art. They are usually applied to the hair in the form of a base matrix containing a surfactant. Direct dyes are nitro-dyes (nitro compounds) such as nitro-aminobenzene or nitro-aminophenol derivatives; disperse dyes are nitro-arylamines, amino-anthraquinones or azo dyes;

· Anthraquinone dyes; · ant rach rach; rach rach rach rach rach rach rach rach rach rach rach rach rach rach rach; naphthoquinone dyes; and basic dyes such as acridine orange C.I. 46005.

The nitro-dyes are added to the coloring compositions to enhance the color and to impart an aesthetic tone by adding to the coloring composition prior to use.

Other examples of direct effect dyes are: Arianor dyes - basic (basic) brown 17, C.I. (color index) no. 12.251; basic red 76 - C.I. 12.245; basic brown 16 - C.I. 12.250; basic yellow 57 - C.I. 12.719 and basic blue 99 - C.I. 56.059; and other direct dyes such as acid yellow 1 - C.:I. 10.316 (D&C Yellow No. 7); acid yellow 9 - C.I. 13.015; basic violet C.I. 45.170; dispersion yellow 3 - C.I. 11.855; basic yellow 57 C.1.12.719; dispersion yellow 1 - C.I. 10.345; basic violet C.I. 42.515; basic violet 3 - C.I. 42.535; greenish green C.I. 42.090 (blue FD&C No. 1); yellowish red C.I. 14700 (FD&C Red No. 4); yellow C.I. 19,140 (FD&C Yellow No.5); yellowish orange C.I. 15.985 (Yellow FD&C # 6); bluish green C.I. 42.053 (FD&C Green No. 3); yellowish red C.I. 16.035 (Red FD&C No. 40); bluish green C.I. 61,570 (D&C No. 3 Green); orange C.I. 45.370 (D&C Orange No. 5); red C.I. 15,850 (D&C Red No. 6); bluish red C.I. 15.850 (D&C red # 7; (faint) bluish red CI 45.380 (D&C red 22)) bluish red CI 45.410 (D&C red 28); bluish red CI 73.360 (D&C red 30); reddish purple CI 17.200 (D&C red 33); dirty blue-red CI 15.880 (D&C red 34); bright yellow-red CI 12.085 (D&C red 36); bright orange CI 15.510 (D&C orange 4); greenish yellow CI 47.005 ( yellow D&C No. 10), blue green CI 59.040 (D&C No. 8 green), bluish violet CI 60.730 (ext. violet D&C No. 2), greenish yellow CI 10.316 (ext. yellow D&C No. 7).

The dye-reactive fibers are Procion ^R , Drimarine ^R , Cibacron ^R , Levafix ^R and Remazol ^R , supplied by ICI, Sandoz, Ciba-Geigy, Bayer and Hoechst.

Among the natural dyes and plant dyes, the invention includes: henna (Lawsonia alba, Egyptian Privet), camomile (Matricaria chamomila or Anthemis nobilis), indigo, and campaign wood and walnut shell extract.

Transient hair dyes or hair colorants have dye molecules so large that they cannot diffuse into the hair shaft and only act on the hair surface. They are usually applied by a process whereby the dye solution is allowed to dry on the hair. As such, these dyes tend to be less resistant to the effects of washing and cleaning of hair with surfactants, and are relatively easy to wash out of the hair. Transient hair dyes can be used in the formulations 4 4 · 4 4 · 4 4

4, 444 according to the present invention; Examples of preferred transient hair dyes are given below.

Semi-permanent (semi-permanent) hair dyes usually have a smaller molecule and effect over transient (temporary) dyes, but still a larger molecule than permanent (oxidative) dyes. Semi-permanent dyes act in the same way as oxidative dyes, especially in that they have the ability to diffuse into the hair shaft. However, the semi-permanent dyes generally have a smaller molecule than the above-mentioned conjugated oxidative dyes, and as such are destined to gradually diffuse out of the hair again. This process speeds up simple hair washing and cleaning, and it can generally be said that the semi-permanent dyes are largely washed out of the hair after the fifth to eighth washes. This semi-permanent dye system can also be incorporated into the compositions of the present invention. Suitable semi-permanent dyes useful in the compositions of the present invention are: HC blue 2, HC yellow 4, HC red C, disperse violet 4, disperse black 9, HC blue 7, HC yellow 2, disperse blue 3, disperse violet 1, and mixtures thereof (note: HC = hair color). The following are examples of semi-permanent dyes:

_X C ₂ H ₄ OH

N

NO,

N (C ₂ H ₄ OH) ₂

Blue

Yellow

June

Conventional semi-permanent dye systems contain mixtures of large and small molecule dyes. The diameter of the hair is not the same from root to tip, so small molecules diffuse into the hair at both the root and the tip but do not hold in the tip, while larger molecules usually only diffuse at the tip of the hair. This combination of molecular sizes is used to achieve a consistent (same) color result from the root to the tip of the hair during the initial dyeing process and during subsequent washing.

Catalytic converter · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

The hair coloring compositions of the invention optionally comprise a catalyst for some inorganic peroxide oxidizing agents and for optional preformed peroxide oxidizing agents.

Thickeners

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

Thinner

For the compositions of the present invention, the preferred diluent is water. However, the compositions of the invention may contain one or more solvents as additional diluent material. Generally speaking, solvents suitable for the coloring compositions of the invention must be selected to be miscible with water and not harm the skin. Such solvents suitable as additional diluents are C 1-6. ₂ of mono- or poly-hydric (polyhydric) alcohols and their ethers, glycerine, wherein preferred are monohydric and dihydric alcohols and their ethers. Of these compounds, those having 2 to 10 carbon atoms are preferred. Thus, a preferred group is ethanol, isopropanol, n-propanol, butanol, propylene glycol, ethylene glycol monoethyl ether, 1,2-hexanediol, butoxyethanol, benzyl alcohol, and mixtures thereof. The preferred diluent in the compositions of the invention is water. By the principal diluent in the present invention is meant a diluent having a proportion greater than that of all other diluents.

• · ·· ·· ·· ··

98 99 9 9 9 9 9 9

9 · 9 9 9 9 9

9 · 999999

9 · · 99

999 999

The diluent content is 5 to 99.98%, preferably 15 to 99.5%, more preferably 30 to 99%, and most preferably 50 to 99% of the total weight of the composition according to the invention.

Enzymes

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

Suitable enzymatic materials are commercially available lipases, cutinases, amylases, neutral and alkaline proteases, esterases, cellulases, pectinases, lactases and peroxidases commonly added to detergent compositions. Suitable enzymes are described in USP 3,519,570 and 3,533,139.

Peroxidases are hemoproteins specific for peroxides, but using a long range of substances and donors. Peroxide decomposing catalase is added because it has similar structure and properties and is able to initiate some oxidation with hydrogen peroxide. Decomposition of Η ₂ Ο ₂ can be viewed as oxidation of one molecule by another. It is abundant in aerobic cells, where it may have some important function. Coenzyme peroxidases are not hemoproteins, and at least one of them is flavoprotein. Other flavoproteins, such as xanthine oxidase, also utilize H ₂ O ₂ among other acceptors, and coenzyme peroxidases resemble these rather than classical peroxidases because they are not specific for H2O2. Suitable peroxidases for the compositions of the invention are horseradish peroxidase, Japanese radish peroxidase, cow's milk peroxidase, mouse liver peroxidase, ligninase, and haloperoxidases such as chloro- and bromo-peroxidase.

The enzymes are preferably added in an amount sufficient to produce up to 50 mg, more preferably 0.01 mg to 10 mg of active enzyme per gram of the hair care composition of the invention. In other words, the peroxidase enzyme according to the invention is added in an amount of 0.0001 to 5%, more preferably 0.001 to 1%, and most preferably 0.01 to 1% of the active enzyme by weight of the total composition.

Commercially available proteases are supplied by the company. Novo Industries A / S (Denmark) under the trade names Alcalase, Savinas, Primase, Durazy and Esperase, GistBrocades under the trade names Maxatase, Maxacal and Maxapem, and Genencor International. The protease enzyme is added to the composition of the invention in an amount of from 0.0001% to 4% active enzyme by weight of the composition.

• 000

• 00 00

0 0 0 0 0

0 0 0 0 0 0 000.000

0 0000 00 00

Amylases include, for example, alpha-amylases obtained from a special strain of B. licheniformis, described in more detail in GB 1,269,839 (Novo). Preferred commercially available amylases are, for example, under the tradename Rapidase (supplied by Gist-Brocades), and under the trad. Termamyl and BAN (supplied by Novo Industries A / S). The amylase enzyme is added to the composition of the invention in an amount of 0 0001 to 2% active enzyme by weight of the composition.

The lipolytic enzyme may be present in an amount of active enzyme of 0.0001 to 2%, more preferably 0.001 to 1%, and most preferably 0001 to 0.5% by weight of the composition.

Lipases may be of fungal or bacterial origin, and are obtained, for example, from Humicola sp., Thermomyces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomonas fluorescens. Lipases from chemically or genetically modified mutants can also be used according to the invention. A preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is described in EP-B0218272.

Another preferred lipase useful in the invention is obtained by cloning the gene from Humicola lanuginosa and culturing the gene in Aspergillus oryzae as the host, as described in European Patent Application EP-A-0258 068; this lipase is commercially available from Novo Industries A / S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in USP 4,810,414 (Huge-Jensen et al.), Issued March 7, 1989.

Surfactants

The compositions of the present invention further comprise a surfactant surfactant system. Suitable surfactants added to the compositions of the invention generally have a lipophilic chain of 8 to 22 carbon atoms, and anionic, cationic, nonionic, amphoteric, zwitterionic surfactants, and mixtures thereof can be selected.

i) Anionic surfactants

Anionic surfactants suitable for use in the compositions of the invention include alkyl sulfates, ethoxylated alkyl sulfates, alkyl glyceryl ether sulfonates, methyl acyl taurates, fatty acyl glycinates, N-acylglutamates, acyl isethionates, alkyl sulfosuccinates, alkyl ethoxy sulfosuccinates, alpha-sulfonated fatty acids salts and / or esters thereof, alkyl38

Ethoxycarboxylates, alkyl phosphate esters, ethoxylated alkyl phosphate esters, acyl sarcosinates, hydrotropes such as alkyl xylene sulfonates and condensates of fatty acids and proteins, and mixtures thereof. The alkyl and / or acyl chain lengths of these surfactants are C 1-6. ₂₂ , preferably C ₁₂ . ₁₈ , and more preferably C12-14ii) Nonionic surfactants

The compositions of the invention may also comprise a water-soluble nonionic surfactant (s). Surfactants of this class are C12-14 fatty acid mono- and diethanolamides, sucrose polyesters, and polyhydroxy fatty acid amides of the general formula

Preferred N-alkyl, N-alkoxy- or N-aryloxy-polyhydroxy fatty acid amide surfactants of the above formula are those in which R is C 5,31 hydrocarbyl, more preferably C 6-19 hydrocarbyl, including straight and branched chain alkyl and alkenyls or a mixture thereof, and R ⁹ is usually hydrogen, C 1-8 -alkyl or -hydroxyalkyl, preferably methyl, or a group of the formula -R 1 -OR ² , wherein R ¹ is C ₂ . ₈ hydrocarbyl straight, branched chain and cyclic (including aryl), and is preferably a _C2 -4 alkylene, and wherein R is C ₈ - straight, branched and cyclic hydrocarbyl including aryl and oxy-hydrocarbyl, wherein C 1-4 alkyl, especially methyl or phenyl, is preferred. Z ² is a polyhydroxyhydrocarbyl group having a linear hydrocarbyl chain having at least two hydroxyls (in the case of gylceraldehyde) or at least three hydroxyls (in the case of other reducing sugars) directly linked to the chain, or an alkoxylated derivative thereof (preferably ethoxylated or propoxylated). Preferred Z is derived from a reducing sugar in a reduction-amination reaction, with Z being most preferably a glycityl group. Preferred reducing sugars are glucose, fructose, maltose, lactose, galactose, mannose and xylose, as well as glyceraldehyde. As raw material, high dextrose (glucose) corn syrup, high fructose corn syrup, or high maltose corn syrup, as well as the individual sugars listed above may be used. This is not meant to exclude other suitable raw materials. More preferably, Z ² is selected from the following groups: -CH ₂ - (CHOH) _n -CH ₂ OH, -CH (CH ₂ OH) - (CHOH) _n -CH ₂ H, CH ₂ (CHOH) ₂ (CHOR ') ( CHOH) _-CH2 OH, where n is an integer of 1 to 5 (inclusive), R 'is

9999 * 9 99 ·· 99 · · 999 9 9 99 9

9 9 99999

9999 9999 999 99 99 999 999 9999 99 99

H or a cyclic mono- or poly-saccharide, and alkoxylated derivatives thereof. As mentioned above, the most preferred are glycityls in which n = 4, in particular -CH 2 - (CHOH) 4 -CH 2 OH.

The most preferred polyhydroxy fatty acid amide has the formula R ⁸ (CO) N (CH 3) CH 2 (CHOH) 4 CH 2 OH, wherein R ⁸ is a C 6-19 alkyl or alkenyl group with a direct o

string. In the compounds of this formula, the group R-CO-N <may be, for example, coconut, stearic, oleic, lauric, myristic, capric, palmitic, talicic acid amide, etc.

Nonionic oil-derived surfactants suitable for use in the present invention are water-soluble vegetable and animal emollients such as polyethylene glycol chain inserted triglycerides, ethoxylated mono- and diglycerides, polyethoxylated lanolines and ethoxylated butter derivatives. A preferred class of nonionic oil-derived surfactants useful in the present invention has the general formula:

O

II

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

Suitable ethoxylated oils and fats of this class are polyethylene glycol derivatives of glyceryl cocoate, glyceryl caproate, glyceryl caprylate, glyceryl tallate, glyceryl palmitate, glyceryl stearate, glyceryl laurate, glyceryl oleate, glyceryl oleate, glyceryl glycerate oil, with glyceryl talonate and glyceryl coconut being preferred.

Preferred nonionic surfactants based on the polyethoxylated C9.15 fatty alcohol contain on average 5 to 50 ethyleneoxy groups per mole of surfactant.

Suitable polyethoxylated C8. 15 fatty alcohols are based on polyethylene glycol: C9-n-Pareth-3, _C-9 .n Pareth-4, _C-9 .n Pareth-5, _C-9 .n Pareth-6, C9-n-Pareth- 7, C9.11Pareth-8

Cii_i -Pareth _5-3, C | U5-Pareth-4, Cn-i5-Pareth-5, Cu.i5-Pareth-7, Cn_i5-Pareth-8-Pareth9 Cius, Cu-15-Pareth-lo, Cn 15-Pareth-11, Cn 15-Pareth-12, C 15-Pareth-13, C 11 -15-Pareth-14. PEG 40 hydrogenated castor oil is available under the trade name Cremophor ^R from BASF. PEG 7 glyceryl coconut and PEG 20 glyceryl laurate are available from Henkel under the trade names Cetiol ^R HE and Lamacit ^R -GML 20. C ₉ .u-Pareth-8 is commercially available from Shell Ltd. under the tradename Dobanol ^R 91-8. For use according to the invention

ΦΦΦΦ · · · φ · ΦΦΦ · φ φ φ φ φ φ φ φ φ φ

Most preferred are polyethylene glycol ethers of cetaryl alcohol such as Ceteareth 25, which is available from BASF under the trade name Cremaphor A25. Nonoxynol surfactants may also be used.

Also suitable for the invention are nonionic surfactants derived from compound vegetable fats extracted from the fruit of the buttery (Shea Tree: Butyrospermum Karkii Kotschy), and derivatives thereof. Similarly, ethoxylated derivatives of mango, cocoa butter, and illipe butter may be used according to the invention. Although these substances are referred to as ethoxylated nonionic surfactants, it is to be understood that a certain proportion thereof remains unethoxylated vegetable oil or fat.

Other suitable nonionic oil-based surfactants are ethoxylated almond oil, peanut oil, rice bran oil, wheat germ oil, linseed oil, jojoba oil, apricot, nut, pistachio, sesame, rapeseed oil, juniper oil, corn, peach, poppy, pine, castor, soybean, avocado, safflower oil (safflower), coconut, hazelnut, olive oil, grape seed oil and sunflower oil.

iii) Amphoteric surfactants

Amphoteric surfactants suitable for use herein are:

(a) imidazoline surfactants of formula 1 /:

wherein R ¹ is C 7-2 -alkyl or -alkenyl, R ² is hydrogen or CH ₂ Z, and each Z is independently COOM or CH ₂ COOM, and M is hydrogen, an alkali metal, an alkaline earth metal, ammonium or alkanolammonium; and / or ammonium derivatives of formula 2 /:

C _? H ₄ OH ^{+ 1 '} COH (CH ₂ ) ₂ NCH ₂ Z

I 2

R ² wherein R ¹ , R ² and Z are the same as above;

• ·

(b) aminoalkanoates of formula (3):

R'NH (CH ₂ ) nCOOM iminodialkanoates of formula 4 /:

R'N (CH ₂ ) _m COOM and iminopolyalkanoates of formula 5 /:

R ¹ - [N (CH ₂ ) _p ] q N [CH ₂ CO ₂ M] ₂ CH ₂ CO ₂ M where n, m, p and q are integers from 1 to 4, and R ¹ and M are independently selected the group specified above; and

(c) mixtures thereof.

Suitable amphoteric surfactants of type a) are sold under the trade names Miranol and Empigen and are believed to contain a complex mixture of substances. In practice, a complex mixture of cyclic and non-cyclic compounds exists, so both definitions are provided for completeness, but non-cyclic species are most preferred from the aspect of the invention.

Examples of suitable amphoteric surfactants of type a) are compounds of formula 1 (or 2) wherein R ¹ is C 8 H 11 (especially iso-capryl), C 9 H 19 - and C 11 H 23 -alkyl. Particularly preferred are compounds wherein R ¹ is C 11 H 23, Z is COOM and R ² is hydrogen H, compounds wherein R ¹ is C 11 H 23, Z is COOM and R ² is CH ² COOM, and compounds wherein R ¹ is C 11 H ₂ 3, Z is COOM and R ² is H.

In the CTFA nomenclature, materials suitable for use in the present invention are coco-amphocarboxypropionate, coco-amphocarboxypropionic acid, and in particular coco-amfoacetate and coco-amphodacetic acid (otherwise referred to as coco-amphocarboxyglycinate). Specific commercial products are sold under the trade names Ampholak 7TX (sodium carboxymethyl-tallo-polypropylamine), Empigen CDL60 and CDR60 (Albright & Wilson), Miranol H2M Conc., Miranol C2M Conc. NP, Miranol C2M Conc. OP; Miranol C2M SF; Miranol CM Special (Rhone-Poulenc); Alkateric 2CIB (Alkaril Chemicals); Amphoterge W-2 (Lonza Inc); Monateric CDX-38; Monateric CSH-32 (Mona Industries); Rewoteric AM-2C (Rewo Chemical Group); and Schercotic MS-2 (Scher Chemicals). Further examples of amphoteric surfactants suitable for use herein include Octoxynol-l -polyoxyetyln ^R (1) octylphenyl ether; Nonoxynol-4 ^R -polyoxyethylene (4) -nonylphenyl ether, and Nonoxynol-9 polyoxyethylene (9) -nonylphenyl ether.

* · · «« ♦ ♦ * * * * * * * * * * * * · · · ·

It is understood that numerous commercially available amphoteric surfactants of this type are produced and sold in the form of an electronutral complex, e.g., with a hydroxide counterion or with anionic sulfate or sulfonate surfactants, which are in particular of the sulfated C8-alcohol or C8-is-acylglyceride type. Note that the concentrations and mass fractions of amphoteric surfactants disclosed herein are based on uncomplexed surfactant forms, so that the counterion content of the respective anionic surfactant is considered to be part of the total anionic surfactant component.

Examples of preferred amphoteric surfactants of type b) are the N-alkyl polytrimethylene polycarboxymethylamines available under the trade names Ampholak X07 and Ampholak 7CX by Berol Nobel, as well as the salts of especially triethanolamine and the salts of N-lauryl-betaaminopropionic acid and N-lauryl-imino-dipino-diphionopropionic acid. . These materials are supplied by Henkel under the trade names Deriphat and Rhone-Poulenc under the trade names Mirataine.

iv) Both ionic surfactants

The water-soluble zwitterionic auxiliary surfactants useful in the compositions of this invention are alkyl betaines of formula R ⁵ R ⁶ R ⁷ N (CH 2) _n COOM, and amidobetaines of formula 6 / below:

R ⁵ CON (CH ₂ ) n N (CH ₂ ) _n CO ₂ M wherein R ⁵ is C 1-2 alkyl or alkenyl, R ⁶ and R ⁷ are independently C 1-3 alkyl, M is H, an alkali metal, alkaline earth metal, ammonium or alkanolammonium, and m is an integer from 1 to 4. Preferred betaines are coco-amido-propyldimethylcarboxymethyl-betaine, laurylamidopropyl-dimethylcarboxymethyl-betaine, and betaine Tego ^R.

The water-soluble auxiliary sultain surfactants suitable for the compositions of the present invention are alkyl sulfates of formula 7 / below:

R ² ! + ¹

R ¹ CON (CH ₂ ) _n (CH ₂ ) _n CH (OH) CH ₂ SO ₃ MR ³

4444 4 _ 4 44 44 44 • ·· 44 4 4 · · · ·

4 '4 4 4 4 4 4 • · · · «4 ··· 443 · 4 4 4 4«

444 444 4444 44 44 where R ¹ is C 7-22 -alkyl or -alkenyl, R ² and R ³ are independently C 1-3 -alkyl, M is H, an alkali or alkaline earth metal, ammonium or alkanolammonium, and the amine is numbers from 1 to

4. For use according to the invention, coco-amido-propylhydroxy sultain is preferred.

The water-soluble auxiliary amine oxide surfactants useful in the compositions of this invention are the alkyl amine oxide R ⁵ R ⁶ R ⁷ NO, and the amidoamine oxides of formula 8 / below:

R ⁵ CON (CH ₂ ) 2 wherein R ⁵ is C 22-22 alkyl or -alkenyl, R ⁶ and R ⁷ are independently C 1-3 alkyl, M is H, alkali metal, alkaline earth metal, ammonium or alkanolammonium , and m is a number from 1 to 4. Preferred aminoxyds are cocosamido-propylaminoxyd, lauryl-dimethylaminoxyd and myristyl-dimethylaminoxyd.

Other preferred additive materials

Some other preferred optional materials are added to the coloring compositions described herein, each in an amount of 0.001% to 5%, more preferably 0.01% to 3%, and most preferably 0.05% to 2% of the total weight of the composition. These materials are proteins and polypeptides, and mixtures thereof, water-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 ( oxalic acid), sulphated castor oil, salicylic acid and sodium thiosulphate, hydrogen peroxide stabilizers, humectants such as hyaluronic acid, chitin, and starch crosslinked sodium polyacrylates such as Sanwet ^R , IM-1000, IM-1500 and IM-2500, supplied by spol. Celanese Superabsorbent Materials, Portsmith, VA, USA, which are described in US-A-4,076,663, as well as methylcellulose, starch, higher fatty alcohols, paraffin oils, fatty acids, and the like; solvents + antibacterial agents such as Oxeco (phenoxyisopropanol); furthermore, low temperature phase modifiers such as ammonium ion sources (e.g., NH 4 Cl), viscosity adjusting agents such as magnesium sulfate and other electrolytes; quaternary amine compounds such as distearyl-, dilauryl-, dihydrogenated beef tallow, dimethylammonium chloride, diacetyl diethylammonium methylsulfate, ditalo-dimethylammonium methylsulfate, diso-dimethylammonium chloride, and dicocoso-dimethylammonium chloride; furthermore, hair conditioning agents such as silicones, higher alcohols, cationic polymers and the like; enzyme stabilizers such as water-soluble calcium sources or borates, coloring agents, TiO ₂ , and TiO ₂ coated mica, perfumes and perfume solvents, and zeolites such as Valfour

BV400 and derivatives thereof, and agents for masking Ca / Mg ions such as polycarboxylates, aminopolycarboxylates, polyphosphonates, etc., and water softening agents such as sodium citrate. Other preferred optional materials are anti-dandruff active agents such as ZPT, and fragrances.

Examples

In the following, the invention is illustrated by the examples which follow. In these examples, various standard assays are used and are discussed below.

I Determination of initial color and color change (measurement Δ E)

The instrument used to measure both the initial color and the color change of the substrate (hair / skin) stained with the low pH dye composition of the invention is a Hunter Colorquest Spectrophotometer. The value used to express the degree of discoloration of the substrate is delta E (Δ E). The delta value defined herein is the true sum of the values L, a, and b, such that

Ε = (ΔΙ? + Aa ² + Δ b ² ) ⁴ where L is a measure of lightness and darkness (color intensity), where L = 100 is the white equivalent and L = O is the black equivalent. Furthermore, "a" is a measure of the quotient of red and green (shade, color tone) so that a positive value equals red and a negative value equals green, and "b" is a measure of the proportion of yellow and blue by a positive value equals yellow and a negative value equals blue.

Measurements can be made on the Hunter Laboratory Colorimeter, which is a full sensing spectro-colorimeter for wavelengths of 400 - 700 nanometers, which records the color of the test hair strands in the values "L", "a" and "b". The instrument is set to: mod. • • • 4 4 · 4 · 4 · 4 · 4 · 4 · 4 · 4 · 4 · 444444 ·· · 4 4 4 4 4 ··· ··· 4444 ·· 44

0/45; port size - 2.54 cm (1 inch); field of view size - 2.54 cm (1 inch); light - D65; viewing angle - 10 °; UV lamp filter - none.

The hair strand is placed in a sample holder that is designed to have a uniform orientation during measurement. Any equivalent colorimeter may be used, but care must be taken to ensure that hair does not move during measurement. The hair must be spread out to cover a 2.54 cm (1 inch) port for color measurement. The pressure holder is placed on the hair holder to control the location of the port holder. The dots are aligned and aligned with the input (port) mark and read at each point.

Eight measurements are made on one strand of hair, 4 on each side, and the whole procedure is performed on three strands of hair.

II Standard (normalized) hair strand

The compositions of the present invention can be used to dye hair in all colors, types and conditions. Different hair strands can be tested for clarification purposes. The approximate values L, a and b of the two test hair strands are measured:

L and b Light brown (after permanent treatment and discoloration) cca 60 cca 9 cca 32 40% gray dark brown 35-37 4,6-5,5 1,5-12,7

Yak-style hair may also be used (without or after permanent treatment and / or discoloration). These have values: L = 82-83, a = -0.5 to -0.7, b = 11 to 12.

III Hair Coloring Method

For staining, 4 grams of 20.3 cm (8 inches) long hair (or 2 grams of 10.16 cm (4 inches) long hair) is suspended above a suitable container. Thereafter, the test dye is prepared (i.e., all components are mixed together in separate containers), and about 2 grams of dye product is applied directly to the test hair strand. The cream is rubbed into the strand of hair for about one minute and then left on the hair for 30 minutes. After washing with plain water for 1 to 2 minutes, the dyed strand of hair is washed (according to shampooing formula IV). (See below) and dried. Drying can be natural (without the use of heat) or using a dryer. The color development (from the initial color) of the dyed, washed and dried hair strands is then determined using a Hunter spectrophotometer.

To give a red shade (tone) to pre-hardened and pre-bleached light brown hairs (having L, a, b values of 60, 9 and 32), a preferred initial shade of dyed hair is a shade with a tone value (are tg b / a) of 25 to 70, more preferably 30 to 65, and most preferably 35 to 60, and wherein the initial color intensity (L) is greater than 10 and less than 70, more preferably greater than 15 and less than 65, and most preferably greater than 20 and less than 60.

To give a brown or black shade (tone) to pre-hardened and light brown hairs (which have L, a, b values of 60, 9 and 32), the preferred initial shade of dyed hair is a shade with a tone value of less than 25, more preferably less than 20, and wherein the initial ink intensity L is greater than 1 and less than 50, more preferably greater than 5 and less than 45.

To give a light brown shade (tone) to pre-hardened and light brown hairs (having Δ L, a, b values: 60, 9, 32) the preferred initial shade of dyed hair is a shade with a tone value of 70 to 110, and with an initial color intensity (L) of greater than 20 and less than 95, more preferably greater than 25 and less than 90.

A significant color change upon application of the coloring compositions of the present invention is considered to be the hair color change after permanent conditioning and preparation discoloration, expressed as delta E, wherein the delta E value is greater than 5 or 8, more preferably greater than 10, even more preferably greater than 12. , most preferably greater than 15, and most preferably greater than 20.

Method of washing the hair strand

The strands of dyed hair are subjected to a repeated wash cycle consisting of the following procedure:

grams of 8-inch (20.3 cm) test strand of colored hair (or 2 grams of 4-inch (10.16 cm) test strand is clamped over a suitable container and washed thoroughly for about 10 seconds with lukewarm water (34 ° C) ° C (100 ° F) and a pressure of 32 liters = 1.5 gallons / minute) After which a shampoo (about 0.1 ml of conditioner shampoo per gram of hair) is applied directly to the wet hair strand. The hair is rinsed with tap water for 30 seconds The shampooing and frothing process is repeated for a final wash of 60 seconds The excess water can be removed (wringed) using your fingers and the test strand is then allowed to dry either naturally or • •·· ·· ·· • in a preheated drying cabinet at 60 ° C (140 ° F) • • • • • • • • • • • • • ) (for 30 minutes) On a dyed, washed and dried strand l The color is then determined from the times (delta E decrease).

During each test cycle, each strand of hair must be tested at the same temperature, pressure and water hardness.

The delta E decrease results for reddish-colored (brown, hair, L, a, b, 60, 9, and 32) long-lasting and pre-bleached hairs (with a tone value between 25 and 70) are preferred when delta E less than 5, more preferably less than 4.5, even more preferably less than 4.0, and most preferably less than 3.0 or 2.0, and further if the color change% ΔE after 20 washes is less than 20%, more preferably less more than 15%, and most preferably less than 10%.

The delta E diminution results for permanently and prepainted light brown hairs (with L, ab values: 60, 9 and 32) colored brown or black (with a tone value less than 25) are advantageous if the delta E less than 2.3, more preferably less than 2.0, and most preferably less than 1.7, and further, if the% ΔE change after 20 washes is less than 4.5%, more preferably less than 4%, and most preferably less than 3.5%.

The results of delta E reduction in the case of permanently and preparatively stained) light brown hair (with L, a, b values: 60, 9 and 32) dyed to a light brown shade (with a tone value between 70 and 110) are advantageous if delta E less than 2.6, more preferably less than 2.3, and further if the% color change ΔE is less than 15%, more preferably less than 12%, even more preferably less than 10%, and most preferably less than 8%.

In preferred embodiments of the invention, the color change of the dyed hair over a period of time (delta E loss) is less than 15%, preferably less than 12%, more preferably less than 10%, and most preferably less than 8%.

V Prescription (protocol) to perform permanent wave

The following method is used to perform permanent hair waving (which is then usually bleached):

grams of a 20.3 cm (8 inch) strand of hair are suspended above a suitable container. Apply a permanent solution supplied under the trade name "Zotos" to the hair until the hair is completely saturated. Then the hair strands are saturated once more. The strands are then placed on a plastic backing for 20 minutes and rinsed for 1.5 to 2 minutes with plain water heated to 37 ° C. The hair strands are then wrung dry and wiped with a towel, and again

4444 4 4 44 44 ··

4 4 4 4 4 4 4 · 4 4 4 44444 444 44 444 444

4 4 4 4 4 5

444 444 4444 44 44 are suspended above the container and saturated with the commercially available "Zotos" neutralizer. They are then placed again on a plastic tray for 5 minutes and then rinsed again with water heated to 37 ° C for 1.5 to 2 minutes. The hair strands are then shampooed twice and allowed to dry.

VI Prescription staining protocol

Pre-curled hair is dried for 20 minutes and hanged over the edge of the container. A maximum of 9 or 10 strands of hair are processed at a time. According to the instructions, the "Born Blonde" bleacher is prepared (mixed) and 10 g of this material is applied to each strand of hair, which is thoroughly rubbed into the hair. Each strand is loosely packed into a layer of loops and allowed to stand for 30 minutes. It is then rinsed for 2 minutes with plain water at 37 [deg.] C. and shampooed at once.

Example 1

In this example, a composition 1 prepared according to the invention is shown; composition 1 has a low oxidant content and low pH. Further, the composition is compared to a commercial high pH product for skin staining.

The following coloring components were used in formulation 1:

component i) component ii) C / pyrazolone

component ii) B / benzoylacetanilide

component (ii) A / alpha-naphthol 9 9 9 9 9 9 9 9 9

Formulation 1 according to the invention has the following composition:

weight% Ceteareth 25 1.57 Cetyl alcohol 2.36 Stearyl alcohol 2.36 and) 2.1 Pyrazolone (ii) C / 0.22 alpha-naphthol (ii) A / 0.012 Benzoylacetanilide (ii) B / 0.61 Ethanol 7.7 NH ₄ OH 0 Hydrogen peroxide 1.1 Sodium sulphite 0.4 EDTA 0.4 water to 100

Formulation 1 has a pH of 3.8.

The formulation was compared to a commercial high-oxidizing, high-pH formulation: this formulation entitled "Santiago" Recital was supplied by LOreal.

Prior to staining, human skin L, a and b values were measured. 0.2 o was applied to the skin

g / cm @ 2 of composition, and the treatment time was 30 minutes. The composition was then rinsed with water, and L, a and b were again measured to calculate the initial delta E, which represents the difference in skin color before and after dyeing.

The results are shown in Table 1:

Formulation 1 L and b Δ E initial Without skin in the beginning 64.5 10.6 11.9 visible spots skin after dyeing 63.21 10.5 12.8 1.6 LOreal Santiago L and b Δ E initial skin in the beginning 65.8 11.3 13.0 Significant spots skin after dyeing 55.4 16.6 15.2 12.00

• · · · ·

It can be seen from Table 1 that the delta E value is considerably greater when using a commercial formulation than when using formulation 1 of the invention. The commercial formulation shows significant stains on the skin, while the formulation 1 of the invention shows substantially no visible stains, even after application for 30 minutes.

Example 2

The following formulation was tested:

Stearyl alcohol 2.7% Cetyl alcohol 2.7% Ceteareth 25 1,8% Ammonium hydroxide 0% N-ethyl-2-methyl- (methanesulfonamide) -p-phenyldiamine 3% Phenylmethylpyrazolinone 0.17% Acetoacetanilid 1.3% 1-Naphthol 0.004% Sodium sulphite 0.2% EDTA 0.2% Water up to 100% PH 4,5

This formulation was applied to the permanently and pre-bleached light brown hair for 30 minutes.

L% 27.4, a = 14.7, b = 11.5, delta E (increase) = 39.4. The resulting color was dark golden brown (titian).

Example 3

The following formulation was tested:

Stearyl alcohol 1,62% Cetyl alcohol 1,62% Ceteareth-25 1.11% Ammonium hydroxide 1,8% 2,6-dichloro-p-aminophenyl HCl 1.0% 3-Methyl-pyrazolinone 0.8% N, N-dimethyl acetoacetamide 2%

• 9 · 999

9 9 9

n-propyl gallate 0.8% Ascorbic acid 0.4% EDTA 0.2% Hydrogen peroxide 3% Citric acid 0.24% Water up to 100% pH 5.2

The composition was applied to yak-style permanent hair and pale-brown hair.

The results are as follows:

Hair lock L and b ΔΕ Yak permanent before staining 82.8 -0.6 11.7 Yak permanent after staining 50.6 6.1 15.6 33.1 silvery Copper ba rva Hair lock L and b Δ E Light brown hardy and bleached before staining 60.1 9.7 32.1 Light brown hardy and bleached after staining 43.9 11.1 24.4 18.1 dark p your color-blond

9 9 9 9 9 9 9 9 9 9 9 9 9 9

999 9999 9999 9 · 9 ·

Claims (3)

PATENT CLAIMS (1) individually packaged coloring components containing: i) one or more generators as defined in claim 28, and ii) one or more copulators as defined in claim 28, and (1) individually packaged coloring components containing: i) one or more generators as defined in claim 1, and ii) one or more copulators as defined in claim 1, and What is claimed is: 1. A composition for coloring hair (i) one or more generators selected from amino-aromatic systems capable of oxidizing and undergoing a single electrophilic shock; and (ii) one or more copolymers selected from: A / from phenols and naphthols having an active leaving group in the para position relative to the hydroxyl group, B / z 1,3-diketones containing a group wherein Z is an active leaving group, and C / z compounds containing a group wherein Z is an active leaving group and X is an active leaving group or a non-leaving substituent, in the presence of an oxidizing agent ( each) the generator reacts with the (each) copolymer essentially only in the position at which Z and X are active when X is active, and iii) from 0.0001 to 0.05 of an inorganic peroxide oxidizing agent moles per 100 g of composition. 2) a separately packaged oxidation component, wherein the kit is designed to have a pH of at most 6 after mixing of the compositions 1) and 2). 30. A method of coloring hair, which method is used i) one or more generators as defined in claim 28, and ii) one or more copulators as defined in claim 28, and 99 99 9 9 9 9 9 9 9 9 9 9 9 · 9 · 9 9 999 999 9 9 9 9 9 9 99 999 999 9999 99 99 (iii) an inorganic peroxide oxidising agent, and that (i), (ii) and (iii) are applied to hair to be dyed, the mixture applied to the hair having a pH of not more than 6 The kit, method and system method of any one of claims 24 to 27, further comprising the properties set forth in claims 2 to 20. The composition, kit and method of any one of claims 28 to 30, further comprising the properties defined in claims 2 to 18 and 21 to 23. 2) separately packaged oxidizing components, wherein the individually packaged oxidizing component comprises the inorganic peroxide oxidant in such a molar ratio and the whole set is made such that after combining the coloring and oxidizing component, the combined composition comprises an inorganic peroxide oxidizing agent in an amount of 0.0001 moles to 0.05 mol per 100 g of the resultant composition. 25. A method of coloring hair which is used i) one or more generators as defined in claim 1, and ii) one or more copolymers as defined in claim 1, and iii) an inorganic peroxide oxidizing agent, wherein i), ii) and iii) are applied to the hair to be dyed, and the amount % of the inorganic peroxide oxidizing agent is 0.0001 to 0.05 moles per 100 g of total composition used. 26. A method of dyeing hair, wherein the hair must be subjected to a permanent preparation prior to dyeing. 27. A systemic method for coloring hair comprising only (i) one or more generators as defined in claim 1; and (ii) one or more copolymers as defined in claim 1; and (iii) an inorganic peroxide oxidizing agent in an amount of 0.0001 mol to 0.05 mol per 100 g of composition containing no other oxidative coloring agents, the system being able to produce a wide range of color shades by using other coloring agents. 28. A hair coloring composition comprising: (i) one or more generators selected from oxidising systems capable of undergoing a single electrophilic impact, and (ii) one or more copolymers selected A / from phenols and naphthols with a para-group to the hydroxy group, B / from 1,3-diketones containing a group Wherein Z is an active leaving group, C / containing a group in which Z is an active leaving group, and X is either an active leaving group or a non-leaving substituent, wherein in the presence of an oxidizing agent the generator or each reacts with the copolymer or each and X) when X is the active leaving group; and iii) an inorganic peroxide oxidizing agent, wherein the composition has a pH of at most 6. 29. A set of hair dye compositions comprising: Hair coloring composition according to claim 1, characterized in that one or more of the developers i) is selected from Ν, Ν-disubstituted p-phenylenediamines. 3. A hair coloring composition according to claim 1, wherein one or more of the developers i) is selected from a compound of the formula: And compounds of the formula wherein Y is selected from -NO ₂ , -COOH, -COOR, -COR and OH, and R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ independently of one another are selected from H, methyl, ethyl, n-propyl, i-propyl, F, Cl, OH, -COOH, -COOR, and -COR. Composition according to any one of the preceding claims, characterized in that one or more copolymers (A) are selected from compounds of the general formula wherein R ¹ , R ² , R ^{3 and} R ⁴ are independently selected from OH, H, methyl , ethyl, n-propyl, i-propyl, t-butyl, -COOH and -COR. Composition according to any one of the preceding claims, characterized in that compounds of the general formula (I) are chosen as the coupling agent (B) in which R ⁵ is methyl, ethyl, n-propyl, i-propyl, t-butyl or phenyl, and R 5. ⁶ is NR ₂ , wherein R 2 are independently methyl, ethyl, -propyl, i -propyl, t -butyl or phenyl, or R ⁵ is C 1-4 -alkyl and R ⁶ is C 1-4 -alkyl or C 1-4 -alkoxy. Composition according to any one of the preceding claims, characterized in that the compound (I) is selected from compounds having the general formula wherein R ⁷ and R ⁸ are independently methyl, ethyl, n-propyl, i-propyl, t- butyl, or 99 9 9 9 9 9 9 9 9 99 99 99 9 Substituted or unsubstituted phenyl. Composition according to any one of the preceding claims, characterized in that it comprises at least one type B / and / or at least one type C /. Composition according to any one of the preceding claims, characterized in that it comprises at least one type B / coupler. Composition according to any one of the preceding claims, characterized in that it comprises at least two type A /, B / and C / copolymers. Composition according to any one of the preceding claims, characterized in that it comprises at least one A /, B / and C / type copolymer. Composition according to any one of the preceding claims, characterized in that it contains the generator (i) in an amount of 0.01 to 7 wt. %, copolymer A / in an amount of 0.001 to 1 wt. % copolymer B / in an amount of 0.005 to 4 wt. %, and / or the copolymer C) in an amount of 0.01 to 4 wt. %. Composition according to any one of the preceding claims, characterized in that it contains only one developer compound (i). Composition according to any one of the preceding claims, characterized in that it comprises at most two copulators of each of types A (B) and (C). Composition according to any one of the preceding claims, characterized in that it contains at most 0.1 wt. % of an oxidative dye composition which is not of type (i), A (B) and (C). Composition according to any one of the preceding claims, characterized in that it contains at most 0.1 wt. % of an oxidative colorant which, under hair dyeing conditions, may undergo a reaction more than once. Composition according to any one of the preceding claims, characterized in that X in the copolymer (C) is a non-cleavable substituent. Composition according to any one of the preceding claims, characterized in that its pH is in the range of 1.5 to 5.8. Composition according to any one of the preceding claims, characterized in that it contains less than 0.3 wt. % ammonia. Composition according to any one of claims 1 to 16, characterized in that its pH is at least 6.1, more preferably 6.5. A composition according to any one of claims 1 to 16, characterized in that it contains ammonium ion or ammonium hydroxide in an amount of at least 0.01 wt. %. · · · · Φ ΦΦ ΦΦ 99 • • 99 99 99 99 99 99 99 99 99 99 99 99 99 99 A composition according to any one of the preceding claims, characterized in that it contains hydrogen peroxide as the oxidizing agent. Composition according to any one of the preceding claims, characterized in that it contains at most 0.1 wt. 0% of any oxidative dye that could react with itself under hair dyeing conditions. A composition according to any one of the preceding claims, characterized in that the developer molecules (i) react essentially only with the copolymer molecules A /, B / and / or C /, and not with the molecules of another developer, intended under hair dyeing conditions. 24. A set of hair dye compositions comprising: 3. The composition, kit, method and systemic method, characterized in that i) is selected from compounds containing a single primary amino group and only reacts at the site of the primary amino group under hair dyeing conditions.