Coloration product having improved wash fastness

Abstract

The present invention relates to one-component products for direct, oxidant-free dyeing of keratin fibers, in particular human hair, which product contains, in addition to at least one direct dye, a mixture of water and one or more monovalent C2-C3 alcohols in selected amounts and at least one amphoteric surfactant.

Description

[0001] Tinting agents with improved washfastness

[0002] The present invention relates to one-component agents for the direct, oxidant-free coloring of keratin fibers (hereinafter also referred to as coloring agents), in particular human hair, which contain, in addition to at least one direct dye, a mixture of water and one or more monohydric C2-C3 alcohols in selected amounts and at least one amphoteric surfactant.

[0003] These dyes are particularly suitable for improving the washfastness of at least one direct dye.

[0004] Altering the shape and color of keratin fibers, especially hair, represents an important area of ​​modern cosmetics. This allows the appearance of hair to be adapted to both current fashion trends and the individual's wishes. Depending on the coloring requirements, hair coloring specialists are familiar with various coloring systems. For permanent, intensive colorings with good fastness properties and good gray coverage, oxidation dyes are typically used. Such dyes typically contain oxidation dye precursors, so-called developer components, and coupler components, which, under the influence of oxidizing agents such as hydrogen peroxide, form the actual dyes. Oxidation dyes are characterized by excellent, long-lasting coloring results, but are also associated with a certain degree of hair damage.

[0005] If the user wants to reduce hair damage or only temporarily change the hair color, they can use colorants based on direct dyes. In this case, the fully formed pigments diffuse from the dye into the hair fiber. Compared to oxidative hair coloring, the colors obtained with direct dyes are less durable and wash out more quickly. The gray coverage achieved with direct dyes also generally requires improvement. However, the advantage of direct dyes is the reduced hair damage caused by coloring with direct dyes.

[0006] Depending on the desired color result, the specialist uses direct dyes from different dye classes. The direct dyes known from the state of the art belong, for example, to the class of nitro dyes, anthraquinone dyes, azo dyes, triarylmethane dyes, or methine dyes. All of these dye classes should meet specific requirements for use in the cosmetics sector. Direct dyes should deliver an intensive color result and possess the best possible fastness properties. The color result obtained with direct dyes should be affected as little as possible by environmental influences, i.e., the dyes should, for example, exhibit good washfastness, lightfastness, and rubfastness.Chemical influences to which the keratin fibers may be exposed after the coloring process (such as perms) should also change the color result as little as possible.

[0007] EP 1 219 285 A2 disclosed compositions for hair coloring with direct dyes containing, in addition to water, ethanol and a liquid polyethylene glycol, such as PEG-400, also known as PEG-8. According to the description, these agents have an alkaline pH in the range of 8-12 and serve as the first component of an oxidative hair colorant, which must be mixed with a hydrogen peroxide solution before application to the hair to be colored.

[0008] From WO 2021 / 121823 A1, tint conditioners containing a direct dye, amphoteric surfactant, fatty alcohol, a non-ionic ethoxylate surfactant and a water-soluble magnesium salt were known, which had improved washfastness.

[0009] The object of the present invention was to provide a surfactant-containing dyeing agent, particularly in the form of a tint conditioner, based on direct dyes, which is compatible with a wide variety of different direct dyes and ensures high washfastness of the resulting dyeing. Furthermore, the agent should allow for the widest possible color variety, chromaticity, and color intensity.

[0010] Surprisingly, it has now been found that a large number of different direct dyes can be used individually or in combination with one another in a surfactant-containing cosmetic composition, in particular a tinting conditioner with improved coloring performance, if the surfactant-containing cosmetic composition comprises the at least one direct dye in combination with at least one amphoteric surfactant and at least one monohydric C2-C3 alcohol in a total amount of 2.5 - 20 wt.%, based on the weight of the composition.

[0011] Surprisingly, it was found that by adding one or more monohydric C2-C3 alcohols in a total amount of 2.5-20 wt.%, based on the weight of the one-component agent, the washfastness of the keratin fiber coloration achieved with the one-component agent according to the invention, which, measured at 20°C, has an acidic pH in the range of pH 0.5 to pH 6.4, could be improved. This improvement was achieved particularly compared to one-component colorants that contained a polyhydric alcohol, in particular PEG-8, instead of one or more monohydric C2-C3 alcohols. Without wishing to be bound by this theory, it is assumed that the polarity and surface energy of the aqueous medium of the colorant are increased more by PEG-8 and similar polyhydric alcohols than by ethanol or 2-propanol (isopropanol). The surface energy is always positive because energy is always required to break bonds.Since every system strives for the state of lowest free energy to be thermodynamically stable, every system strives to avoid or minimize surfaces with high surface energy. Without wishing to be bound by this theory, it is suspected that the improvement in washfastness achieved by replacing the dihydric alcohols PEG-8 (polyethylene glycol-8 with 8 ethylene glycol units) or 1,3-butylene glycol with ethanol or 2-propanol is related to the reduced polarity or reduced surface energy of the aqueous medium.

[0012] Surface energy y of different solvents

[0013] The present invention therefore relates to a one-component agent for the direct, oxidant-free coloring of keratin fibers, in particular human hair, containing

[0014] (a) at least one direct dye,

[0015] (b) 70 - 93 wt% water,

[0016] (c) one or more monohydric C2-C3 alcohols in a total amount of 2.5 - 20 wt.%, and

[0017] (d) at least one amphoteric surfactant, in particular at least one alkyl betaine, wherein the agent contains a maximum of 0.6% by weight of polyhydric alcohols and is preferably free of polyhydric alcohols, and wherein the agent has a pH of 0.5 to 6.4, preferably 1.0 to 6.0, particularly preferably 2.0 to 5.5, in each case measured at 20°C, wherein all quantities relate to the weight of the one-component agent.

[0018] A second subject matter of the present invention is a process for the direct, oxidizing agent-free coloring of keratinic fibers, in particular human hair, in which a one-component agent containing at least one direct dye, 70 - 93 wt.% water, one or more monohydric C2-C3 alcohols in a total amount of 2.5 - 20 wt.% and at least one amphoteric surfactant, wherein the agent contains a maximum of 0.6 wt.% of polyhydric alcohols and has a pH of 0.5 to 6.4, preferably 1.0 to 6.0, particularly preferably 2.0 to 5.5, is applied to the keratinic fibers without an oxidizing agent other than atmospheric oxygen being used in the process.

[0019] A third object of the present invention is the use of a one-component agent containing at least one direct dye, 70 - 93 wt.% water, one or more monohydric C2-C3 alcohols in a total amount of 2.5 - 20 wt.% and at least one amphoteric surfactant, wherein the agent contains a maximum of 0.6 wt.% of polyhydric alcohols and has a pH of 0.5 to 6.4, preferably 1.0 to 6.0, particularly preferably 2.0 to 5.5, for the direct, oxidant-free coloring of keratin fibers, in particular human hair.

[0020] Keratin fibers, or keratin fibers, include fur, wool, feathers, and especially human hair. Although these products are primarily suitable for dyeing keratin fibers, there is nothing in principle to prevent their use in other areas as well.

[0021] The term “agents for coloring” keratin fibers refers to coloring agents that color the keratin fibers based on direct dyes.

[0022] The one-component agent according to the invention for direct, oxidant-free dyeing contains, in each case based on its weight, water in an amount of 70-93% by weight, preferably 75-90% by weight, particularly preferably 78-86% by weight, extraordinarily preferably 80-85% by weight.

[0023] As the first essential ingredient, the agent according to the invention contains at least one direct dye (a).

[0024] The direct dye(s) (a) is / are preferably present in a total amount of from 0.001 to 7% by weight, preferably from 0.01 to 5.5% by weight, more preferably from 0.08 to 3.4% by weight, more preferably from 0.1 to 2% by weight, more preferably from 0.3 to 1.5% by weight and particularly preferably from 0.6 to 1% by weight, in each case based on the weight of the colorant.

[0025] Direct dyes (a) can be divided into anionic, cationic, and non-ionic direct dyes. Direct dyes are typically selected from nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones, triarylmethane dyes, or indophenols and their physiologically acceptable salts.

[0026] Dyes that carry exclusively anionic charges are referred to by those skilled in the art as acid dyes. The terms anionic dye and acid dye are therefore used synonymously for the purposes of this invention. Anionic dyes and acid dyes are understood to be direct dyes that contain at least one carboxylic acid group (-COOH) and / or at least one sulfonic acid group (-SO3H). Depending on the pH, the protonated forms (-COOH, -SO3H) of the carboxylic acid or sulfonic acid groups are in equilibrium with their deprotonated forms (-COO-, -SO3"). With decreasing pH, the proportion of protonated forms increases. If direct dyes are used in the form of their salts, the carboxylic acid groups or sulfonic acid groups are in deprotonated form and are neutralized with corresponding stoichiometric equivalents of cations (such as Na cation or K cation) to maintain electroneutrality.An anionic dye does not carry any cationic charges.

[0027] Als geeignete Säurefarbstoffe können beispielsweise eine oder mehrere Verbindungen aus der folgenden Gruppe ausgewählt werden: Acid Yellow 1 (D&C Yellow 7, Citronin A, Ext. D&C Yellow No. 7, Japan Yellow 403, CI 10316, COLIPA n° B001), Acid Yellow 3 (COLIPA n°:C 54, D&C Yellow N° 10, Quinoline Yellow, E104, Food Yellow 13), Acid Yellow 9 (CI 13015), Acid Yellow 17 (CI 18965), Acid Yellow 23 (COLIPA n° C 29, Covacap Jaune W 1100 (LCW), Sicovit Tartrazine 85 E 102 (BASF), Tartrazine, Food Yellow 4, Japan Yellow 4, FD&C Yellow No. 5), Acid Yellow 36 (CI 13065), Acid Yellow 121 (CI 18690), Acid Orange 6 (Cl 14270), Acid Orange 7 (2-Naphthol orange, Orange II, Cl 15510, D&C Orange 4, COLIPA n° C015), Acid Orange 10 (Cl 16230; Orange G sodium salt), Acid Orange 11 (Cl 45370), Acid Orange 15 (Cl 50120), Acid Orange 20 (Cl 14600), Acid Orange 24 (BROWN 1 ; Cl 20170; KATSU201 ; no sodium salt; Brown No.201 ; RESORCIN BROWN; ACID ORANGE 24; Japan Brown 201 ; D & C Brown No.1), Acid Red 14 (CI14720), Acid Red 18 (E124, Red 18; Cl 16255), Acid Red 27 (E 123, Cl 16185, C-Rot 46, Echtrot D, FD&C Red Nr.2, Food Red 9, Naphtholrot S), Acid Red 33 (Red 33, Fuchsia Red, D&C Red 33, Cl 17200), Acid Red 35 (Cl CI18065), Acid Red 51 (Cl 45430, Pyrosin B, Tetraiod- fluorescein, Eosin J, lodeosin), Acid Red 52 (Cl 45100, Food Red 106, Solar Rhodamine B, Acid Rhodamine B, Red n° 106 Pontacyl Brilliant Pink), Acid Red 73 (Cl Cl 27290), Acid Red 87 (Eosin, Cl 45380), Acid Red 92 (D&C Red; Red 104; AKA231 ; RED 28; SUREDYE; 11969 Red; PHLOXINE;CI 45405;CI 45410; EOSINE B); Acid Red 95 (Cl 45425, Erythrosine, Simacid Erythrosine Y), Acid Red 184 (Cl 15685), Acid Red 195; Pigment Red 57:1 (E180;D&CRED7; Cl 15850; Rubine 4BN; Cl 15850:1 ; PIGMENT RED 57; Litholrubine BK; LITHOLRUBINE RB; LITHOLRUBINE BCA; Lithol Rubine B); Acid Violet 43 (Jarocol Violet 43, Ext.D&C Violet n° 2, Cl 60730, COLIPA n° C063), Acid Violet 49 (Cl 42640), Acid Violet 50 (Cl 50325), Acid Blue 1 (Patent Blue, Cl 42045), Acid Blue 3 (Patent Blau V, Cl 42051), Acid Blue 7 (Cl 42080), Acid Blue 104 (Cl 42735), Acid Blue 9 (E 133, Patentblau AE, Amidoblau AE, Erioglaucin A, Cl 42090, Cl Food Blue 2), Acid Blue 62 (Cl 62045), Acid Blue 74 (E 132, Cl 73015), Acid Blue 80 (Cl 61585), Acid Green 3 (Cl 42085, Foodgreenl), Acid Green 5 (Cl 42095), Acid Green 9 (Cl 42100), Acid Green 22 (Cl 42170), Acid Green 25 (Cl 61570, Japan Green 201 , D&C Green No. 5), Acid Green 50 (Brillantsäuregrün BS, Cl 44090, Acid Brilliant Green BS, E 142), Acid Black 1 (Black n° 401 , Naphthalene Black 10B, Amido Black 10B, Cl 20470, COLIPA n° B15), Acid Black 52 (Cl 15711), Food Yellow 8 (Cl 14270), Food Blue 5, D&C Yellow 8, D&C Green 5, D&C Orange 10, D&C Orange 11 , D&C Red 21 , D&C Red 27, D&C Red 33, D&C Brown 1 , Bromphenolblau und / oder Tetrabromphenolblau.

[0028] In einer weiteren besonders bevorzugten Ausführungsform ist ein erfindungsgemäßes Mittel dadurch gekennzeichnet, dass es (a) mindestens einen anionischen direktziehenden Farbstoff aus der Gruppe, bestehend aus Acid Yellow 1 , Acid Yellow 3, Acid Yellow 9, Acid Yellow 17, Acid Yellow 23, Acid Yellow 36, Acid Yellow 121 , Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 11 , Acid Orange 15, Acid Orange 20, Acid Orange 24, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 33, Acid Red 35, Acid Red 51 , Acid Red 52, Acid Red 73, Acid Red 87, Acid Red 92, Acid Red 95, Acid Red 184, Acid Red 195, Acid Violet 43, Acid Violet 49, Acid Violet 50, Acid Blue 1 , Acid Blue 3, Acid Blue 7, Acid Blue 104, Acid Blue 9, Acid Blue 62, Acid Blue 74, Acid Blue 80, Acid Green 3, Acid Green 5, Acid Green 9, Acid Green 22, Acid Green 25, Acid Green 50, Acid Black 1 , Acid Black 52, Food Yellow 8, Food Blue 5, D&C Yellow 7, D&C Yellow 8, D&C Orange 4, D&C Green 5, D&C Orange 10, D&C Orange 11 ,D&C Red 21, D&C Red 27, D&C Red 33, D&C Violet 2 and D&C Brown 1,

[0029] A composition according to the invention is particularly preferably characterized in that it comprises at least one anionic direct dye (a) from the group Acid Orange 7, Acid Red 33, Acid Red 92; Acid Violet 43, Acid Blue 9, Acid Blue 62 and Acid Black 1.

[0030] The anionic, direct dye(s) (a) are preferably present in a total amount of from 0.001 to 7% by weight, preferably from 0.01 to 5.5% by weight, more preferably from 0.1 to 3.4% by weight and particularly preferably from 0.3 to 2% by weight, in each case based on the weight of the colorant.

[0031] Further preferred dyes according to the invention are characterized in that they contain at least one cationic direct dye as the direct dye (a). Dyes that carry exclusively cationic charges are also commonly referred to as basic dyes.

[0032] Als Beispiele für geeignete basische (kationische) Farbstoffe sind zu nennen: Basic Blue 6 (Cl-No. 51 ,175), Basic Blue 7 (Cl-No. 42,595) Basic Blue 9 (Cl-No. 52,015), Basic Blue 26 (Cl-No. 44,045), Basic Blue 41 (Cl-No. 11 ,154), Basic Blue 99 (Cl-No. 56,059), HC Blue 15, HC Blue 16 (Bluequat-Bromid), Cationic Blue 347, Basic Brown 4 (Cl-No. 21 ,010), Basic Brown 16 (Cl-No. 12,250), Basic Brown 17 (Cl- No. 12,251), Natural Brown 7 (Cl-No. 75,500), Basic Green 1 (Cl-No. 42,040), Basic Red 2 (Cl-No. 50,240), Basic Red 22 (Cl-No. 11 ,055), Basic Red 51 , Basic Red 76 (Cl-No. 12,245), Basic Violet 1 (Cl- No. 42,535), Basic Violet 2, Basic Violet 3 (Cl-No. 42,555), Basic Violet 10 (Cl-No. 45,170), Basic Violet 14 (Cl-No. 42,510), Basic Yellow 57 (Cl-No. 12,719), Basic Yellow 87 und Basic Orange 31 , sowie Kombinationen der genannten Farbstoffe.

[0033] One or more dyes from the group HC Blue 15, HC Blue 16 (Bluequat bromide), Cationic Blue 347, Basic Violet 2, Basic Red 51, Basic Red 76, Basic Yellow 57, Basic Yellow 87, Basic Orange 31, and Basic Brown 17 have proven to be particularly suitable.

[0034] A composition according to the invention is very particularly preferably characterized in that it contains at least one cationic, direct dye (a) from the group HC Blue 15, HC Blue 16, Basic Red 76, Basic Yellow 57, Basic Red 51, Basic Orange 31, Basic Yellow 87 and Basic Brown 17. The cationic, direct dye(s) (a) are preferably present in a total amount of 0.001 to 7% by weight, preferably 0.01 to 5.5% by weight, more preferably 0.1 to 3.4% by weight and particularly preferably 0.3 to 2% by weight, in each case based on the weight of the colorant.

[0035] Further colorants preferred according to the invention are characterized in that they contain at least one non-ionic direct dye as direct dye (a). This can, for example, be selected from the group 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, HC Blue 15, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis-(2-hydroxyethyl)-amino-2-nitrobenzene, 3-Nitro-4-(2-hydroxyethyl)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-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, N,N'-bis-(2-hydroxyethyl)-2-nitro-p-phenylenediamine, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-4-nitrophenol.

[0036] A composition according to the invention is very particularly preferably characterized in that it comprises at least one non-ionic, direct dye (a) from the group HC Red 1, HC Red 3, HC Red 7, HC Red 13, HC Orange 1, HC Yellow 2, HC Yellow 13, HC Blue 2, HC Blue 11, HC Blue 12, HC Blue 14, HC Violet 2, Disperse Violet 1, 4-[(3-hydroxypropyl)amino]-3-nitrophenol and 4-amino-3-nitrophenol.

[0037] The non-ionic, direct dye(s) (a) are preferably present in a total amount of 0.001 to 7% by weight, preferably 0.01 to 5.5% by weight, more preferably 0.1 to 3.4% by weight and particularly preferably 0.3 to 2% by weight, in each case based on the weight of the colorant.

[0038] Preferred direct dyes (a) are: Basic Red 76, HC Blue 16, Basic Yellow 57, Basic Red 51, Basic Orange 31, Basic Yellow 87, 4-hydroxypropylamino-3-nitrophenol, HC Red 13, HC Red 3, HC Blue 12, HC Orange 1, HC Blue 16 (bluequat bromide), HC Yellow 2, N,N'-bis-(2-hydroxyethyl)-2-nitro-p-phenylenediamine, 4-amino-3-nitrophenol, Ext. D&C Violet 2, HC Violet 2, Basic Brown 17, Basic Red 76 and Basic Yellow 57, and mixtures thereof. More preferred are Basic Red 76, HC Blue 16, Basic Yellow 57, Basic Red 51, Basic Orange 31, Basic Yellow 87, 4-hydroxypropylamino-3-nitrophenol, 4-amino-3-nitrophenol, HC Red 13, HC Violet 2, and mixtures thereof. Especially preferred are HC Blue 16, Basic Violet 2, Basic Yellow 57, Basic Red 51, Basic Orange 31, Basic Yellow 87, 4-hydroxypropylamino-3-nitrophenol, HC Red 13, and 4-amino-3-nitrophenol, and mixtures thereof.

[0039] In a preferred embodiment, the agent according to the invention comprises a combination of several direct dyes. By combining a large number of direct dyes, shades across the entire color spectrum can be created. Several purely anionic, purely cationic, or purely non-ionic dyes can be combined with one another, as can combinations of anionic, cationic, and / or non-ionic dyes.

[0040] Suitable dyes for combination with one another can be selected, for example, from HC Red 3, HC Blue 12, HC Orange 1, HC Blue 16 (Bluequat bromide), HC Yellow 2, N,N'-bis-(2-hydroxyethyl)-2-nitro-p-phenylenediamine, Ext. D&C Violet 2, Basic Brown 17, Basic Red 76, Basic Yellow 57, Basic Red 51, Basic Orange 31 and Basic Yellow 87.

[0041] In general, the above-mentioned information regarding the amounts of anionic, cationic, or non-ionic direct dyes to be used also applies mutatis mutandis when combining several direct dyes. It is preferable that the stated quantities for the total amounts of direct dyes (a) to be used are not exceeded, even in dye mixtures comprising direct dyes.

[0042] In cosmetic compositions, direct dyes interact in different ways with the other components of the compositions.

[0043] The monohydric C2-C3 alcohols play a significant role here. In a total amount of 2.5-20 wt.%, they combine with water in an amount of 70-93 wt.%, each based on the weight of the composition according to the invention, to create the optimal polarity and surface energy to achieve direct dyeing of the keratin fibers with high washfastness.

[0044] In a preferred embodiment of the invention, the one-component agent according to the invention is characterized in that the at least one monohydric C2-C3 alcohol is selected from ethanol, isopropanol, propan-1-ol, propan-2-ol, and mixtures of these alcohols.

[0045] In a further preferred embodiment of the invention, the one-component agent according to the invention is characterized in that the at least one monohydric C2-C3 alcohol is selected from ethanol, isopropanol, and mixtures of these alcohols, with ethanol being particularly preferred.

[0046] In a further preferred embodiment of the invention, the one-component agent according to the invention is characterized in that one or more monohydric C2-C3 alcohols are contained in a total amount of 4 - 17 wt.%, preferably 5 - 15 wt.%, particularly preferably 7 - 13 wt.%, extraordinarily preferably 9 - 12 wt.%, in each case based on the weight of the one-component agent.

[0047] The one-component agents according to the invention are therefore characterized by containing a maximum of 0.6% by weight of polyhydric alcohols. Preferred one-component agents according to the invention are free of polyhydric alcohols, i.e., they contain 0% by weight of polyhydric alcohols.Polyhydric alcohols include polyhydric C2 - C8 alkanols with 2 - 6 hydroxyl groups and polyethylene glycols with at least 3 ethylene oxide units, in particular 1,2-propylene glycol, 2-methyl-1,3-propanediol, glycerin, butylene glycols such as 1,2-butylene glycol, 1,3-butylene glycol and 1,4-butylene glycol, pentylene glycols such as 1,2-pentanediol and 1,5-pentanediol, hexanediols such as 1,6-hexanediol, hexanetriols such as 1,2,6-hexanetriol, 1,2-octanediol, 1,8-octanediol, dipropylene glycol, tripropylene glycol, diglycerin, triglycerin, erythritol, sorbitol, PEG-3, PEG-4, PEG-6, PEG-7, PEG-8, PEG-9, PEG-10, PEG-12, PEG-14, PEG-16, PEG-18, and PEG-20; sugars such as fructose, glucose, maltose, maltitol, mannitol, inositol, sucrose, trehalose, and xylose. Oligosaccharides and polysaccharides with more than 10 sugar units are not considered polyhydric alcohols according to the present invention.

[0048] As the comparative tests show, polyhydric alcohols do not contribute to improving wash fastness.

[0049] Surface-active ingredients such as surfactants or emulsifiers also influence the washfastness of the dye.

[0050] Surfactants and emulsifiers are amphiphilic (bifunctional) compounds consisting of at least one hydrophobic and at least one hydrophilic moiety. The hydrophobic moiety is typically a hydrocarbon chain. Depending on the type of surfactant, the hydrophilic moiety can have a negative charge, a positive charge, a negative and a positive charge, or no charge at all. Surfactants and emulsifiers within the meaning of the present application are amphiphilic (bifunctional) compounds consisting of at least one hydrophobic and at least one hydrophilic moiety. The hydrophobic moiety is preferably a hydrocarbon group with 8-28 carbon atoms, which can be saturated or unsaturated, linear or branched. This Ca-C28 alkyl group is particularly preferably linear. Basic properties of surfactants and emulsifiers are oriented absorption at interfaces, aggregation into micelles, and the formation of lyotropic phases.In anionic surfactants, the hydrophilic moiety contains at least one negatively charged hydrophilic head group. Anionic surfactants contain exclusively negative charges.

[0051] Cationic surfactants are defined as surfactants with one or more positive charges. Cationic surfactants contain only positive charges.

[0052] Zwitterionic (amphoteric) surfactants comprise at least one negatively charged and at least one positively charged group in the hydrophilic moiety. These are spatially separated and located next to each other, with the surfactant as a whole being electrically neutral.

[0053] In addition, there are non-ionic (non-ionogenic) surfactants, which are characterized by the absence of electrical charges in the molecules.

[0054] Accordingly, various such compositions are disclosed in the prior art. EP 1935455A1 discloses a composition comprising a substantive dye in combination with at least one bioheteropolysaccharide, at least one cationic surfactant, and at least one amphoteric surfactant. WO 2013 / 041485 A2 describes a composition comprising at least one dye, for example a substantive dye, at least one fatty substance in the form of a long-chain dialkyl carbonate or dialkenyl carbonate, at least one alkyl polyglycoside, and at least one cationic and / or amphoteric polymer. Cleaning compositions with different combinations of surfactants are described, for example, in WO 2016 / 040158 A1, WO 2013 / 082413 A1, and WO 2014 / 149019 A1. None of these compositions is specifically suitable for the improved washfastness of substantive dyeings.

[0055] In the course of the present development work, it was discovered that the presence of an amphoteric surfactant can further enhance the effect of the invention. The one-component agents according to the invention therefore contain at least one amphoteric surfactant (d).

[0056] In a further preferred embodiment of the invention, the one-component agent according to the invention is therefore characterized in that the at least one amphoteric surfactant (d) is contained in a total amount of 0.3 to 3.0 wt.%, preferably 0.5 to 2.0 wt.%, particularly preferably 0.7 to 1.0 wt.%, in each case based on the weight of the agent.

[0057] The total amount of surfactants in the agent according to the invention is preferably 0.3 to 5 wt.%, more preferably 0.5 to 4 wt.%, further preferably 0.7 to 3 wt.%, and extraordinarily preferably 1 to 2 wt.%, in each case based on the weight of the agent.

[0058] As previously explained, amphoteric surfactants (d) comprise at least one negatively charged and at least one positively charged group in the hydrophilic moiety of the molecule. Examples of preferred amphoteric surfactants (d) are betaines, N-alkyl-N,N-dimethylammonium glycinates, N-acylaminopropyl-N,N-dimethylammonium glycinates, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines, each containing 8 to 24 carbon atoms in the alkyl group.

[0059] In a preferred embodiment, at least one betaine, in particular at least one alkyl betaine, is used as the amphoteric surfactant (d). This is particularly preferably an alkylamidoalkyl betaine of the following formula (I): where

[0060] R represents a linear or branched, saturated or unsaturated hydrocarbon radical having 5 to 20, preferably 8 to 14 carbon atoms, and n is an integer from 0 to 10, in particular 0 to 4.

[0061] In a preferred embodiment, R is a linear hydrocarbon radical, in particular a linear, saturated hydrocarbon radical.

[0062] In a very particularly preferred embodiment, an alkylamidoalkylbetaine of the formula (I) with R = -C10H21, -C11H23 or -C12H25 and n = 0, 1 or 2 is used, in particular an alkylamidoalkylbetaine of the formula (I) with R = -C11H23 and n = 1 is used as amphoteric surfactant (d), also known as cocamidopropylbetaine.

[0063] In a particularly preferred embodiment, an agent according to the invention is therefore characterized in that it contains (d) at least one amphoteric surfactant selected from the group of alkylamidoalkyl betaines of the formula (I), in particular cocamidopropyl betaine ((CiiH23)C(O)NH(C3H6)N(NH2)2CH2C(O)O).

[0064] Preferably, the aqueous commercial product preparation of the amphoteric surfactant (d) is substantially free of sodium chloride, i.e. it comprises < 0.5 wt.%, preferably < 0.4 wt.%, particularly preferably < 0.2 wt.% sodium chloride, in each case based on the total weight of the aqueous commercial product preparation of the amphoteric surfactant (d).

[0065] For example, high-purity, low-sodium chloride cocamidopropyl betaine with an active ingredient content of 35 wt.% cocamidopropyl betaine and a sodium chloride content of < 0.5 wt.% is available under the trade name EMPIGEN® Total Active TC / U from the manufacturer Huntsman Corporation.

[0066] In a particularly preferred embodiment, the colorant according to the invention is substantially free of sodium chloride, ie it comprises < 0.2 wt.%, in particular < 0.1 wt.%, more preferably < 0.05 wt.%, particularly preferably < 0.02 wt.%, extraordinarily preferably 0.005 to 0.015 wt.% sodium chloride, more extraordinarily preferably 0 wt.% sodium chloride, in each case based on the total weight of the colorant.

[0067] Preferred one-component colorants according to the invention are characterized in that they contain at least one non-ionic oil-in-water emulsifier selected from ethoxylated Cs-C24 alkanols with 10 - 100 mol of ethylene oxide per mol. The ethoxylated Ca-C24 alkanols have the formula R 1 O(CH2CH2O) n H, where R 1stands for a linear or branched alkyl and / or alkenyl radical with 8-24 carbon atoms and n, the number of ethylene oxide units per molecule, for numbers from 10-100, preferably 10-30 mol of ethylene oxide to 1 mol of caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, and brassidyl alcohol, as well as their technical mixtures. Adducts of 10-100 mol of ethylene oxide to technical fatty alcohols with 12-18 carbon atoms, such as coconut, palm, palm kernel, or tallow fatty alcohol, are also suitable.

[0068] Particularly preferred are the Ci2-Cia alkanols with 10 - 30 units of ethylene oxide per molecule and mixtures of these substances, in particular Ceteth-12, Ceteth-20, Ceteth-30, Steareth-12, Steareth-20, Steareth-30, Laureth-12 and Beheneth-20.

[0069] Particularly preferred one-component colorants according to the invention are characterized in that the non-ionic oil-in-water emulsifier, which is selected from ethoxylated Ca-C24 alkanols with 10 - 100 mol of ethylene oxide per mol, is contained in a total amount of 0.1 - 5 wt.%, particularly preferably 0.3 - 3 wt.% and extraordinarily preferably 0.7 - 2 wt.%, based on the total composition.

[0070] In a further, particularly preferred embodiment, the agent according to the invention comprises only small amounts of anionic surfactants. The agent according to the invention preferably comprises anionic surfactants in a total amount of 0 to <0.2 wt.%, more preferably 0 to <0.15 wt.%, and in particular 0 to <0.1 wt.%, based on the total weight of the agent. Most preferably, the agent is free of anionic surfactants.

[0071] The one-component colorants according to the invention are tinting agents, preferably tinting conditioners, designed to color the hair as gently as possible. An acidic medium is required for this. The one-component colorants according to the invention therefore have a pH in the range of 0.5 to 6.4, preferably 1.0 to 6.0, particularly preferably 2.0 to 5.5, each measured at 20°C.

[0072] The pH value can be measured, for example, using a glass electrode, which is usually designed as a combination electrode. The pH values ​​used in the present invention are pH values ​​measured at a temperature of 20 °C.

[0073] Acidifying agents that can be used to adjust the pH value are organic acids such as citric acid, succinic acid, acetic acid, ascorbic acid, benzoic acid, lactic acid, malic acid and maleic acid, as well as mineral acids such as hydrochloric acid, sulfuric acid or phosphoric acid.

[0074] To buffer the pH of the agent, alkalizing agents can also be added, which are preferably selected from the group consisting of ammonia, alkanolamines, basic amino acids, and inorganic alkalizing agents such as (alkali earth) metal hydroxides, (alkali earth) metal metasilicates, (alkali earth) metal phosphates, and (alkali earth) metal hydrogenphosphates. Preferred inorganic alkalizing agents are magnesium carbonate, sodium hydroxide, potassium hydroxide, sodium silicate, and sodium metasilicate. Organic alkalizing agents that can be used according to the invention are preferably selected from monoethanolamine, 2-amino-2-methylpropanol, and triethanolamine. The basic amino acids that can be used as alkalizing agents according to the invention are preferably selected from the group consisting of arginine, lysine, ornithine, and histidine, particularly preferably arginine.However, in the course of the investigations relating to the present invention, it has been found that further preferred agents according to the invention are characterized by additionally containing an organic alkalizing agent. One embodiment of the first subject matter of the invention is characterized in that the agent additionally contains at least one alkalizing agent selected from the group consisting of ammonia, alkanolamines, and basic amino acids, in particular ammonia, monoethanolamine, and arginine or its compatible salts.

[0075] Furthermore, it has proven advantageous if the colorants contain at least one stabilizer or complexing agent. Particularly preferred stabilizers are phenacetin, alkali metal benzoates (sodium benzoate), and salicylic acid. Furthermore, all prior art complexing agents can be used. Complexing agents preferred according to the invention are nitrogen-containing polycarboxylic acids, especially EDTA and EDDS, and phosphonates, especially 1-hydroxyethane-1,1-diphosphonate (HEDP) and / or ethylenediaminetetramethylenephosphonate (EDTMP) and / or diethylenetriaminepentamethylenephosphonate (DTPMP), or their sodium salts.

[0076] Furthermore, preferred agents according to the invention can contain as film formers one or more cationic compounds from the group Polyquaternium-1, Polyquaternium-2, Polyquaternium-3, Polyquaternium-

[0077] 4, Polyquaternium-5, Polyquaternium-6, Polyquaternium-7, Polyquaternium-8, Polyquaternium-9

[0078] Polyquaternium-10, Polyquaternium-11, Polyquaternium-14, Polyquaternium-16, Polyquaternium-17

[0079] Polyquaternium-18, Polyquaternium-22, Polyquaternium-24, Polyquaternium-27, Polyquaternium-28

[0080] Polyquaternium-32, Polyquaternium-33, Polyquaternium-37, Polyquaternium-39, Polyquaternium-44

[0081] Polyquaternium-46, Polyquaternium-53, Polyquaternium-55, Polyquaternium-64, Polyquaternium-67

[0082] Contains polyquaternium-68, polyquaternium-69 and / or polyquaternium-86 as film formers.

[0083] Polyquaternium-6 is particularly preferred as a film former. This improves the properties of the product and the quality of the resulting color.

[0084] Preferably, at least one cationic polyquaternium compound is contained in a total amount of 0.1 to 3 wt.%, particularly preferably 0.2 to 2 wt.%, more preferably 0.3 to 1.5 wt.% and in particular in an amount of 0.5 to 1 wt.%, further preferably 0.2 to 0.7 wt.%, in each case based on the weight of the agent.

[0085] Furthermore, preferred agents according to the invention may further contain at least one linear 1-alkanol having 4 to 40 carbon atoms, preferably in an amount—based on the total weight of the agent—of 5 to 25 wt.%. Such linear 1-alkanols having 4 to 40 carbon atoms support the washfastness of the dye.

[0086] Particularly preferred agents according to the invention are characterized in that the at least one linear 1-alkanol having 4 to 40 carbon atoms is selected from octan-1-ol (octyl alcohol, caprylic alcohol), decan-1-ol (decyl alcohol, capric alcohol), dodecan-1-ol (dodecyl alcohol, lauryl alcohol), tetradecan-1-ol (tetradecyl alcohol, myristyl alcohol), hexadecan-1-ol (hexadecyl alcohol, cetyl alcohol, palmityl alcohol), octadecan-1-ol (octadecyl alcohol, stearyl alcohol), eicosan-1-ol (eicosyl alcohol, arachidyl alcohol), docosan-1-ol (docosyl alcohol, behenyl alcohol), (13E)-docosen-1-ol (brassidyl alcohol) and (13Z)-docos-13-en-1-ol (erucyl alcohol) as well as mixtures of this.

[0087] It has surprisingly been found that a hydrocarbon oil or hydrocarbon wax content can reduce the washfastness of the dye. Therefore, further preferred agents according to the invention are characterized by not containing hydrocarbon oil or hydrocarbon wax.

[0088] Furthermore, it was surprisingly discovered that a content of ethoxylated silicone compounds, such as in particular PEG-12 dimethicone, can reduce the washfastness of the dye. Therefore, further preferred agents according to the invention are characterized by not containing any ethoxylated silicone compound.

[0089] The agent according to the invention can be formulated in various forms. For example, it can be applied as a gel, an emulsion, a solution, or even in the form of a coloring foam. The use of gels (shampoo) represents a particularly appealing and convenient application form for the user and is therefore preferred. The gel can be applied directly to the keratin fibers to be colored, and the application process can be easily integrated into the user's daily hygiene routine. Therefore, the formulation of the agent as a tinting conditioner is particularly preferred.

[0090] A second subject matter of the present invention is a process for the direct, oxidizing agent-free coloring of keratinic fibers, in particular human hair, in which a one-component agent containing at least one direct dye, 70 - 93 wt.% water, one or more monohydric C2-C3 alcohols in a total amount of 2.5 - 20 wt.% and at least one amphoteric surfactant, wherein the agent contains a maximum of 0.6 wt.% of polyhydric alcohols and has a pH of 0.5 to 6.4, preferably 1.0 to 6.0, particularly preferably 2.0 to 5.5, is applied to the keratinic fibers without an oxidizing agent other than atmospheric oxygen being used in the process.

[0091] With regard to further preferred embodiments of the methods, what has been said regarding the agents according to the invention and preferred according to the invention applies mutatis mutandis.

[0092] A third object of the present invention is the use of a one-component agent containing at least one direct dye, 70 - 93 wt.% water, one or more monohydric C2-C3 alcohols in a total amount of 2.5 - 20 wt.% and at least one amphoteric surfactant, wherein the agent contains a maximum of 0.6 wt.% of polyhydric alcohols and has a pH of 0.5 to 6.4, preferably 1.0 to 6.0, particularly preferably 2.0 to 5.5, for the direct, oxidant-free coloring of keratin fibers, in particular human hair.

[0093] With regard to further preferred embodiments of the use, what has been said regarding the agents according to the invention and preferred according to the invention applies mutatis mutandis.

[0094] Experimental part

[0095] Influence of PEG-8, ethanol and isopropanol on the washfastness of direct dyeing

[0096] Oil-in-water emulsions were prepared from the ingredients listed in Tables 1, 2, and 3 below. First, the fatty phase components (cetearyl alcohol, coconut fatty alcohol, marula oil) were heated together with the emulsifier (ceteareth-20) and, separately, the aqueous phase components (water, cocamidopropyl betaine) were heated to 80°C, then homogenized, then cooled to approximately 35-45°C, and finally mixed with the remaining ingredients. The pH was approximately 4.5, measured at 20°C.

[0097] Unless otherwise stated, the quantities in Tables 1 to 3 are given in percent by weight based on the total weight. The data refer to the active ingredient content, with the exception of ethanol, which was used as a standard 96% by volume commercial product.

[0098] Table 1: One-component agents for direct, oxidant-free coloring of keratin fibers: Comparative compositions V1 to V5 (amounts in wt.%)

[0099] Table 2: One-component agent for direct, oxidant-free coloring of keratin fibers: Comparison V6 and compositions according to the invention E1 to E4 (amounts in wt.%)

[0100] Table 3: One-component agent for direct, oxidant-free coloring of keratin fibers: Comparison V7 and compositions according to the invention E5 to E8 (amounts in wt.%)

[0101] Washfastness

[0102] The tests on the washfastness of the dyes were carried out on Kerling 9 / 0 root hair strands and on Kerling 10 / 0 hair strands (entire length).

[0103] The dye formulations prepared as described above were applied to the hair strands (4 g of dye per 1 g of hair) and left there at 20°C for 30 minutes. The hair strands were then thoroughly rinsed with water and dried in a stream of air. After dyeing and drying, the hair strands were colorimetrically measured.

[0104] The dyed hair strands were then washed twelve times with a commercially available shampoo (Schauma 7-Herbal Shampoo) using a standardized procedure. After 6 and 12 shampoo washes, the hair strands were air-dried and colorimetrically measured. The color difference (AE) between the dyed, unshampooned strand and the dyed, shampooed strand was calculated using the following formula:

[0105] Lv, av, bv: Color metric values ​​before shampooing

[0106] Ln, an, bn: Colorimetric values ​​after 6 or 12 shampoo washes

[0107] The chromaticity (chroma c, color direction) is calculated from the measured values ​​a (CIE) and b (CIE) according to the following formula:

[0108] The measured value L (CIE) is a measure of the brightness or intensity of a color. Small measured values ​​indicate high intensity. The lower the L value, the greater the intensity of the color.

[0109] The measurement AE, the so-called color difference, describes the washfastness of the color. The greater the color difference AE between the colored, unshampooned strand and the colored, shampooed strand, the greater the color removal or washout of the color due to shampooing. Therefore, the washfastness is better, the lower the value of the color difference AE. Color differences of AE < 1 are imperceptible to the human eye. Color differences of AE < 2 are only visible to the trained eye. Color differences of AE > 2 are also visible to the untrained eye.

[0110] The measured and calculated data are summarized in Tables 4 to 6.

[0111] Table 4: Colorimetric results of the wash fastness tests for formulations V1, V2, V3, V4 and V5 (zero to 10 wt% PEG-8, see Table 1) Result: Addition of PEG-8 at different concentrations showed no improvement in wash fastness; the AE values ​​fluctuate too much.

[0112] Table 5: Colorimetric results of the wash fastness tests for formulations V6 and E1 to E4 (zero to 10 wt% ethanol, see Table 2)

[0113] Result:

[0114] The addition of ethanol resulted in an improvement in wash fastness; the AE values ​​of the ethanol-containing dyes E1 to E4 are lower than those of the solvent-free comparison dye V6. Table 6: Colorimetric results of the wash fastness tests for formulations V7 and E5 to

[0115] E8 (zero to 10 wt% 2-propanol, see Table 3)

[0116] Result:

[0117] The addition of 2-propanol resulted in an improvement in wash fastness; the AE values ​​of the 2-propanol-containing dyes E5 to E8 are lower than those of the solvent-free comparison dye V7.

Claims

Patent claims 1. A one-component agent for the direct, oxidant-free coloring of keratin fibers, in particular human hair, containing (a) at least one direct dye, (b) 70 - 93 wt% water, (c) one or more monohydric C2-C3 alcohols in a total amount of 2.5 - 20 wt.%, and (d) at least one amphoteric surfactant, in particular at least one alkyl betaine, characterized in that the agent contains a maximum of 0.6% by weight of polyhydric alcohols and is preferably free of polyhydric alcohols, and further characterized in that the agent has a pH of 0.5 to 6.4, preferably 1.0 to 6.0, particularly preferably 2.0 to 5.5, in each case measured at 20°C, all quantities being based on the weight of the one-component agent.

2. One-component agent according to claim 1, characterized in that the at least one monohydric C2-C3 alcohol is selected from ethanol, isopropanol, propan-1-ol, propan-2-ol, and mixtures of these alcohols.

3. Agent according to one of claims 1 or 2, characterized in that the at least one monohydric C2-C3 alcohol is selected from ethanol, isopropanol, and mixtures of these alcohols, with ethanol being preferred.

4. One-component agent according to one of claims 1 to 3, characterized in that the at least one monohydric C2-C3 alcohol is contained in a total amount of 4 - 17 wt.%, preferably 5 - 15 wt.%, particularly preferably 7 - 13 wt.%, extraordinarily preferably 9 - 12 wt.%, in each case based on the weight of the one-component agent.

5. One-component agent according to one of claims 1 to 4, characterized in that the at least one amphoteric surfactant (d) is contained in a total amount of 0.3 to 3.0 wt.%, preferably 0.5 to 2.0 wt.%, particularly preferably 0.7 to 1.0 wt.%, in each case based on the weight of the agent.

6. Agent according to one of claims 1 to 5, characterized in that the amphoteric surfactant (d) is an alkyl betaine, preferably an alkylamidoalkyl betaine, in particular a C8-14-alkylamido-(C2-6)-alkyl betaine, particularly preferably cocamidopropyl betaine ((C11H23)C(O)NH(C 3 H6)N(NH2)2CH 2 C(O)O).

7. Agent according to one of claims 1 to 6, characterized in that the at least one direct dye is present in a total amount of 0.001 to 7 wt.%, preferably 0.01 to 5.5 wt.%, more preferably from 0.08 to 3.4 wt.%, more preferably from 0.1 to 2 wt.%, more preferably from 0.3 to 1.5 wt.% and particularly preferably from 0.6 to 1 wt.%, in each case based on the weight of the one-component colorant.

8. Agent according to one of claims 1 to 7, characterized in that the agent further comprises at least one linear 1-alkanol having 4 to 40 carbon atoms, preferably in an amount - based on the total weight of the agent - of 5 to 25% by weight.

9. Agent according to one of claims 1 to 8, characterized in that the at least one linear 1-alkanol having 4 to 40 carbon atoms is selected from octan-1-ol (octyl alcohol, caprylic alcohol), decan-1-ol (decyl alcohol, capric alcohol), dodecan-1-ol (dodecyl alcohol, lauryl alcohol), tetradecan-1-ol (tetradecyl alcohol, myristyl alcohol), hexadecan-1-ol (hexadecyl alcohol, cetyl alcohol, palmityl alcohol), octadecan-1-ol (octadecyl alcohol, stearyl alcohol), eicosane-1-ol (eicosyl alcohol, arachidyl alcohol), docosane-1-ol (docosyl alcohol, behenyl alcohol), (13E)-docosen-1-ol (brassidyl alcohol) and (13Z)-docos-13-en-1-ol (erucyl alcohol) and mixtures thereof.

10. Agent according to one of claims 1 to 9, characterized in that it does not contain any hydrocarbon oil or hydrocarbon wax.

11. Agent according to one of claims 1 to 10, characterized in that no ethoxylated silicone compound is contained.

12. Agent according to one of claims 1 to 11, characterized in that it further contains at least one cationic or amphoteric polymer, in particular polyquaternium-6, preferably in an amount - based on the total weight of the agent - of 0.1 to 1 wt.%, preferably of 0.2 to 0.7 wt.%.

13. Agent according to one of claims 1 to 12, characterized in that at least one non-ionic oil-in-water emulsifier is contained, which is selected from ethoxylated C8-C24 alkanols with 10 - 100 moles of ethylene oxide per mole.

14. A method for the direct, oxidant-free coloring of keratin fibers, in particular human hair, in which a one-component agent according to any one of claims 1 to 13 is applied to the keratin fibers without using an oxidant other than atmospheric oxygen in the method.

15. Use of a one-component agent according to any one of claims 1-13 for the direct, oxidant-free coloring of keratin fibers, in particular human hair.

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