Inorganic-organic diamine crosslinker for improving the condition of hair during use of oxidative hair treatment agents

Abstract

The present invention relates to an agent for oxidative hair dyeing or bleaching which is gentle on hair, and an oxidative hair dyeing or bleaching method which is gentle on hair and in which keratin fibers are protected from oxidative effects.

Description

[0001] “Inorganic-organic diamine crosslinker for improving hair texture during the application of oxidative hair treatment agents”

[0002] The present invention relates to a hair-protecting agent for oxidative hair coloring or bleaching and to a gentle method for oxidative hair coloring or bleaching, in which keratin fibers are protected from oxidative influences or oxidative hair damage is repaired.

[0003] When hair is dyed or bleached using oxidative methods, the aggressive agents can cause damage to the keratin fiber. In particular, the natural hydrophobicity of the keratin fiber is reduced, as the dyeing or bleaching agents must first penetrate the hair to take effect. However, the water-repellent effect is, on the one hand, a natural protection for the hair, and, on the other, closely linked to consumer-desired parameters such as shine, softness, feel, and hair "fall."

[0004] To overcome these disadvantages, so-called pre-treatment products are available on the market, which are intended to protect the hair from aggressive influences. However, these often weigh down the hair or impair the success of the subsequent lightening or coloring process; in particular, the washfastness of the color can be impaired by the pre-treatment product. Numerous after-treatment products are also known, which attempt to repair the hair damage caused by oxidative coloring. However, all of these methods require a multi-step application process, namely the application of another hair treatment product either before or after the coloring process. This is often perceived as annoying by consumers, since the oxidative coloring treatment itself is very complex, with multiple steps and a processing time of up to 60 minutes.

[0005] The object of the present invention was to provide an agent and a method for oxidative hair coloring with a hair-protecting treatment that overcomes the aforementioned disadvantages without negatively affecting the color result of the oxidative coloring treatment. In particular, a coloring agent and a method were to be provided that do not weigh down the hair and cause as little hair damage as possible. Furthermore, the achieved hair protection should be as time-consuming as possible and, if possible, be carried out simultaneously with the coloring step itself.

[0006] The use of organic acids, such as succinic acid, in hair care is state of the art. These are widely used in shampoos and especially in conditioners to provide conditioning effects. For example, patent application WO 2005 / 115314A1 discloses a process for restructuring keratin fibers, in which the keratin fibers are brought into contact with cystine and at least one dicarboxylic acid having 2 to 10 carbon atoms. Patent application DE 10051774 A1 describes the use of short-chain carboxylic acids with a molecular weight of less than 750 g / mol in cosmetic products as an active ingredient for restructuring keratin fibers. Patent application EP1174112A discloses hair treatment products that, in addition to an organic acid, contain an organic solvent, a cationic surfactant, and a higher alcohol as further mandatory ingredients and are used to repair hair pores.

[0007] EP3501489A1 describes the consecutive application of an ether-free diamine followed by a dicarboxylic acid as part of an oxidative hair treatment to reduce hair damage. WO2016179017A1 discloses an agent containing 4,9-dioxadodecane-1,12-diamine and citric acid, which reduces hair damage as part of an oxidative hair treatment.

[0008] It has now been discovered that oxidative coloring and bleaching agents containing, in addition to typical ingredients such as water, ammonium hydroxide and / or selected amino alcohols as alkalizing agents and a peroxide compound such as hydrogen peroxide, phosphoric acid and at least one alpha, omega-ether diamine with 12 or 13 carbon atoms and 2 or 3 oxygen atoms in the molecule, lead to significantly improved hair protection during oxidative hair treatment without impairing the results of the oxidative coloring or bleaching treatment. It has surprisingly been discovered that the content of phosphoric acid in combination with at least one alpha, omega-ether diamine with 12 or 13 carbon atoms and 2 or 3 oxygen atoms in the molecule protects the hair during coloring and / or bleaching from damage caused by the high pH of the agent and by the oxidizing agent.This was evident, among other things, from the fact that the denaturation temperature of the keratin fibers was increased, indicating cross-linking within the keratin structure and thus stabilization and strengthening of the hair internally, compared to the application of non-inventive coloring and bleaching agents. The cysteic acid content was also reduced with the agents according to the invention compared to the comparison agents without inorganic-organic cross-linking agents, indicating damage repair. Particularly surprising according to the invention was the fact that the at least one alpha, omega-ether diamine b) with 12 or 13 carbon atoms and 2 or 3 oxygen atoms in the molecule must be present as a salt neutralized with phosphoric acid a) to be particularly effective.

[0009] The present invention relates, in a first embodiment, to an oxidative coloring or bleaching agent for keratinic fibers, in particular for human hair, comprising a) phosphoric acid, b) at least one alpha, omega-ether diamine having 12 or 13 carbon atoms and 2 or 3 oxygen atoms in the molecule, c) furthermore at least one alkalizing agent selected from ammonium hydroxide, amino-Ci-Ce-alkanols, amino-Ci-Ce-alkanediols, basic amino acids and sodium silicates and mixtures thereof, d) optionally at least one oxidation dye precursor and / or at least one direct dye, e) water and f) at least one peroxide compound.A further subject of the present invention is a process for the oxidative coloring and / or lightening of keratin fibers, in particular human hair, in which a coloring or bleaching agent is applied to the keratin fibers, in particular to the human hair, and is rinsed out again after a contact time of 0.1 to 60 minutes, preferably 1 to 45 minutes, particularly preferably 10 to 30 minutes, said coloring or bleaching agent comprising a) phosphoric acid, b) at least one alpha, omega-ether diamine having 12 or 13 carbon atoms and 2 or 3 oxygen atoms in the molecule, c) furthermore at least one alkalizing agent selected from ammonium hydroxide, amino-Ci-Ce-alkanols, amino-Ci-Ce-alkanediols, basic amino acids and sodium silicates and mixtures thereof, d) optionally at least one oxidation dye precursor and / or at least one direct dye, e) water and f) at least one peroxide compound.

[0010] Another object of the present invention is a process for the oxidative coloring and / or lightening of keratin fibers, in particular human hair, which comprises the following process steps:

[0011] I. Providing a composition (A) comprising a) phosphoric acid, b) at least one alpha, omega-ether diamine having 12 or 13 carbon atoms and 2 or 3 oxygen atoms in the molecule and c) water, wherein the molar ratio of phosphoric acid to the total amount of at least one alpha, omega-ether diamine having 12 or 13 carbon atoms and 2 or 3 oxygen atoms in the molecule is in the range of 1 - 10, preferably 1.5 - 5, particularly preferably 2 - 4 and wherein the composition (A) has a pH in the range of 3.0 to 7.2, preferably 3.4 - 6.0, particularly preferably 4.0 to 5.0, in each case measured at 20°C,

[0012] II. Providing a composition (B) comprising d) at least one alkalizing agent selected from ammonium hydroxide, amino-Ci-Ce-alkanols, amino-Ci-Ce-alkanediols, basic amino acids and sodium silicates and mixtures thereof, e) optionally water and f) optionally at least one oxidation dye precursor and / or at least one direct dye,

[0013] III. Providing a composition (C) comprising g) at least one peroxide compound, which is preferably hydrogen peroxide,

[0014] IV. Mixing of compositions (A), (B) and (C) together, immediately after

[0015] V. Application of the mixture of (A), (B) and (C) to the keratin fibers, in particular to the human hair, and

[0016] VI. Rinse after an exposure time of 0.1 to 60 minutes, preferably 1 to 45 minutes, particularly preferably 10 to 30 minutes,

[0017] VII. if necessary, further hair treatments such as styling, conditioning and / or drying.

[0018] Phosphoric acid and alpha, omega-ether diamine with 12 or 13 carbon atoms and 2 or 3 oxygen atoms in the molecule

[0019] Phosphoric acid in combination with at least one alpha, omega-ether diamine having 12 or 13 carbon atoms and 2 or 3 oxygen atoms in the molecule results in significantly reduced hair damage caused by the coloring or bleaching agents according to the invention compared to coloring or bleaching agents without phosphoric acid and alpha, omega-ether diamine.

[0020] Coloring and bleaching agents preferred according to the invention as well as compositions (A) preferred according to the invention (see below) as well as methods preferred according to the invention for coloring or lightening keratin fibers and uses preferred according to the invention are characterized in that the alpha, omega-ether diamine b) with 12 or 13 carbon atoms and 2 or 3 oxygen atoms in the molecule is selected from 4,7,10-trioxa-1,13-tridecanediamine and 4,9-dioxadodecane-1,12-diamine and mixtures of these substances, with 4,7,10-trioxa-1,13-tridecanediamine being particularly preferred.

[0021] It has been found to be crucial that alpha, omega-etherdiamine cannot be used alone or separately from phosphoric acid, as it is too alkaline in itself. Before adding it to the coloring or bleaching agents according to the invention, a mixture of phosphoric acid and alpha, omega-etherdiamine is first prepared, which is then added to a coloring or bleaching agent to achieve the effect according to the invention. In this mixture of phosphoric acid and alpha, omega-ether diamine, the molar ratio of phosphoric acid to the total amount of alpha, omega-ether diamine is in the range of 1 - 10, preferably 1.5 - 5, particularly preferably 2 - 4, and this mixture, which is also referred to below as composition (A), has a pH in the range of 3.0 to 7.2, preferably 3.4 - 6.0, particularly preferably 4.0 to 5.0, in each case measured at 20°C.The composition (A) according to the invention is further characterized in that it is configured as follows:.

[0022] - 2 to 20% by weight, preferably 4 to 10% by weight, particularly preferably 6 to 8% by weight, of phosphoric acid, converted to undissociated phosphoric acid and based on the weight of composition (A), furthermore

[0023] - in a total amount of 2 to 20 wt.%, preferably 5 to 15 wt.%, particularly preferably 7 to 10 wt.% of at least one alpha, omega-ether diamine having 12 or 13 carbon atoms and 2 or 3 oxygen atoms in the molecule, based on the weight of composition (A), and

[0024] - water, preferably in an amount of 50-96% by weight, particularly preferably 60-90% by weight and extraordinarily preferably from 70 to 85% by weight of water, in each case based on the weight of composition (A),

[0025] - wherein the molar ratio of phosphoric acid to the total amount of alpha, omega-ether diamine having 12 or 13 carbon atoms and 2 or 3 oxygen atoms in the molecule is in the range of 1 - 10, preferably 1.5 - 5, particularly preferably 2 - 4 and

[0026] - wherein the composition (A) has a pH in the range from 3.0 to 7.2, preferably 3.4 to 6.0, particularly preferably 4.0 to 5.0, in each case measured at 20°C.

[0027] In a preferred embodiment of the invention, the composition (A) contains no further acid besides phosphoric acid and no further diamine besides the at least one alpha, omega-ether diamine having 12 or 13 carbon atoms and 2 or 3 oxygen atoms in the molecule.

[0028] Coloring and bleaching agents preferred according to the invention are characterized in that, based on the weight of the agent, they contain 0.1 - 10 wt.%, preferably 0.2 - 5 wt.%, particularly preferably 0.3 - 1 wt.% phosphoric acid, converted to undissociated phosphoric acid.

[0029] Further coloring and bleaching agents preferred according to the invention are characterized in that, based on the weight of the agent, at least one alpha, omega-ether diamine having 12 or 13 carbon atoms and 2 or 3 oxygen atoms in the molecule is contained in a total amount of 0.1 - 10 wt.%, preferably 0.2 - 5 wt.%, particularly preferably 0.3 - 1 wt.%, in each case converted to the unprotonated amine.

[0030] Alkalizing agent

[0031] The coloring or bleaching agents according to the invention further contain at least one alkalizing agent selected from ammonium hydroxide, amino-Ci-Ce-alkanols, amino-Ci-Ce-alkanediols, basic amino acids and sodium silicates and mixtures thereof.

[0032] According to the invention, the alpha, omega-ether diamines with 12 or 13 carbon atoms and 2 or 3 oxygen atoms in the molecule are not considered alkalizing agents.

[0033] To achieve the desired long-lasting coloring or lightening of the keratin fibers, the coloring or bleaching agent according to the invention must have a pH in the range of 6.5 to 11.0, preferably 8 to 10.5, particularly preferably 8.5 to 10, each measured at 20°C. At these pH values, the outer keratin fiber layer opens optimally to absorb the oxidation dye precursors, and the desired effect of the peroxide compound unfolds optimally.

[0034] Ammonia is preferably used in the form of an aqueous solution. Corresponding aqueous ammonia solutions can be 10 to 35 percent by weight solutions (calculated in wt. %, 100 g of aqueous ammonia solution accordingly contain 10 to 35 g of ammonia). Ammonia is preferably used in the form of a 20 to 30 percent by weight solution, particularly preferably in the form of a 25 percent by weight solution.

[0035] In a particularly preferred embodiment, the coloring or bleaching agent according to the invention is characterized in that it contains ammonium hydroxide in an amount of 0.20 to 2.5 wt.%, preferably 0.5 to 2.0 wt.%, more preferably 1.0 to 1.5 wt.% and particularly preferably 0.31 to 0.8 wt.% - based on the total weight of the coloring or bleaching agent according to the invention.

[0036] In addition to or instead of ammonium hydroxide, preferred coloring or bleaching agents according to the invention contain as alkalizing agent at least one organic amine selected from amino-Ci-Ce-alkanols, in particular monoethanolamine, amino-Ci-Ce-alkanediols, in particular 2-amino-2-methylpropan-1-ol, 2-amino-2-methylpropan-1,3-diol, 2-aminopropan-1-ol, 3-aminopropan-1-ol, 1-aminopropan-2-ol (MIPA) and 2-amino-2-(hydroxymethyl)propan-1,3-diol (TRIS), as well as basic amino acids, in particular arginine, lysine and histidine, with monoethanolamine, 2-amino-2-methylpropan-1-ol, 2-amino-2-methylpropan-1,3-diol, arginine and lysine and mixtures thereof being particularly preferred.

[0037] To achieve maximum odor coverage and to optimize the fastness properties, the at least one organic amine serving as an alkalizing agent is present in a total amount of 0.2-6.5 wt.%, preferably 0.5-4.0 wt.%, more preferably 0.7 to 2.5 wt.%, and particularly preferably 0.8 to 1.6 wt.%, based on the total weight of the coloring or bleaching agent according to the invention. As already mentioned, the content of at least one alpha, omega-ether diamine having 12 or 13 carbon atoms and 2 or 3 oxygen atoms in the molecule is not counted as an alkalizing agent according to the invention.

[0038] Sodium silicates, as defined in the present invention, are chemical compounds composed of sodium oxide and silicon dioxide, which can occur in various molar ratios (monosilicate, metasilicate, and polysilicate). An example of a sodium silicate is the sodium salt of orthosilicic acid with the molecular formula Na4SiO4, which is also referred to as sodium orthosilicate.

[0039] Further examples of suitable sodium silicates are disodium metasilicate or sodium metasilicate with the molecular formula Na2SiO3, disodium disilicate with the molecular formula Na2Si2O5 or disodium trisilicate with the molecular formula Na2Si3O?

[0040] Amorphous silicates can be produced by melting silicon dioxide and alkali oxide in molar ratios between 1:1 and 4:1. The resulting solids are dissolved at approximately 150 °C and 5 bar vapor pressure to obtain a solution of the sodium silicates in water. These solutions are alkali water glasses.

[0041] Alkali water glasses are glassy (amorphous) sodium silicates or their aqueous solutions that solidify from a melt. These are also called soda water glasses. Soda water glasses are also included in the definition of sodium silicates within this invention.

[0042] The molar composition of water glasses is usually 2 to 4 mol SiO2 to 1 mol alkali oxide (Na2O).

[0043] An example of a preferred sodium silicate is sodium silicate, which is in the form of its aqueous solution, has a Na2O content of 7.5 to 8.8 wt% and a SiO2 content of 25.0 to 28.5 wt% and has the CAS No. 1344-09-5 (Chemical Abstracts Number).

[0044] Further coloring or bleaching agents preferred according to the invention contain at least one sodium silicate in a total amount of 0.1 to 9 wt.%, preferably 0.2 to 8 wt.%, particularly preferably 1 to 7.5 wt.%, in each case based on the total weight of the coloring or bleaching agent according to the invention.

[0045] Furthermore, other alkalizing agents, such as potassium hydroxide and sodium hydroxide, may be contained, usually in a total amount of 0.05 to 1.5% by weight, preferably 0.1 to 0.6% by weight, in each case based on the total weight of the coloring or bleaching agent according to the invention.

[0046] Water

[0047] The coloring or bleaching agents according to the invention contain water, preferably in an amount of 30 - 90 wt.%, preferably 50 - 85 wt.%, more preferably 60 - 80 wt.%, in each case based on the total weight of the coloring or bleaching agent according to the invention.

[0048] Peroxide compounds

[0049] The formation of pigments in oxidative dyes, or the breakdown of the hair's natural pigment melanin for bleaching, occurs only through the influence of a peroxide compound as an oxidizing agent. Hydrogen peroxide is typically used for this purpose. Hydrogen peroxide can only be used in the form of an aqueous solution.

[0050] Coloring or bleaching agents preferred according to the invention are characterized in that they contain 0.5 to 13% by weight, more preferably 1 to 7% by weight, particularly preferably 2 to 6% by weight and very particularly preferably 3 to 4.5% by weight of hydrogen peroxide (calculated as 100% H2O2), in each case based on the total weight of the coloring or bleaching agent according to the invention.

[0051] Bleaching agents or particularly strong lightening dyes may also contain highly oxidizing peroxide compounds such as potassium, sodium and / or ammonium persulfate.

[0052] It has proven advantageous if the oxidizing agent preparations according to the invention additionally contain at least one stabilizer or complexing agent to stabilize the hydrogen peroxide. Particularly preferred stabilizers are, in particular, EDTA, EDDS (ethylenediamine disuccinic acid), MGDA (methylglycinediacetic acid), GLDA (glutamate diacetic acid), IDS (iminodisuccinic acid), and phosphonates, in particular 1-hydroxyethane-1,1-diphosphonate (HEDP) and / or ethylenediaminetetramethylenephosphonate (EDTMP) and / or diethylenetriaminepentamethylenephosphonate (DTPMP), and preferably their sodium salts, particularly preferably tetrasodium iminodisuccinate (Na4-IDS), trisodium methylglycinediacetate (Nas-MGDA), tetrasodium glutamate diacetate (Na4-GLDA), and trisodium ethylenediamine disuccinate (Nas-EDDS).

[0053] If the agents according to the invention are agents for the oxidative dyeing of keratin fibers, in particular human hair, they contain at least one oxidation dye precursor to form the dyes.

[0054] Oxidation dye precursors include developer-type and coupler-type oxidation dye precursors. Particularly suitable oxidation dye precursors of the developer type are selected from at least one compound from the group p-phenylenediamine, p-toluenediamine, 2-(2-hydroxyethyl)-p-phenylenediamine, 2-(1,2-dihydroxyethyl)-p-phenylenediamine, N,N-bis-(2-hydroxyethyl)-p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, N-(4-amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amine, N,N'-bis-(2-hydroxyethyl)-N,N'-bis-(4-aminophenyl)-1,3-diamino-propan-2-ol, bis-(2-hydroxy-5-aminophenyl)methane, 1,3-bis-(2,5-diaminophenoxy)propan-2-ol, N,N'-bis-(4-aminophenyl)-1,4-diazacycloheptane, 1,10-bis-(2,5-diaminophenyl)-1,4,7,10-tetraoxadecane, p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(1,2-dihydroxyethyl)phenol, 4-Amino-2-(diethyl-aminomethyl)phenol, 4,5-diamino-1-(2-hydroxyethyl)pyrazole, 2,4,5,6-tetraaminopyrimidine,4-Hydroxy-2,5,6-triaminopyrimidine, 2-Hydroxy-4,5,6-triaminopyrimidine, 2,3-Diamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2- a]pyrazol-1-one and their physiologically acceptable salts.

[0055] Particularly suitable oxidation dye precursors of the coupler type are selected from the group 3-aminophenol, 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 5-amino-4-chloro-2-methylphenol, 5-(2-hydroxyethyl)-amino-2-methylphenol, 2,4-dichloro-3-aminophenol, 2-aminophenol, 3-phenylenediamine, 2-(2,4-diaminophenoxy)ethanol, 1,3-bis(2,4-diaminophenoxy)propane, 1-methoxy-2-amino-4-(2-hydroxyethylamino)benzene, 1,3-bis(2,4-diaminophenyl)propane, 2,6-bis(2'-hydroxyethylamino)-1-methylbenzene, 2-({3-[(2-Hydroxyethyl)amino]-4-methoxy-5-methylphenyl}amino)ethanol, 2-({3-[(2-Hydroxyethyl)amino]-2-methoxy-5-methylphenyl}amino)ethanol,

[0056] 2-({3-[(2-Hydroxyethyl)amino]-4,5-dimethylphenyl}amino)ethanol, 2-[3-Morpholin-4-ylphenyl)amino]- ethanol, 6-Hydroxybenzomorpholin, 3-Amino-4-(2-methoxyethoxy)-5-methylphenylamin, 1-Amino-3-bis-(2- hydroxyethyl)aminobenzol, Resorcin, 2-Methylresorcin, 4-Chlorresorcin, 1 ,2,4-Trihydroxybenzol, 2-Amino-

[0057] 3-hydroxypyridin, 3-Amino-2-methylamino-6-methoxypyridin, 2,6-Dihydroxy-3,4-dimethylpyridin, 3,5- Diamino-2,6-dimethoxypyridin, 1-Phenyl-3-methylpyrazol-5-on, 1-Naphthol, 1 ,5-Dihydroxynaphthalin, 2,7- Dihydroxynaphthalin, 1 ,7-Dihydroxynaphthalin, 1 ,8-Dihydroxynaphthalin, 2-(1 ,3-Benzodioxol-5- ylamino)ethanol (INCI: Hydroxyethyl-3,4-methylenedioxyaniline), 4-Hydroxyindol, 6-Hydroxyindol, 7- Hydroxyindol, 4-Hydroxyindolin, 6-Hydroxyindolin, 7-Hydroxyindolin oder Gemischen dieser Verbindungen oder deren physiologisch verträglichen Salzen.

[0058] In a preferred embodiment, the coloring agents according to the invention contain one or more oxidation dye precursors in a total amount of 0.01 to 4.0 wt.%, preferably from 0.1 to 3.5 wt.%, more preferably from 0.6 to 3.1 wt.% and most preferably from 1.2 to 2.2 wt.%, based on the total weight of the coloring or bleaching agent according to the invention.

[0059] In a further preferred embodiment, the agents according to the invention additionally contain at least one further direct dye. Direct dyes can be divided into anionic, cationic, and nonionic direct dyes. The direct dyes are preferably selected from nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones, triarylmethane dyes, or indophenols and their physiologically acceptable salts. The direct dyes are each preferably present in a total amount of 0.001 to 2% by weight, based on the total weight of the coloring or bleaching agent according to the invention. Direct dyes are used in oxidative coloring agents to shade the achieved color tone, and in oxidative bleaching agents to balance out undesirable red tones that can arise during the degradation of the hair's natural melanin.

[0060] Preferred anionic direct dyes are the compounds known under the international names or trade names Acid Yellow 1, Yellow 10, Acid Yellow 23, Acid Yellow 36, Acid Orange 7, Acid Red 33, Acid Red 52, Pigment Red 57:1, Acid Blue 7, Acid Green 50, Acid Violet 43, Acid Black 1, Acid Black 52, Bromophenol Blue and Tetrabromophenol Blue.

[0061] Preferred cationic substantive dyes are cationic triphenylmethane dyes, such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14, aromatic systems substituted with a quaternary nitrogen group, such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, cationic anthraquinone dyes, such as HC Blue 16 (Bluequat B) and substantive dyes containing a heterocycle having at least one quaternary nitrogen atom, in particular Basic Yellow 87, Basic Orange 31 and Basic Red 51. The cationic substantive dyes marketed under the trademark Arianor are also preferred cationic substantive dyes according to the invention.

[0062] Non-ionic nitro and quinone dyes and neutral azo dyes are particularly suitable as non-ionic direct dyes. Preferred non-ionic direct dyes are the compounds known under the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 7, HC Red 10, HC Red 11, HC Red 13, HC Red BN, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, as well as 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis-(2-hydroxyethyl)-amino-2-nitrobenzene, 3-nitro-4-(2-hydroxy- ethyl)aminophenol, 2-(2-hydroxyethyl)amino-4,6-dinitrophenol, 4-[(2-hydroxyethyl)amino]-3-nitro-1-methylbenzene, 1-amino-4-(2-hydroxyethyl)amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1-(2'- Ureidoethyl)amino-4-nitrobenzene, 2-[(4-amino-2-nitrophenyl)amino]benzoic acid, 4-[(3-

[0063] Hydroxypropyl)amino]-3-nitrophenol, 4-nitro-o-phenylenediamine, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-4-nitrophenol.

[0064] A further subject of the present invention is a process for the oxidative coloring and / or lightening of keratin fibers, in particular human hair, in which a coloring or bleaching agent is applied to the keratin fibers, in particular to the human hair, and is rinsed out again after a contact time of 0.1 to 60 minutes, preferably 1 to 45 minutes, particularly preferably 10 to 30 minutes, wherein this coloring or bleaching agent a) phosphoric acid, b) at least one alpha, omega-ether diamine having 12 or 13 carbon atoms and 2 or 3 oxygen atoms in the molecule, with 4,7,10-trioxa-1,13-tridecanediamine being particularly preferred, c) furthermore at least one alkalizing agent selected from ammonium hydroxide, amino-Ci-Ce-alkanols, amino-Ci-Ce-alkanediols, basic amino acids and sodium silicates and Mixtures thereof, d) if applicable.at least one oxidation dye precursor and / or at least one direct dye, e) water and f) at least one peroxide compound.

[0065] For the process according to the invention for the oxidative coloring and / or lightening of keratin fibers, in particular human hair, and its preferred embodiments, what has been said regarding the coloring and bleaching agents according to the invention and those preferred according to the invention applies mutatis mutandis.

[0066] The method according to the invention for the oxidative coloring and / or lightening of keratin fibers, in particular human hair, can optionally be followed by further hair treatment steps, for example the application of a conditioner, a hair shaping agent, for example a straightening agent or a waving agent, another hair coloring agent, for example for coloring or bleaching highlights, rinsing steps and drying steps, for example rubbing or pressing dry with a towel, blow-drying or drying with a hair dryer.

[0067] It is preferred according to the invention to initially store the hair-protecting combination according to the invention of phosphoric acid and at least one alpha, omega-ether diamine having 12 or 13 carbon atoms and 2 or 3 oxygen atoms in the molecule, with 4,7,10-trioxa-1,13-tridecanediamine being particularly preferred, as explained above, separately from the preparation which contains the at least one alkalizing agent and optionally at least one oxidation dye precursor and / or at least one direct dye, and separately from the oxidizing agent preparation which contains at least one peroxide compound, and to prepare the coloring or bleaching agent according to the invention or preferred according to the invention by mixing the three components only shortly before starting the process according to the invention or preferred according to the invention for the oxidative coloring and / or lightening of the keratin fibers.

[0068] A further subject of the present application is therefore a process for the oxidative coloring and / or lightening of keratin fibers, in particular human hair, which comprises the following process steps:

[0069] I. Providing a composition (A) comprising a) phosphoric acid, b) at least one alpha, omega-ether diamine having 12 or 13 carbon atoms and 2 or 3 oxygen atoms in the molecule, with 4,7,10-trioxa-1,13-tridecanediamine being particularly preferred, and c) water, wherein the molar ratio of phosphoric acid to the total amount of alpha, omega-ether diamine is in the range of 1-10, preferably 1.5-5, particularly preferably 2-4, and wherein the composition (A) has a pH in the range of 3.0 to 7.2, preferably 3.4-6.0, particularly preferably 4.0 to 5.0, in each case measured at 20°C,

[0070] II. Providing a composition (B) comprising d) at least one alkalizing agent selected from ammonium hydroxide, amino-Ci-Ce-alkanols, amino-Ci-Ce-alkanediols, basic amino acids and sodium silicates and mixtures thereof, e) optionally water and f) optionally at least one oxidation dye precursor and / or at least one direct dye, wherein the composition (B), if it contains more than 10% by weight of water, based on its weight, has a pH in the range of 6.5 to 11.0, preferably 8 - 10.5, particularly preferably 8.5 to 10.0, in each case measured at 20°C,

[0071] III. Providing a composition (C) comprising g) at least one peroxide compound, which is preferably hydrogen peroxide, wherein the composition (C) preferably has a pH in the range of 2.5 to 6.5, preferably 3.0 - 5.5, particularly preferably 3.5 to 5.0, in each case measured at 20°C,

[0072] IV. Mixing of compositions (A), (B) and (C) together, immediately after

[0073] V. Application of the mixture of (A), (B) and (C) to the keratin fibers, in particular to the human hair, and

[0074] VI. Rinse after an exposure time of 0.1 to 60 minutes, preferably 1 to 45 minutes, particularly preferably 10 to 30 minutes,

[0075] VII. if necessary, further hair treatments such as styling, conditioning and / or drying.

[0076] Mixing ratios of composition (A), composition (B) and composition (C) It has proven useful according to the invention if the weight ratio of composition (A), which contains water and the hair-protecting combination of phosphoric acid and at least one alpha, omega-ether diamine having 12 or 13 carbon atoms and 2 or 3 oxygen atoms in the molecule, preferably 4,7,10-trioxa-1,13-tridecanediamine, to the oxidatively coloring and / or oxidatively lightening mixture of composition (B), containing at least one alkalizing agent and optionally oxidation dye precursors and / or direct dyes, and composition (C), containing at least one peroxide compound, in the range of [weight of A] / [weight of B + weight of C] such as 1:4 to 1:50, preferably 1:5 to 1:25, particularly preferably 1:9 to 1:20, extraordinarily preferably 1:10 to 1:15.

[0077] Dyeing or lightening processes preferred according to the invention with the at least three aforementioned compositions (A), (B) and (C) are characterized in that the phosphoric acid is present in the composition (A) in an amount of 2 to 20 wt.%, preferably 4 to 10 wt.%, particularly preferably 6 to 8 wt.%, in each case converted to the undissociated phosphoric acid and based on the weight of the composition (A).

[0078] Dyeing or lightening processes preferred according to the invention with the at least three aforementioned compositions (A), (B) and (C) are further characterized in that at least one alpha, omega-ether diamine having 12 or 13 carbon atoms and 2 or 3 oxygen atoms in the molecule is present in the composition (A) in a total amount of 2 to 20% by weight, preferably 5 to 15% by weight, particularly preferably 7 to 10% by weight, in each case converted to the unprotonated amine and based on the weight of the composition (A).

[0079] Further dyeing or lightening processes preferred according to the invention with the at least three aforementioned compositions (A), (B) and (C) are characterized in that composition (A) contains 50-96% by weight, particularly preferably 60-90% by weight and extraordinarily preferably from 70 to 85% by weight of water, in each case based on the weight of composition (A).

[0080] Further dyeing or lightening processes preferred according to the invention with the at least three aforementioned compositions (A), (B) and (C) are characterized in that the composition (A) has a pH in the range from 3.0 to 7.2, preferably 3.4 - 6.0, particularly preferably 4.0 to 5.0, in each case measured at 20°C.

[0081] Further dyeing or lightening processes preferred according to the invention with the at least three aforementioned compositions (A), (B) and (C) are characterized in that the composition (B) has a pH in the range from 6.5 to 11.0, preferably 8 - 10.5, particularly preferably 8.5 to 10.0, in each case measured at 20°C.

[0082] Further dyeing or lightening processes preferred according to the invention with the at least three aforementioned compositions (A), (B) and (C) are characterized in that the composition (C) has a pH in the range from 2.5 to 6.5, preferably 3.0 - 5.5, particularly preferably 3.5 to 5.0, in each case measured at 20°C.

[0083] Further dyeing or lightening processes preferred according to the invention with the at least three aforementioned compositions (A), (B) and (C) are characterized in that the composition (C) contains 1.0 to 23.0 wt.%, more preferably 2.5 to 21.0 wt.%, particularly preferably 4.0 to 20.0 wt.% and very particularly preferably 5.0 to 18.0 wt.% hydrogen peroxide (calculated as 100% H2O2), in each case based on the weight of the composition (C).

[0084] For the process according to the invention for the oxidative coloring and / or lightening of keratinic fibers, in particular human hair, with the compositions (A), (B) and (C) mentioned above and its preferred embodiments, what has been said about the coloring and bleaching agents according to the invention and those preferred according to the invention applies mutatis mutandis - apart from the changed quantitative details mentioned above.

[0085] A further object of the present invention is the use of a composition (A) according to one of claims 12 or 13 for reducing and / or repairing hair damage caused by oxidative hair treatment agents.

[0086] The reduction and repair of hair damage has been experimentally demonstrated by DSC measurements (Differential Scanning Calorimetry).

[0087] This takes advantage of the fact that the less damaged hair is, the higher its denaturation temperature is. The following example is intended to illustrate the subject matter of the invention in more detail, without limiting it to this.

[0088] Bleaching agent Lift 9+ with phosphoric acid and 4,7,10-trioxa-1,13-tridecanediamine (amount in wt.%)

[0089] A bleaching agent according to the invention was prepared by mixing the above-mentioned components of a bleaching kit, applied to hair, and rinsed out after a 45-minute exposure time. The bleaching agent contained 32% by weight of bleaching powder (composition (B)), 64% by weight of hydrogen peroxide developer (composition (C)), and 4% by weight of composition (A) according to the invention. For comparison, hair was bleached with a comparison bleaching agent consisting of 32% by weight of bleaching powder (composition (B)), 64% by weight of hydrogen peroxide developer (composition (C)), and 4% by weight of water. Lightening performance

[0090] The bleaching agent according to the invention achieved better lightening (higher AL value, higher AE value) than the comparison bleaching agent, as demonstrated by colorimetric measurements.

[0091] Denaturation temperature

[0092] DSC (Differential Scanning Calorimetry) measurements showed that the hair bleached according to the invention had a higher denaturation temperature than hair bleached with the control bleaching agent. The increased denaturation temperature is evidence of reduced hair damage.

Claims

Patent claims 1. Oxidative coloring or bleaching agent for keratinic fibers, in particular for human hair, containing a) phosphoric acid, b) at least one alpha, omega-ether diamine having 12 or 13 carbon atoms and 2 or 3 oxygen atoms in the molecule, c) furthermore at least one alkalizing agent selected from ammonium hydroxide, amino-Ci-Ce-alkanols, amino-Ci-Ce-alkanediols, basic amino acids and sodium silicates and mixtures thereof, d) optionally at least one oxidation dye precursor and / or at least one direct dye, e) water and f) at least one peroxide compound.

2. Coloring or bleaching agent according to claim 1, characterized in that, based on the weight of the agent, 0.1 - 10 wt.%, preferably 0.2 - 5 wt.%, particularly preferably 0.3 - 1 wt.% phosphoric acid is contained, converted to undissociated phosphoric acid.

3. Coloring or bleaching agent according to claim 1 or 2, characterized in that the alpha, omega-ether diamine b) having 12 or 13 carbon atoms and 2 or 3 oxygen atoms in the molecule is selected from 4,7,10-trioxa-1,13-tridecanediamine and 4,9-dioxadodecane-1,12-diamine and mixtures of these substances, with 4,7,10-trioxa-1,13-tridecanediamine being preferred.

4. Coloring or bleaching agent according to one of claims 1 - 3, characterized in that, based on the weight of the agent, the at least one alpha, omega-ether diamine b) having 12 or 13 carbon atoms and 2 or 3 oxygen atoms in the molecule is contained in a total amount of 0.1 - 10 wt.%, preferably 0.2 - 5 wt.%, particularly preferably 0.3 - 1 wt.%, in each case converted to the unprotonated amine.

5. Coloring or bleaching agent according to one of claims 1-4, characterized in that, based on the weight of the agent, 30-90 wt.%, preferably 50-85 wt.%, more preferably 60-80 wt.% water is contained.

6. Coloring or bleaching agent according to one of claims 1-5, characterized in that hydrogen peroxide is contained as the peroxide compound.

7. Coloring or bleaching agent according to one of claims 1-6, characterized in that as peroxide compound at least one oxidizing agent selected from the inorganic salts of a Peroxosulfuric acid, as well as mixtures of these salts.

8. Coloring or bleaching agent according to one of claims 1-7, characterized in that hydrogen peroxide and at least one inorganic salt of a peroxosulfuric acid are contained as peroxide compounds.

9. Coloring or bleaching agent according to one of claims 1-8, characterized in that the at least one alpha, omega-ether diamine b) having 12 or 13 carbon atoms and 2 or 3 oxygen atoms in the molecule is contained as a salt neutralized with the phosphoric acid a).

10. Coloring or bleaching agent according to one of claims 1-9, characterized in that besides phosphoric acid no further acid is contained and besides the at least one alpha, omega-ether diamine b) with 12 or 13 carbon atoms and 2 or 3 oxygen atoms in the molecule no further diamine is contained.

11. A process for the oxidative coloring and / or lightening of keratin fibers, in particular human hair, in which a coloring or bleaching agent according to any one of claims 1 to 10 is applied to the keratin fibers, in particular to the human hair, and is rinsed out again after a contact time of 0.1 to 60 minutes, preferably 1 to 45 minutes, particularly preferably 10 to 30 minutes.

12. Composition (A) containing - 2 to 20% by weight, preferably 4 to 10% by weight, particularly preferably 6 to 8% by weight, of phosphoric acid, converted to undissociated phosphoric acid and based on the weight of composition (A), furthermore - in a total amount of 2 to 20 wt.%, preferably 5 to 15 wt.%, particularly preferably 7 to 10 wt.% of at least one alpha, omega-ether diamine having 12 or 13 carbon atoms and 2 or 3 oxygen atoms in the molecule, based on the weight of composition (A), and - water, preferably in an amount of 50-96% by weight, particularly preferably 60-90% by weight and extraordinarily preferably from 70 to 85% by weight of water, in each case based on the weight of composition (A), - wherein the molar ratio of phosphoric acid to the total amount of alpha, omega-ether diamine is in the range of 1 - 10, preferably 1.5 - 5, particularly preferably 2 - 4 and - wherein the composition (A) has a pH in the range from 3.0 to 7.2, preferably 3.4 to 6.0, particularly preferably 4.0 to 5.0, in each case measured at 20°C.

13. Composition (A) according to claim 12, characterized in that besides phosphoric acid no further acid is contained and besides the at least one alpha, omega-ether diamine having 12 or 13 carbon atoms and 2 or 3 oxygen atoms in the molecule no further diamine is contained.

14. A process for the oxidative coloring and / or lightening of keratin fibers, in particular human hair, comprising the following process steps: I. Providing a composition (A) comprising a) phosphoric acid, b) at least one alpha, omega-ether diamine having 12 or 13 carbon atoms and 2 or 3 oxygen atoms in the molecule and c) water, wherein the molar ratio of phosphoric acid to the at least one alpha, omega-ether diamine having 12 or 13 carbon atoms and 2 or 3 oxygen atoms in the molecule is in the range of 1 - 10, preferably 1.5 - 5, particularly preferably 2 - 4 and wherein the composition (A) has a pH in the range of 3.0 to 7.2, preferably 3.4 - 6.0, particularly preferably 4.0 to 5.0, in each case measured at 20°C, II. Providing a composition (B) comprising d) at least one alkalizing agent selected from ammonium hydroxide, amino-Ci-Ce-alkanols, amino-Ci-Ce-alkanediols, basic amino acids and sodium silicates and mixtures thereof, e) optionally water and f) optionally at least one oxidation dye precursor and / or at least one direct dye, wherein the composition (B), if it contains more than 10% by weight of water, based on its weight, has a pH in the range of 6.5 to 11.0, preferably 8 - 10.5, particularly preferably 8.5 to 10.0, in each case measured at 20°C, III. Providing a composition (C) comprising g) at least one peroxide compound, which is preferably hydrogen peroxide, wherein the composition (C) preferably has a pH in the range of 2.5 to 6.5, preferably 3.0 - 5.5, particularly preferably 3.5 to 5.0, in each case measured at 20°C, IV. Mixing of compositions (A), (B) and (C) together, immediately after V. Application of the mixture of (A), (B) and (C) to the keratin fibers, in particular to the human hair, and VI. Rinse after an exposure time of 0.1 to 60 minutes, preferably 1 to 45 minutes, particularly preferably 10 to 30 minutes, VII. if necessary, further hair treatments such as styling, conditioning and / or drying.

15. The method according to claim 14, characterized in that the composition (A) is as in claim 12 or 13.

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