Method for dyeing keratin fibers using self-oxidizing dyes and aliphatic di- or polyamino compounds

Abstract

The invention relates to a method for dyeing keratin fibers, in particular human hair, the dyeing process being induced by means of atmospheric oxygen, wherein the following are applied to the keratin fibers: - at least one self-oxidizing dye (SOF), and - at least one aliphatic di- or polyamino compound (DA) of formula (I) and / or the salt (I) thereof, in which R1 and R2 independently of one another represent a hydrogen atom, a C1-C6-alkyl group, or a hydroxy-C1-C6-alkyl group or R1 and R2, together with the two carbon atoms to which R1 and R2 are bonded, and the linker L form a 5 -, 6-, or 7-membered, saturated, carbocyclic or heterocyclic ring, L represents a direct bond or a saturated or unsaturated, linear or branched C1-C12-alkylene group, which may optionally also be substituted with one or more hydroxy groups and / or interrupted by one or more oxygen atoms and / or by one or more -NR3- groups, and R3 represents hydrogen, a C1-C6-alkyl group, a hydroxy-C1-C6-alkyl group, or an amino-C1-C6-alkyl group.

Description

[0001] Henkel AG & Co. KGaA

[0002] 2024P00325WO

[0003] Methods for dyeing keratinous fibers with self-oxidizing dyes and aliphatic di- or polyamino compounds

[0004] The present application is in the field of cosmetics and relates to a process for the atmospheric oxygen-induced coloring of keratinous fibers, in particular human hair, in which at least one self-oxidizing dye (SOF) and at least one aliphatic di- or polyamino compound (DA) of a specific formula (I) and / or its salt are applied to the keratinous fibers.

[0005] A second subject matter of the present application relates to a ready-to-use dye comprising at least one self-oxidizing dye (SOF) and at least one aliphatic diol or polyamino compound (DA) of formula (I) and / or its salt.

[0006] A third subject matter of the present application is the use of at least one aliphatic di- or polyamino compound (DA) of formula (I) and / or its salt for accelerating and / or enhancing the oxygen-induced formation of dyes starting from self-oxidizing dyes.

[0007] Altering the shape and color of keratin fibers, especially hair, is an important area of ​​modern cosmetics. Depending on the desired color, professionals are familiar with various dyeing systems for changing hair color. For permanent, intense colorations with good colorfastness and gray coverage, oxidation dyes are typically used. These dyes usually contain oxidation dye precursors, so-called developer components and coupler components, which react with oxidizing agents such as hydrogen peroxide to form the actual dyes. Oxidation dyes are characterized by very long-lasting color results.

[0008] Another oxidative dyeing process can be carried out using atmospheric oxygen as the sole oxidizing agent. In this process, oxidation dye precursors, which have a lower redox potential than the usual couplers and developers, are applied to the hair. Because the dye precursors of this class are extremely sensitive to oxidation and can even be oxidized in air, they are also referred to as self-oxidizing dyes (SOF). After application to the keratin fibers, the dyes are typically oxidized by atmospheric oxygen in an alkaline environment, subsequently forming deeply colored condensation or coupling products on the hair. Particularly well-known examples of this dye class are 5,6-dihydroxyindoline and 5,6-dihydroxyindole. Since dyes are based on indole or...Since indolin-based products also represent the precursors of the natural hair pigment melanin, they can restore the natural hair color to users with graying hair.

[0009] The oxidative coupling reaction typically occurs at alkaline pH values, so ready-to-use dyes are usually adjusted to a pH value between 9.5 and 10.5. For example, in publication WO 93 / 09759 A1, ammonia is used to adjust to an alkaline pH value of 9.5.

[0010] The use of a combination of 5,6-dihydroxyindoline with aliphatic monoamine compounds such as monoethanolamine, isopropanolamine, butylamine or benzylamine is also known from the publication EP 1 254 650 B1.

[0011] Document WO 99 / 66890 A1 describes hair dyes containing 5,6-dihydroxyindoline and amino acids or oligopeptides.

[0012] A long-standing disadvantage of all these air-oxidative dyeing processes is the very slow color development. Because atmospheric oxygen is a much weaker oxidizing agent than the hydrogen peroxide typically used, the air-oxidative coupling reaction takes hours or even several days. To achieve a dark shade on gray hair, multiple applications of the dye are therefore usually necessary, with the hair's shade gradually deepening with each application. The desired final color depth is only achieved with these dyes after several treatments. While some users appreciate a gradual and therefore more subtle color development, the majority want the final color result immediately after the first application and find the need for repeated applications inconvenient.However, when using atmospheric oxygen as an oxidizing agent, it has not been possible to obtain the final color result directly after the first application.

[0013] The objective of the present application was to find a method for dyeing keratin fibers using self-oxidizing dyes, which functions with atmospheric oxygen as the sole oxidizing agent and ensures rapid and complete color development. The desired color shade should be visible after a single application and, ideally, immediately after rinsing off the dye. This method should enable the dyeing of keratin fibers in the darkest and most intense colors possible. Surprisingly, it has now been shown that the acceleration of the atmospheric oxygen-induced dye formation reaction of self-oxidizing dyes is made possible by certain aliphatic di- or polyamino compounds of formula (I).

[0014] A first subject matter of the present application is therefore a method for the oxygen-induced dyeing of keratinous fibers, in particular human hair, in which the following are applied to the keratinous fibers:

[0015] - at least one self-oxidizing dye (SOF), and

[0016] - at least one aliphatic di- or polyamino compound (DA) of formula (I) and / or its salt where

[0017] R1 and R2 independently represent a hydrogen atom, a Ci-Ce alkyl group or a hydroxy-Ci-Ce alkyl group, or R1 and R2 together with the two carbon atoms to which they are bonded and the linker L form a 5-, 6- or 7-membered, saturated, carbocyclic or heterocyclic ring,

[0018] L represents a direct bond or a saturated or unsaturated, linear or branched Ci-Ci2 alkylene group, which may optionally be substituted with one or more hydroxyl groups and / or interrupted by one or more oxygen atoms and / or by one or more -NR3- groups, and

[0019] R3 represents a hydrogen atom, a Ci-Ce alkyl group, a hydroxy-Ci-Ce alkyl group, or an amino-Ci-Ce alkyl group.

[0020] It has been found that applying the combination of self-oxidizing dye (SOF) and aliphatic di- or polyamine compound (DA) of formula (I) to hair results in a significantly accelerated dye formation. A shade that normally develops over several days without the use of the di-Z-polyamine (DA) was achieved in its final color depth just one hour after dyeing with the di-Z-polyamine (DA). Furthermore, the color intensity could be increased even further by the combined application of the two components (SOF) and (DA). The fact that the oxidative coupling reaction of the self-oxidizing dyes (SOF) is not only accelerated but also intensified by the di- / polyamines (DA) was particularly surprising to the person skilled in the art.

[0021] Keratinous fibers

[0022] Keratinous fibers include hair, wool, and fur. Human hair is particularly often considered a keratinous fiber.

[0023] Method for atmospheric oxygen-induced coloring

[0024] In the inventive process for the oxygen-induced coloring of keratinous fibers, in particular human hair, the self-oxidizing dye(s) (SOF) and one or more aliphatic di- or polyamino compounds (DA) of formula (I) and / or their salts are applied to the keratinous fibers.

[0025] For the purposes of this application, a coloration induced by atmospheric oxygen is understood to mean that the oxygen contained in the air is used as the sole oxidizing agent.

[0026] Therefore, no oxidizing agents such as hydrogen peroxide and peroxodisulfates are used in the process according to the invention.

[0027] Therefore, the process is characterized by the fact that no composition containing one or more peroxo compounds is applied to the keratinous fibers.

[0028] The peroxo compounds can be inorganic or organic. The best-known inorganic peroxo compounds are hydrogen peroxide, ammonium peroxodisulfate, sodium peroxodisulfate, and potassium peroxodisulfate. Organic peroxo compounds include, for example, the adduct of hydrogen peroxide and urea, or benzoyl peroxide. None of these compounds are used in the process according to the invention.

[0029] Self-oxidizing dyes

[0030] In the process according to the invention, at least one self-oxidizing dye (SOF) is applied to the keratinous fibers or human hair.

[0031] Self-oxidizing dyes are aromatic compounds with more than two substituents on the ring. They possess a very low redox potential and are therefore oxidized even in air. To lower the redox potential, the aromatic ring of the self-oxidizing dye (SOF) carries several donor substituents, such as a hydroxyl group, a Ci-Ce alkoxy group, an amino group, a Ci-Ce alkylamino group, a Di-Ci-Ce alkylamino group, or even a Ci-Ce alkyl group or Ci-Ce alkylene group.

[0032] A self-oxidizing dye (SOF) within the meaning of the present application is therefore an oxidation dye precursor comprising an aromatic ring, in particular a benzene ring, from which at least three direct bonds extend to one or more oxygen atoms and / or nitrogen atoms.

[0033] The oxygen and / or nitrogen atoms are part of a substituent, which may be a hydroxyl group, a Ci-Ce alkoxy group, an amino group, a Ci-Ce alkylamino group, or a Di-Ce-Ce alkylamino group. For example, the aromatic ring of 5,6-dihydroxyindoline carries two hydroxyl groups and has a further direct bond to a nitrogen atom, which is bonded to a C2 alkylene group. This C2 alkylene group, in turn, forms a saturated five-membered ring with the nitrogen atom and the aromatic ring.

[0034] Indole derivatives with one or more hydroxy and / or amino groups also belong to the self-oxidizing dyes (SOF). Since indole is a particularly electron-rich heteroaromatic, even those indole derivatives substituted with at least one strong donor substituent, such as a hydroxyl group and / or an amino group, are readily oxidized by atmospheric oxygen.

[0035] Particularly suitable self-oxidizing dyes can be selected, for example, from the group consisting of 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid, 6-hydroxyindoline, 6-aminoindoline, 4-aminoindoline, 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, 5,6-dihydroxyindol-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole, and 4-aminoindole. 2,4-Trihydroxybenzene, aminoresorcinol, aminohydroquinone, diaminophenols and 3,4,5-trihydroxybenzoic acid.

[0036] In a particularly preferred embodiment, a process according to the invention is characterized in that the self-oxidizing dye (SOF) is selected from the group consisting of 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindoline, 6-aminoindoline, 4-aminoindoline, 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole, and 4-aminoindole. 1,2,4-Trihydroxybenzene, aminoresorcinol, aminohydroquinone, diaminophenols, 3,4,5-trihydroxybenzoic acid, and the physiologically acceptable salts of these compounds.

[0037] In a particularly preferred embodiment, a process according to the invention is characterized in that the self-oxidizing dye (SOF) is selected from the group consisting of 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 5,6-dihydroxyindol, N-methyl-5,6-dihydroxyindol, N-ethyl-5,6-dihydroxyindol, N-propyl-5,6-dihydroxyindol, N-butyl-5,6-dihydroxyindol, 1,2,4-trihydroxybenzene, aminoresorcinol, aminohydroquinone, diaminophenols, and the physiologically acceptable salts of these compounds.

[0038] The physiologically compatible salts of self-oxidizing dyes are salts suitable for use in cosmetic products (i.e., for application to human hair and skin). Particularly suitable physiologically compatible salts include, for example, the hydrobromides, hydrochlorides, hydrogen sulfates, and sulfates of these compounds.

[0039] The most preferred compound is 5,6-Dihydroxyindoline, which is particularly preferred in the form of its hydrobromide. Aliphatic di- or polyamino compounds (DA) of formula (I)

[0040] As a second essential component of the invention, at least one aliphatic di- or polyamino compound (DA) of formula (I) and / or its salt is applied to the keratinous fibers in the process according to the invention. where

[0041] R1 and R2 independently represent a hydrogen atom, a Ci-Ce alkyl group or a hydroxy-Ci-Ce alkyl group, or R1 and R2 together with the two carbon atoms to which they are bonded and the linker L form a 5-, 6- or 7-membered, saturated, carbocyclic or heterocyclic ring,

[0042] L represents a direct bond or a saturated or unsaturated, linear or branched Ci-Ci2 alkylene group, which may optionally be substituted with one or more hydroxyl groups and / or interrupted by one or more oxygen atoms and / or by one or more -NR3- groups, and R3 represents a hydrogen atom, a Ci-Ce alkyl group or a hydroxy-Ci-Ce alkyl group.

[0043] The di- or polyamine compound (DA) of formula (I) accelerates the atmospheric oxygen-induced oxidation of the self-oxidizing dyes (SOF), so that the development of the color, which takes place relatively slowly without the use of the di- or polyamines according to the invention, can be greatly accelerated.

[0044] As comparative tests have shown, the coupling rate to the dye is also increased, so that the final color development, for which the user usually has to wait several days when using a product without diamines or polyamines, could be accelerated to such an extent that the color development is complete as soon as rinsing or at the latest one hour after rinsing the dye.

[0045] The salts of the aliphatic di- or polyamino compound (DA) of formula (I) are preferably also physiologically compatible salts suitable for use in cosmetic products (i.e., for application to human hair and skin). Particularly suitable physiologically compatible salts include, for example, the hydrochlorides, hydrobromides, hydrogen sulfates, and sulfates of the compounds of formula (I).

[0046] The di- or polyamino compounds (DA) of formula (I) according to the invention are aliphatic, which means that their structure does not include an aromatic ring.

[0047] The R1 group is bonded to the CH group adjacent to the amino group. The R1 group represents a hydrogen atom, a Ci-Ce alkyl group, or a hydroxy-Ci-Ce alkyl group.

[0048] Examples of Ci-Ce alkyl groups include the methyl group, the ethyl group, the propyl group, the butyl group, the pentyl group, and the hexyl group. Examples of suitable hydroxy-C1-C6 alkyl groups include the 2-hydroxyethyl group, the 3-hydroxypropyl group, and the 2-hydroxypropyl group.

[0049] The R2 group is bonded to the CH group adjacent to the other amino group. The R2 group can be chosen independently of the R1 group and represents a hydrogen atom, a Ci-Ce alkyl group, or a hydroxy-Ci-Ce alkyl group.

[0050] The residues R1 and R2 independently represent a hydrogen atom, a Ci-Ce alkyl group, or a hydroxy-Ci-Ce alkyl group. Furthermore, the residues R1 and R2, together with the two carbon atoms to which they are bonded and the linker L, can also form a 5-, 6-, or 7-membered saturated, carbocyclic or heterocyclic ring.

[0051] Examples of carbocyclic saturated rings are a cyclopentyl ring, a cyclohexyl ring, and a cycloheptyl ring. Examples of heterocyclic saturated rings are a pyrrolidinyl ring, a piperidinyl ring, and an azepane ring.

[0052] The acceleration of the coupling reaction of the self-oxidizing dyes (SOF) worked particularly well when di- or polyamino compounds of formula (I) were used, in which the residues R1 and R2 independently represent a hydrogen atom or a methyl group. Restrictions R1 and R2 both represent a hydrogen atom are especially favored.

[0053] In a further particularly preferred embodiment, a method according to the invention is characterized in that at least one aliphatic di- or polyamino compound (DA) of formula (I) and / or its salt is applied to the keratinous fibers, wherein

[0054] R1 and R2 independently represent a hydrogen atom or a methyl group, preferably both representing a hydrogen atom.

[0055] In the structural diagram on the left, the left L is bound to the grouping H2N-CH(R1)-.

[0056] In the structural diagram on the right, the left L is bound to the grouping -CH(R2)-NH2.

[0057] In one embodiment, the linker represents a direct bond. If the linker L represents a direct bond, the di- or polyamino compound (DA) is a compound of the general formula (1a).

[0058] A suitable example is 1,2-diaminocyclohexane, which can alternatively be called 1,2-cyclohexanediamine. 1,2-Diaminocyclohexane contains two stereogenic centers, so that various stereoisomers exist. All stereoisomers are according to the invention. The isomer mixture has the CAS number 694-83-7. The trans isomer mixture has the CAS number 1121-22-8. The cis isomer has the CAS number 1436-59-5. The (1R,2R)-(-)-enantiomer has the CAS number 20439-47-8. The [(1S,2S)-(+)-enantiomer] has the CAS number 21436-03-3.

[0059] In 1,2-diaminocyclohexane, the residues R1 and R2, together with the carbon atoms to which they are bonded, form a 6-membered carbocyclic saturated ring. The linker L represents a direct bond.

[0060] In another embodiment, the linker L represents a saturated or unsaturated, linear or branched Ci-Ci2 alkylene group, which may optionally be substituted with one or more hydroxyl groups and / or interrupted by one or more oxygen atoms and / or by one or more groups -NR3-.

[0061] Examples of a linear Ci-Ci2 alkylene group are the methylene group (-CH2-), the ethylene group (-CH2-CH2-), the propylene group (-CH2-CH2-CH2-), the butylene group (-CH2-CH2-CH2-CH2-), the pentylene group (-CH2-CH2-CH2-CH2-CH2-) or the hexylene group (-CH2-CH2-CH2-CH2-CH2-CH2- )•

[0062] Examples of a well-suited branched C1-C12 alkylene group are the 1,1-dimethylmethylene group -C(CH3)2-, the 1-methylethylene group (-CH(CH3)-CH2-), the 2-methylethylene group (-CH2-CH(CH3)-), the 1-methylpropylene group (-CH(CH3)-CH2-CH2-), the 2-methylpropylene group (-CH2-CH(CH3)-CH2-), the 3-propylmethylene group (-CH2-CH2-CH(CH3)-), the 1,1-dimethylethylene group (-C(CH3)2-CH2), the 1,2-dimethylethylene group (-CH(CH3)-CH(CH3)-), the 2,2-dimethylethylene group (-CH2-C(CH3)2-), the 1,1 -Dimethylpropylene group (-C(CH3)-CH2-CH2-), the 1,2-dimethylpropylene group (-CH(CH3)-CH(CH3)-CH2-), the 1,3-dimethylpropylene group (-CH(CH3)-CH2-CH(CH3)-), the 2,2-dimethylpropylene group (-CH2-C(CH3)2-CH2-), the 1-ethylethylene group (-CH(CH2CH3)-CH2-), the 2-ethylethylene group (-CH2-CH(CH2CH3)-), the 1-ethylpropylene group, (-CH(CH2CH3)-CH2-CH2-), the 2-ethylpropylene group (-CH2-CH(CH2CH3)-CH2-) and the 3-ethylpropylene group (-CH2-CH2-CH(CH2CH3)-).

[0063] The saturated or unsaturated, linear or branched Ci-Ci2 alkylene group can also bear one or more hydroxyl groups. Examples include the groups -CH(OH)-, -CH(OH)-CH2-, -CH2-CH(OH)-, -CH2-CH(OH)-CH2-, -CH(OH)-CH(OH)-, -CH2-CH(OH)-CH2- and -CH(OH)-CH(OH)-CH(OH).

[0064] The linker L can also represent a saturated or unsaturated, linear or branched C1-C12 alkylene group interrupted by one or more oxygen atoms. Examples include the group -CH2-O-CH2-, -CH2-O-CH2-CH2-O-CH2-, -CH2-O-CH2-CH2-O-CH2-, and -CH2-CH2-O-CH2-CH2-. The linker L can also represent a saturated or unsaturated, linear or branched C1-C12 alkylene group interrupted by one or more -NR3- groups. The R3 group represents a hydrogen atom, a Ci-Ce alkyl group, a hydroxy-Ci-Ce alkyl group, or an amino-Ci-Ce alkyl group. Examples of suitable Ci-Ce alkyl groups and hydroxy-Ci-Ce alkyl groups have already been mentioned.

[0065] Examples of suitable amino-O-ce alkyl groups are the 2-aminoethyl group, the 3-aminopropyl group, the 2-aminopropyl group, and the 4-aminobutyl group. The 2-aminoethyl group and the 3-aminopropyl group are particularly preferred.

[0066] The residue R3 is particularly preferred to represent a hydrogen atom, a methyl group, a 2-aminoethyl group or a 3-aminopropyl group.

[0067] Examples include a grouping -CH2-NH-CH2-, a grouping -CH2-NH-CH2- CH2-NH-CH2-, a grouping -CH2-NH-CH2-CH2-NH-CH2-CH2-NH-CH2, a grouping -CH2- NH-CH2-CH2-NH-CH2-CH2-NH-CH2-, a grouping -CH2-CH2-NR3-CH2-CH2- and a grouping -CH2-CH2-CH2-NR3-CH2-CH2-CH2-.

[0068] In a further particularly preferred embodiment, a method according to the invention is characterized in that at least one aliphatic di- or polyamino compound (DA) of formula (I) and / or its salt is applied to the keratinous fibers, wherein

[0069] L for a saturated, linear Ci-Ci2 alkylene group, a saturated, branched

[0070] C3-Ci2 alkylene group, a group -CH(OH)-, a group -CH2- CH(OH)-CH2-, a group -CH2-O-CH2-, a group -CH2-O- CH2-CH2-O-CH2-, a group -CH2-O-CH2-CH2-O-CH2-CH2-O-CH2-, a group -CH2-CH2-O-CH2-CH2-, a group -CH2-NH- CH2-, a group -CH2-NH-CH2-CH2-NH-CH2, a group -CH2-NH-CH2-CH2-NH-CH2-CH2-NH-CH2, a group -CH2-NH-CH2-CH2-NH-CH2-CH2-NH-CH2-, a group -CH2-NH-CH2-CH2-NH-CH2-, a group -CH2-CH2-NR3-CH2-CH2- or a group -CH2-CH2-CH2-NR3-CH2-CH2-CH2- stands.

[0071] In a further particularly preferred embodiment, a method according to the invention is characterized in that at least one aliphatic di- or polyamino compound (DA) of formula (I) and / or its salt is applied to the keratinous fibers, wherein

[0072] L a grouping -CH2-NR3-CH2- or a grouping -CH2-CH2-NR3-

[0073] CH2-CH2- stands, and

[0074] R3 represents a 2-aminoethyl group or a 3-aminopropyl group. The aliphatic di- or polyamino compounds of formula (I) selected from the group consisting of 1,6-diaminohexane, 1,5-diaminopentane, 1,4-diaminobutane, 1,3-diaminopropane, 1,8-diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane, 1,5-diamino-2-methylpentane, 1,3-diaminopentane, 1,3-diamino-2,2-dimethylpropane, 1,3-diamino-2-propanol, 2-(2-aminoethoxy)ethylamine, 2,2'-(ethylenedioxy)diethylamine, bis(3-aminopropyl) ether, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine have proven to be particularly well suited for solving the problem described in the invention. Tris(3-aminopropyl)amine, Tris(2-aminoethyl)amine and the salts of these compounds.

[0075] 1,6-Diaminohexane has the CAS number 124-09-4.

[0076] In 1,6-diaminohexane, residues R1 and R2 both represent a hydrogen atom, and the linker L represents a butylene group (-CH2-CH2-CH2-CH2-). 1,6-Diaminohexane is the most favored form.

[0077] 1,5-Diaminopentane has the CAS number 462-94-2.

[0078] In 1,5-diaminopentane, the residues R1 and R2 both represent a hydrogen atom, and the linker L represents a propylene group (-CH2-CH2-CH2-).

[0079] 1,4-Diaminobutane has the CAS number 1 10-60-1 .

[0080] In 1,4-diaminobutane, the residues R1 and R2 both represent a hydrogen atom, and the linker L represents an ethylene group (-CH2-CH2-).

[0081] 1,3-Diaminopropane has the CAS number 109-76-2.

[0082] In 1,3-diaminopropane, the residues R1 and R2 both represent a hydrogen atom, and the linker L represents a methylene group (-CH2-).

[0083] 1,8-Diaminooctane has the CAS number 373-44-4.

[0084] In 1,3-diaminopropane, the residues R1 and R2 both represent a hydrogen atom, and the linker L represents a hexamethylene group.

[0085] 1,10-Diaminodecane has the CAS number 646-25-3.

[0086] In 1,3-diaminopropane, the residues R1 and R2 both represent a hydrogen atom, and the linker L represents an octamethylene group.

[0087] 1,12-Diamino-dodecane has the CAS number 2783-17-7.

[0088] In 1,12-diaminododecane, the residues R1 and R2 both represent a hydrogen atom, and the linker L represents a decamethylene group.

[0089] 1,5-Diamino-2-methyl-pentane has the CAS number 15520-10-2. In 1,5-Diamino-2-methyl-pentane, the residues R1 and R2 both represent a hydrogen atom, and the linker L represents the branched alkylene group -CH(CH3)-CH2-CH2-.

[0090] 1,3-Diaminopentane has the CAS number 589-37-7.

[0091] 1,3-Diaminopentane: In this system, R1 represents an ethyl group and R2 a hydrogen atom. The linker L represents a methylene group (-CH2-).

[0092] 1 .3-Diamino-2,2-dimethylpropane has the CAS number 7328-91-8.

[0093] In 1,3-Diamino-2,2-dimethylpropane, the residues R1 and R2 both represent a hydrogen atom, and the linker L represents the branched alkylene group -C(CH3)2-.

[0094] 1 .3-Diamino-2-propanol has the CAS number 616-29-5.

[0095] In 1,3-diamino-2-propanol, the residues R1 and R2 both represent a hydrogen atom, and the linker L represents a group -CH(OH)-

[0096] 2-(2-Aminoethoxy)ethylamine has the CAS number 2752-17-2.

[0097] In 2-(2-Aminoethoxy)ethylamine, the residues R1 and R2 both represent a hydrogen atom, and the linker L represents a group -CH2-O-CH2-. The compound can be used either in its pure form or as its dihydrochloride.

[0098] 2,2'-(Ethylenedioxy)diethylamine has the CAS number 929-59-9.

[0099] In - 2,2'-(ethylenedioxy)diethylamine, the residues R1 and R2 both represent a hydrogen atom, and the linker L represents a group -CH2-O-CH2-CH2-O-CH2-.

[0100] Bis(3-Aminopropyl) ether has the CAS number 2157-24-6.

[0101] In bis(3-aminopropyl)ether, both residues R1 and R2 represent a hydrogen atom, and the linker L represents a group -CH2-CH2-O-CH2-CH2-.

[0102] Diethylenetriamine has the CAS number 1 11 -40-0.

[0103] In diethylenetriamine, both residues R1 and R2 represent a hydrogen atom, and the linker L represents a group -CH2-HN-CH2-.

[0104] Triethylenetetramine has the CAS number 1 12-24-3.

[0105] In triethylenetetramine, the R1 and R2 groups both represent a hydrogen atom, and the linker L represents a group -CH2-NH-CH2-CH2-NH-CH2-. Triethylenetetramine can also be used in the form of its dihydrochloride, which has the CAS number 38260-01-4.

[0106] Tetraethylenepentamine has the CAS number 112-57-2. In tetraethylenepentamine, both residues R1 and R2 represent a hydrogen atom, and the linker L represents a group -CH2-NH-CH2-CH2-NH-CH2-CH2-NH-CH2-.

[0107] Tris(3-aminopropyl)amine has the CAS number 4963-47-7.

[0108] In Tris(3-aminopropyl)amine, both residues R1 and R2 represent a hydrogen atom, and the linker L represents a group -CH2-CH2-NR3-CH2-CH2-, where the residue R3 represents a 3-aminopropyl group.

[0109] Tris(2-aminoethyl)amine has the CAS number 4097-89-6.

[0110] In Tris(2-aminoethyl)amine, both residues R1 and R2 represent a hydrogen atom, and the linker L represents a group -CH2-NR3-CH2, where the residue R3 represents a 2-aminoethyl group.

[0111] In a further particularly preferred embodiment, a process according to the invention is characterized in that at least one aliphatic di- or polyamino compound (DA) of formula (I) is applied to the keratinous fibers, which is selected from the group consisting of 1,6-diaminohexane, 1,5-diaminopentane, 1,4-diaminobutane, 1,3-diaminopropane, 1,8-diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane, 1,5-diamino-2-methylpentane, 1,3-diaminopentane, 1,3-diamino-2,2-dimethylpropane, 1,3-diamino-2-propanol, 2-(2-aminoethoxy)ethylamine, 2,2'-(ethylenedioxy)diethylamine, bis(3-aminopropyl) ether, diethylenetriamine, Triethylenetetramine, tetraethylenepentamine, tris(3-aminopropyl)amine, tris(2-aminoethyl)amine and their salts.

[0112] Particularly strong color intensification starting from 5,6-dihydroxyindoline was obtained with 1,6-diaminohexane. For this reason, a process in which 1,6-diaminohexane is applied to the keratinous fibers is most preferred.

[0113] A method in which 1,6-diaminohexane in combination with 5,6-dihydroxyindoline or a salt thereof is applied to the keratinous fibers is also explicitly preferred.

[0114] Molar ratio of self-oxidizing dyes (SOF) to aliphatic di- or polyamines (DA): When applied to keratin fibers, the aliphatic di- or polyamines (DA) interact with the self-oxidizing dyes (SOF). One result of this interaction is the acceleration and enhancement of the atmospheric oxygen-induced dye formation reaction.

[0115] The experiments leading to this invention showed that the extent and speed of dye formation also depend on the molar ratio in which the self-oxidizing dye(s) (SOF) and the aliphatic diamine or polyamine(s) (DA) are used. A very good increase in dye development was already achieved when the molar ratio of the self-oxidizing dye(s) (SOF) applied to the fibers to the diamine or polyamine(s) (DA) of formula (I), i.e., the molar ratio (SOF) / (DA), was in the range of 4:1 to 1:4. Further adjustment of the molar ratio allowed the color intensity to be increased even more.For this reason, it is particularly preferred if the self-oxidizing dye(s) (SOF) and the di- or polyamine(s) (DA) of formula (I) are applied to the fibers in a molar ratio (SOF) / (DA) in the range of 4:1 to 1:4, preferably 3:1 to 1:3, more preferably 2.5:1 to 1:2.5, even more preferably 1:1 to 1:2.5 and most preferably 1:1.5 to 1:2.5.

[0116] In a further particularly preferred embodiment, a method according to the invention is characterized in that the self-oxidizing dye(s) (SOF) and the di- or polyamine(s) (DA) of formula (I) are applied to the keratinous fibers in such quantities that the molar ratio of (SOF) / (DA) is in the range of 4:1 to 1:4, preferably 3:1 to 1:3, more preferably 2.5:1 to 1:2.5, even more preferably 1:1 to 1:2.5 and most preferably 1:1.5 to 1:2.5.

[0117] In the particularly preferred molar ratio (SOF) / (DA) of 1 :1 ,5 to 1 :2.5, the diamine(s) (DA) are applied to the keratinous fibers in a 1.5-fold to 2.5-fold molar excess compared to the self-oxidizing dyes (SOF).

[0118] If, for example, the self-oxidizing dyes are applied to the keratin fibers in a total molar amount of 4 mmol (millimoles), then the total molar amount of the aliphatic di-Z-polyamines (DA) of formula (I) applied to the keratin fibers is most preferably 6 to 10 mmol (millimoles).

[0119] Application of (SOF) and (DA)

[0120] In the process according to the invention, both the self-oxidizing dye(s) (SOF) and the aliphatic di- or polyamino compound(s) (DA) of formula (I) are applied to the keratinous fibers.

[0121] It has been found that the reaction between diamine (DA) and self-oxidizing dyes (SOF) begins directly upon contact between the two components.

[0122] Since the formation of the dyes is intended to begin only during or shortly after the application of the two components to the keratin fibers, it has proven particularly advantageous to package the self-oxidizing dye(s) (SOF) and the aliphatic diol or polyamino compound (DA) of formula (I) separately in two different containers. Shortly before application, a ready-to-use agent is then prepared by mixing the two components and applied to the keratin fibers.

[0123] In a further particularly preferred embodiment, a method according to the invention is therefore characterized in that the self-oxidizing dye(s) (SOF) and the diol or polyamino compound(s) (DA) of formula (I) are provided in separate containers and mixed to form a ready-to-use agent before application.

[0124] For this purpose, both components are particularly preferably incorporated into two different cosmetic products (A) and (B).

[0125] A method for the oxygen-induced dyeing of keratinous fibers, especially human hair, is therefore particularly preferred, in which the following are applied to the keratinous fibers:

[0126] - a first composition (A) containing at least one self-oxidizing dye (SOF), and

[0127] - a second composition (B) containing at least one aliphatic di- or polyamino compound (DA) of formula (I) and / or its salt, wherein the two compositions (A) and (B) are provided in separate containers and mixed to form a ready-to-use product (AB) prior to use.

[0128] The ready-to-use dye preferably contains the self-oxidizing dyes in specific quantity ranges. Particularly good results were obtained when the ready-to-use dye – based on the total weight of the ready-to-use dye – contained one or more self-oxidizing dyes (SOF) in a total amount of 0.01 to 10.5 wt.%, preferably 0.1 to 5.0 wt.%, more preferably 0.2 to 2.0 wt.%, even more preferably 0.3 to 1.8 wt.%, and most preferably 0.6 to 1.4 wt.%.

[0129] It is known to those skilled in the art that the intensity of a developed color shade also depends on the amount of self-oxidizing dyes used in the ready-to-use product.

[0130] If the expert desires a particularly dark shade, he will increase the amount of (SOF) accordingly.

[0131] However, it has been found that the color intensity is only proportional to the amount of SOF used up to a certain limit. The tests showed that the shade achieved on the keratin fibers became darker when the amount of SOF used was increased from 0.5 wt% to 1.0 wt% (based on the total weight of the ready-to-use product). At a quantity of 1.0 wt%, however, the keratin fibers were already so darkly colored that a further increase in the amount of SOF to 1.5 wt% did not result in any further significant increase in color intensity. For this reason, it is preferred if the ready-to-use dye – based on the total weight of the ready-to-use dye – contains one or more self-oxidizing dyes (SOF) in a total amount of 0.01 to 10.5 wt.%, preferably 0.1 to 5.0 wt.%, more preferably 0.2 to 2.0 wt.%, and even more preferably 0.3 to 1.8 wt.%.-% and most preferably contains 0.6 to 1.4 wt. %.

[0132] In a further particularly preferred embodiment, a method according to the invention is characterized in that the ready-to-use dyeing agent - based on the total weight of the ready-to-use dyeing agent - contains one or more self-oxidizing dyes (SOF) in a total amount of 0.01 to 10.5 wt.%, preferably 0.1 to 5.0 wt.%, more preferably 0.2 to 2.0 wt.%, even more preferably 0.3 to 1.8 wt.% and most preferably 0.6 to 1.4 wt.%.

[0133] In a further explicitly preferred embodiment, a method according to the invention is characterized in that the ready-to-use dyeing agent contains 0.01 to 10.5 wt.%, preferably 0.1 to 5.0 wt.%, more preferably 0.2 to 2.0 wt.%, even more preferably 0.3 to 1.8 wt.% and most preferably 0.6 to 1.4 wt.% 5,6-dihydroxyindoline hydrobromide.

[0134] Furthermore, a particularly large increase in color intensity and acceleration of the atmospheric oxygen-induced coupling reaction was achieved when the ready-to-use dye – based on the total weight of the ready-to-use dye – contained one or more di- or polyamines (DA) of formula (I) in a total amount of 0.01 to 20.0 wt.%, preferably 0.1 to 10.0 wt.%, more preferably 0.15 to 5.0 wt.% and most preferably 0.4 to 3.0 wt.%, still more preferably 0.5 to 2.0 wt.% and most preferably 0.6 to 1.4 wt.%.

[0135] In a further particularly preferred embodiment, a method according to the invention is therefore characterized in that the ready-to-use dyeing agent - based on the total weight of the ready-to-use dyeing agent - contains one or more di- or polyamines (DA) of formula (I) in a total amount of 0.01 to 20.0 wt.%, preferably 0.1 to 10.0 wt.%, more preferably 0.15 to 5.0 wt.% and most preferably 0.4 to 3.0 wt.%, even more preferably 0.5 to 2.0 wt.% and most preferably 0.6 to 1.4 wt.%.As previously described, it is also particularly advantageous if the ready-to-use agent contains the self-oxidizing dye(s) (SOF) and the di- or polyamine(s) (DA) of formula (I) in such amounts that the molar ratio of (SOF) / (DA) is in the range of 4:1 to 1:4, preferably 3:1 to 1:3, more preferably 2.5:1 to 1:2.5, even more preferably 1:1 to 1:2.5 and most preferably 1:1.5 to 1:2.5.

[0136] The ready-to-use dye preferably contains water. The pH of the ready-to-use dye is preferably adjusted to a range of 4.0 to 12.0, more preferably 4.7 to 11.5, more preferably 6.5 to 10.0, and most preferably 8.0 to 10.5.

[0137] In a further particularly preferred embodiment, a method according to the invention is characterized in that the ready-to-use dye contains water and has a pH value of 4.0 to 12.0, preferably 4.7 to 11.5, more preferably 6.5 to 10.0 and most preferably 8.0 to 10.5.

[0138] Abstaining from oxidizing agents other than atmospheric oxygen and aromatic diamino compounds

[0139] As previously described, atmospheric oxygen-induced oxidative coloring is understood to mean that the oxygen contained in the air is used as the sole oxidizing agent. Therefore, no oxidizing agents such as hydrogen peroxide and peroxodisulfates are used in the process according to the invention.

[0140] The method according to the invention is therefore preferably characterized in that no composition containing one or more peroxo compounds is applied to the keratinous fibers in the process.

[0141] According to the invention, the term peroxo compounds refers to inorganic and organic compounds characterized by the presence of a peroxy group. The oxygen atoms in these peroxo compounds typically have an oxidation state of -1.

[0142] Peroxo compounds within the meaning of the invention are therefore the compounds of the general formula (0-1)

[0143] Ro-| OO R02 (0-1) where the substituents Ro1 and Ro2 represent a hydrogen atom, an inorganic substituent or an organic substituent.

[0144] Peroxo compounds are oxidizing agents commonly used in oxidative hair coloring to initiate the reaction between developer and coupler that leads to the formation of the dyes.

[0145] The most commonly used peroxide compound in oxidative hair coloring is hydrogen peroxide (with Ro1 and Ro2 being equivalent to hydrogen).

[0146] Another peroxo compound very frequently used in oxidative hair coloring is potassium persulfate (also known as potassium peroxodisulfate), sodium persulfate (also known as sodium peroxodisulfate), and ammonium persulfate (also known as ammonium peroxodisulfate). In the case of the persulfates, the Ro1 and Ro2 residues each represent an -SO3- residue, with the negative charge being neutralized by the presence of the corresponding cations.

[0147] Peroxy compounds also used in some oxidative hair dyes include percarbonates such as sodium percarbonate, potassium percarbonate, and magnesium percarbonate.

[0148] Percarbonates are adducts of hydrogen peroxide to the corresponding carbonates; for example, sodium percarbonate is the adduct of hydrogen peroxide to sodium percarbonate. Thus, percarbonates are also peroxo compounds, with hydrogen peroxide being the underlying percarbonate compound.

[0149] In one embodiment, the colors can be formed exclusively by the self-oxidizing dyes, thus eliminating the need for further developer- or coupler-type oxidation dyes. Developer-type oxidation dyes are, in particular, aromatic diamino compounds. Therefore, it may be preferable to omit developer-type and / or coupler-type oxidation dye precursors.

[0150] In a further preferred embodiment, a method according to the invention is characterized in that no composition containing one or more aromatic diamino compounds is applied to the keratinous fibers in the method.

[0151] Aromatic diamino compounds of the developer type can alternatively also be referred to as p-phenylenediamines. Examples of such compounds are p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N,N-dimethyl-p-phenylenediamine, N,N-diethyl-p-phenylenediamine, N,N-dipropyl-p-phenylenediamine, 4-amino-3-methyl-(N,N-diethyl)aniline, N,N-bis-(β-hydroxyethyl)-p-phenylenediamine, 4-N,N-bis-(β-hydroxyethyl)-amino-2-methylaniline, 4-N,N-bis-(β-hydroxyethyl)-amino-2-chloroaniline, 2-(β-hydroxyethyl)-p- phenylenediamine, 2-(a,ß-dihydroxyethyl)-p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N-(ß-hydroxypropyl)-p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N,N-dimethyl-3-methyl-p-phenylenediamine, N,N-(Ethyl,ß-hydroxyethyl)-p-phenylenediamine, N-(ß,y-dihydroxypropyl)-p-phenylenediamine, N-(4'-aminophenyl)-p-phenylenediamine,N-Phenyl-p-phenylenediamine, 2-(β-Hydroxyethyloxy)-p-phenylenediamine, 2-Methoxymethyl-p-phenylenediamine, 2-(β-Acetylaminoethyloxy)-p-phenylenediamine, N-(β-Methoxyethyl)-p-phenylenediamine, N-(4-Amino-3-methylphenyl)-N-[3-(1 H-imidazol-1-yl)propyl]amine, 5,8-Diaminobenzo-1,4-dioxane and their physiologically acceptable salts.

[0152] Preferred dinuclear developer components of formula (E2) are selected in particular from at least one of the following compounds: N,N'-bis-(β-hydroxyethyl)-N,N'-bis-(4'-aminophenyl)-1,3-diamino-propan-2-ol, N,N'-bis-(β-hydroxyethyl)-N,N'-bis-(4'-aminophenyl)-ethylenediamine, N,N'-bis-(4'-aminophenyl)-tetramethylenediamine, N,N'-bis-(β-hydroxyethyl)-N,N'-bis-(4'-aminophenyl)-tetramethylenediamine, N,N'-bis-(4-(methylamino)phenyl)-tetramethylenediamine, N,N'-diethyl-N,N'-bis-(4'-amino-3'-methylphenyl)-ethylenediamine, bis-(2-hydroxy-5-aminophenyl)-methane, N,N'-Bis-(4'-aminophenyl)-1,4-diazacycloheptane, N,N'-Bis-(2-hydroxy-5-aminobenzyl)-piperazine, N-(4'-Aminophenyl)-p-phenylenediamine and 1,10-Bis-(2',5'-diaminophenyl)-1,4,7,10-tetraoxadecane and their physiologically acceptable salts.

[0153] The process according to the invention is therefore preferably characterized in that no composition is applied to the keratinous fibers which contains one or more compounds from the group consisting of p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N,N-dimethyl-p-phenylenediamine, N,N-diethyl-p-phenylenediamine, N,N-dipropyl-p-phenylenediamine, 4-amino-3-methyl-(N,N-diethyl)aniline, N,N-bis-(β-hydroxyethyl)-p-phenylenediamine, 4-N,N-bis-(β-hydroxyethyl)-amino-2-methylaniline. 4-N,N-Bis-(ß-hydroxyethyl)-amino-2-chloroaniline, 2-(ß-hydroxyethyl)-p-phenylenediamine, 2-(a,ß-dihydroxyethyl)-p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N-(ß-hydroxypropyl)-p- phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N,N-dimethyl-3-methyl-p-phenylenediamine, N,N-(ethyl,ß-hydroxyethyl)-p-phenylenediamine, N-(ß,Contains γ-Dihydroxypropyl)-p-phenylenediamine, N-(4'-Aminophenyl)-p-phenylenediamine, N-Phenyl-p-phenylenediamine, 2-(β-Hydroxyethyloxy)-p-phenylenediamine, 2-Methoxymethyl-p-phenylenediamine, 2-(β-Acetylaminoethyloxy)-p-phenylenediamine, N-(β-Methoxyethyl)-p-phenylenediamine, N-(4-Amino-3-methylphenyl)-N-[3-(1 H-imidazol-1- yl)propyl]amine, 5,8-Diaminobenzo-1,4-dioxane and their salts.

[0154] The use of oxidation dye precursors from the group of p-aminophenols can also be omitted. The process according to the invention is therefore preferably characterized in that no composition is applied to the keratinous fibers which contains one or more compounds from the group consisting of p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-(β-hydroxyethoxy)phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(β-hydroxyethyl-aminomethyl)phenol, 4-amino-2-(α,β-dihydroxyethyl)phenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol, 4-amino-2,6-dichlorophenol. Contains 4-Amino-2-(diethyl-aminomethyl)-phenol and its salts.

[0155] The use of oxidation dye precursors from the group of heterocyclic developers is also preferably avoided.

[0156] The process according to the invention is therefore preferably characterized in that no composition is applied to the keratinous fibers which contains one or more compounds from the group consisting of 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1-(4'-chlorobenzyl)pyrazole,

[0157] 4.5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole,

[0158] 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1-(ß-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3-(4'- methoxyphenyl)-pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1 -isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5-(ß-aminoethyl)amino-1 ,3-dimethylpyrazole and their salts.

[0159] The use of coupler-type oxidation dyes can also be avoided.

[0160] In a further embodiment, the process according to the invention is therefore characterized in that no composition is applied to the keratinous fibers which contains one or more compounds from the group consisting of 2-methylresorcinol, 4-chlororesorcinol, resorcinol, 1-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, 2-chloro-6-methyl-3-aminophenol, and 2,6-dihydroxy-3,4-dimethylpyridine and the salts thereof. Further optional components in compositions (A) and (B) and / or in the ready-to-use dye are also excluded.

[0161] The agents (A) and / or (B) and / or the ready-to-use dye (AB) may optionally also contain further active ingredients, excipients and additives, such as non-ionic, cationic, anionic, zwitterionic and / or amphoteric surfactants, fatty substances such as fatty alcohols, fatty acid triglycerides or hydrocarbons, non-ionic polymers such as vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymers, polyethylene glycols and polysiloxanes;Additional silicones such as volatile or non-volatile, straight-chain, branched or cyclic, cross-linked or non-cross-linked polyalkylsiloxanes (such as dimethicone or cyclomethicone), polyarylsiloxanes and / or polyalkylarylsiloxanes, in particular polysiloxanes with organofunctional groups, such as substituted or unsubstituted amines (amodimethicone), carboxyl, alkoxy and / or hydroxyl groups (dimethicone copolyols), linear polysiloxane(A)-polyoxyalkylene(B) block copolymers, grafted silicone polymers; cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallylammonium chloride polymers;

[0162] Copolymers, dimethylamino-ethyl methacrylate-vinylpyrrolidinone copolymers quaternated with diethyl sulfate, vinylpyrrolidinone-imidazolinium methochloride copolymers, and quaternized polyvinyl alcohol; zwitterionic and amphoteric polymers; anionic polymers such as polyacrylic acids or cross-linked polyacrylic acids; structuring agents such as glucose, maleic acid, and lactic acid; hair-conditioning compounds such as phospholipids, for example, lecithin and cephalins; perfume oils, dimethyl isosorbide, and cyclodextrins; fiber-improving agents, in particular mono-, di-, and oligosaccharides such as glucose, galactose, fructose, and lactose; colorants for coloring the product; anti-dandruff agents such as piroctone olamines, zinc omadine, and climbazole; amino acids and oligopeptides; Protein hydrolysates of animal and / or plant origin, as well as in the form of their fatty acid condensation products or, where applicable, anionically or cationically modified derivatives;Vegetable oils; sunscreens and UV blockers; active ingredients such as panthenol, pantothenic acid, pantolactone, allantoin, pyrrolidone carboxylic acids and their salts, and bisabolol; polyphenols, in particular hydroxycinnamic acids, 6,7-dihydroxycoumarins, hydroxybenzoic acids, catechins, tannins, leucoanthocyanidins, anthocyanidins, flavanones, flavones, and flavonols; ceramides or pseudoceramides; vitamins, provitamins, and vitamin precursors; plant extracts; fats and waxes such as fatty alcohols, beeswax, montan wax, and paraffins; swelling and penetrating agents such as glycerin, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas, and primary, secondary, and tertiary phosphates; opacifying agents such as latex, styrene / PVP, and styrene / acrylamide copolymers; Pearlescent agents such as ethylene glycol mono- and distearate as well as PEG-3 distearate;Pigments and propellants such as propane-butane mixtures, N₂O, dimethyl ether, CO₂, and air. The selection of these additional substances will be made by a person skilled in the art according to the desired properties of the composition. Regarding further optional components and the quantities of these components used, explicit reference is made to the relevant handbooks known to those skilled in the art. The additional active ingredients and excipients are preferably used in the compositions according to the invention in quantities of 0.0001 to 25 wt.% each, in particular from 0.0005 to 15 wt.%, based on the total weight of the application mixture. Ready-to-use coloring agent;

[0163] As previously described, it has proven particularly advantageous to package the self-oxidizing dye(s) (SOF) and the aliphatic di- or polyamino compound (DA) of formula (I) separately in two different containers. Shortly before application, a ready-to-use agent is then prepared by mixing the two components, which is then applied to the keratinous fibers.

[0164] A second subject matter of the present application is therefore a ready-to-use agent for dyeing keratinous fibers, in particular human hair, comprising

[0165] - at least one self-oxidizing dye (SOF), and

[0166] - at least one aliphatic di- or polyamino compound (DA) of formula (I) and / or its salt, wherein the self-oxidizing dye (SOF), the aliphatic di- or polyamino compound (DA) of formula (I) and / or its salts and the ready-to-use agent have already been disclosed in detail in the description of the first subject matter of the invention.

[0167] In particular, the ready-to-use dye is preferably characterized by the fact that it

[0168] - does not contain a peroxo compound, and / or

[0169] - contains no aromatic diamino compounds.

[0170] As previously described, peroxo compounds are understood to be various oxidizing agents of atmospheric oxygen.

[0171] Regarding the other preferred embodiments of the ready-to-use dye according to the invention, what has been said about the method according to the invention applies mutatis mutantis.

[0172] Use of the aliphatic di- or polyamino compound (DA) of formula (I)

[0173] A third subject matter of the present application is the use of at least one aliphatic di- or polyamino compound (DA) of formula (I) and / or its salt for accelerating and / or enhancing the oxygen-induced formation of dyes starting from self-oxidizing dyes, wherein the self-oxidizing dye(s) are preferably selected from the group consisting of 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid, 6-hydroxyindoline, 6-aminoindoline, 4-aminoindoline, 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole, 1,2,4-trihydroxybenzene, aminoresorcinol.Aminohydroquinone, diaminophenols, 3,4,5-trihydroxybenzoic acid and the physiologically acceptable salts of these compounds.

[0174] The aliphatic di- or polyamino compounds (DA) of formula (I) have already been disclosed in detail in the description of the first subject matter of the invention.

[0175] Regarding the other preferred embodiments of the use according to the invention, what has been said about the method according to the invention applies mutatis mutantis.

[0176] Examples

[0177] 1. Production of the ready-to-use dyes (A)

[0178] The following ready-to-use dyes were produced (all values ​​are in wt.% unless otherwise stated):

[0179] Table 1

[0180] 5.6-Dihydroxyindoline (hydrobromide) molecular weight = 232.077 g / mol

[0181] 1,6-Diaminohexane Molecular weight = 116.21 g / mol

[0182] The specified amount of 5,6-dihydroxyindoline (hydrobromide) was dissolved in a buffer solution adjusted to a pH of 10.0. Shortly before use, the specified amount of 1,6-diaminohexane was added, and the solution was made up to 100% by weight with distilled water.

[0183] Analogous to the series of experiments with 0.5 wt% 5,6-dihydroxyindoline (hydrobromide) shown in Table 1, two further series of experiments were carried out with 1.0 wt% and 1.5 wt% dihydroxyindoline (hydrobromide) (Tables 2 and 3).

[0184] Table 2

[0185] Table 3

[0186] 2. Application to hair strands

[0187] To remove any remaining residue (moth powder, preservatives, etc.), strands of hair (Kerling Euronaturhaar white) were pre-washed with a commercially available shampoo (Schauma 7 Herbs), rinsed with water, and then dried. The cleaned strands were stored for at least 72 hours. The ready-to-use dye prepared in step 1 was applied to one strand of hair at a time (volume ratio 1.6 g dye to 0.4 g hair strand) and left to act for 10 minutes. The dye was then rinsed out under running water, and the hair strand was air-dried. The color result was visually assessed under a daylight lamp after one hour and again after one week.

[0188] The color intensity was rated on a scale of 1 to 6 (6 = very high color intensity, 1 = very low color intensity).

[0189] Table 4

[0190] The addition of 1,6-diaminohexane resulted in a higher color intensity immediately after staining. The use of 1,6-diaminohexane thus both enhanced and accelerated the air-induced coupling of 5,6-dihydroxyindoline to the dye. This effect was particularly pronounced at molar ratios (SOF) / (DA) of 1:1.5 and 1:2.

[0191] Table 5

[0192] Table 6

[0193] Even with higher application rates of 1.0 wt% and 1.5 wt% 5,6-dihydroxyindoline (hydrobromide), a darker and more intense coloration on the strands could be achieved after a short period of one hour by adding 1,6-diaminohexane.

Claims

Patent claims 1. Method for the oxygen-induced dyeing of keratinous fibers, especially human hair, in which the following are applied to the keratinous fibers: - at least one self-oxidizing dye (SOF), and - at least one aliphatic di- or polyamino compound (DA) of formula (I) and / or its salt where R1 and R2 independently represent a hydrogen atom, a Ci-Ce alkyl group or a hydroxy-Ci-Ce alkyl group, or R1 and R2 together with the two carbon atoms to which they are bonded and the linker L form a 5-, 6- or 7-membered, saturated, carbocyclic or heterocyclic ring, L represents a direct bond or a saturated or unsaturated, linear or branched Ci-Ci2 alkylene group, which may optionally be substituted with one or more hydroxyl groups and / or interrupted by one or more oxygen atoms and / or by one or more -NR3- groups, and R3 represents a hydrogen atom, a Ci-Ce alkyl group, a hydroxy-Ci-Ce alkyl group, or an amino-Ci-Ce alkyl group.

2. The method according to claim 1, characterized in that the self-oxidizing dye (SOF) is selected from the group consisting of 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid, 6-hydroxyindoline, 6-aminoindoline, 4-aminoindoline, 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, 5,6-dihydroxyindol-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole, 1 2,4-Trihydroxybenzene, aminoresorcinol, aminohydroquinone, diaminophenols, 3,4,5-trihydroxybenzoic acid, and the physiologically acceptable salts of these compounds.

3. Method according to one of claims 1 to 2, characterized in that at least one aliphatic di- or polyamino compound (DA) of formula (I) and / or its salt is applied to the keratinous fibers, wherein R1 and R2 independently represent a hydrogen atom or a methyl group, preferably both representing a hydrogen atom.

4. Method according to any one of claims 1 to 3, characterized in that at least one aliphatic di- or polyamino compound (DA) of formula (I) and / or its salt is applied to the keratinous fibers, wherein L for a saturated, linear Ci-Ci2 alkylene group, a saturated, branched C3-Ci2 alkylene group, a group -CH(OH)-, a group -CH2- CH(OH)-CH2-, a group -CH2-O-CH2-, a group -CH2-O- CH2-CH2-O-CH2-, a group -CH2-O-CH2-CH2-O-CH2-CH2-O-CH2-, a group -CH2-CH2-O-CH2-CH2-, a group -CH2-NH- CH2-, a group -CH2-NH-CH2-CH2-NH-CH2-, a group -CH2-NH-CH2-CH2-NH-CH2-CH2-NH-CH2-, a group -CH2-NH-CH2-CH2-NH-CH2-, a group -CH2-NH-CH2-CH2-CH2-NH-CH2-, a group -CH2-CH2-NR3-CH2-CH2- or a group -CH2-CH2-CH2-NR3-CH2-CH2-CH2- stands.

5. A method according to any one of claims 1 to 4, characterized in that the aliphatic di- or polyamino compound of formula (I) is selected from the group consisting of 1,6-diaminohexane, 1,5-diaminopentane, 1,4-diaminobutane, 1,3-diaminopropane, 1,8-diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane, 1,5-diamino-2-methylpentane, 1,3-diaminopentane, 1,3-diamino-2,2-dimethylpropane, 1,3-diamino-2-propanol, 2-(2-aminoethoxy)ethylamine, 2,2'-(ethylenedioxy)diethylamine, bis(3-aminopropyl) ether, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine. Tris(3-aminopropyl)amine, Tris(2-aminoethyl)amine and their salts.

6. Method according to any one of claims 1 to 5, characterized in that the self-oxidizing dye(s) (SOF) and the di- or polyamine(s) (DA) of formula (I) are applied to the keratinous fibers in such quantities that the molar ratio of (SOF) / (DA) is in the range of 4:1 to 1:4, preferably 3:1 to 1:3, more preferably 2.5:1 to 1:2.5, even more preferably 1:1 to 1:2.5 and most preferably 1:1.5 to 1:2.

5.

7. Method according to any one of claims 1 to 6, characterized in that the self-oxidizing dye(s) (SOF) and the di- or polyamino compound(s) (DA) of formula (I) are provided in separate containers and mixed to form a ready-to-use agent before application.

8. Method according to claim 7, characterized in that the ready-to-use dye – based on the total weight of the ready-to-use dye – comprises a or contains several self-oxidizing dyes (SOF) in a total amount of 0.01 to 10.5 wt.%, preferably 0.1 to 5.0 wt.%, more preferably 0.2 to 2.0 wt.%, even more preferably 0.3 to 1.8 wt.% and most preferably 0.6 to 1.4 wt.%.

9. Method according to one of claims 7 to 8, characterized in that the ready-to-use dye contains one or more diamines or polyamines (DA) of formula (I) in a total amount of 0.01 to 20.0 wt.%, preferably 0.1 to 10.0 wt.%, further preferably 0.15 to 5.0 wt.% and most preferably 0.4 to 3.0 wt.%, even more preferably 0.5 to 2.0 wt.% and most preferably 0.6 to 1.4 wt.%.

10. Method according to one of claims 7 to 9, characterized in that the ready-to-use dye contains water and has a pH value of 4.0 to 12.0, preferably 4.7 to 11.5, more preferably 6.5 to 10.0 and most preferably 8.0 to 10.

5.

11. Method according to any one of claims 1 to 10, characterized in that no composition containing one or more peroxo compounds is applied to the keratinous fibers in the method.

12. Method according to one of claims 1 to 1 1 , characterized in that no composition containing one or more aromatic diamino compounds is applied to the keratinous fibers in the method.

13. Ready-to-use agent for dyeing keratinous fibers, especially human hair, containing - at least one self-oxidizing dye (SOF), and - at least one aliphatic di- or polyamino compound (DA) of formula (I) and / or its salt, wherein the self-oxidizing dye (SOF), the aliphatic di- or polyamino compound (DA) of formula (I) and / or its salts and the ready-to-use agent are described in claims 1 to 10.

14. Ready-to-use agent according to claim 13, characterized in that it - does not contain peroxo compounds, and / or - contains no aromatic diamino compounds.

15. Use of at least one aliphatic di- or polyamino compound (DA) of formula (I) and / or its salt to accelerate and / or enhance the oxygen-induced formation of dyes starting from self-oxidizing dyes, wherein the self-oxidizing dye(s) are preferably selected from the group consisting of 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid, 6-hydroxyindoline, 6-aminoindoline, 4-aminoindoline, 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-Butyl-5,6-dihydroxyindole, 5,6-Dihydroxyindol-2-carboxylic acid, 6-Hydroxyindole, 6-Aminoindole and 4-Aminoindole, 1,2,4-Trihydroxybenzene, Aminoresorcinol, Aminohydroquinone, Diaminophenols, 3,4,5-Trihydroxybenzoic acid, and the physiologically acceptable salts of these compounds.

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