Composition for treating keratin fibers containing at least one organic c1-c6-alkoxysilane, a polysaccharide and a solvent

Abstract

The present invention relates to a composition (M) for treating keratin fibers, in particular human hair, containing – based on the total weight of the composition – (m1) at least one organic C1-C6-alkoxysilane and / or hydrolysis and / or condensation products thereof, and (m2) at least one polysaccharide, and (m3) at least one solvent other than water, and (m4) less than 10% by weight of water.

Description

[0001] Henkel AG & Co. KGaA

[0002] 2024P00209WO

[0003] Agent for treating keratinous fibers containing at least one organic Ci-Ce-alkoxysilane, one polysaccharide and one solvent

[0004] The present application relates to a treatment agent for keratinous fibers, in particular human hair, which contains at least one organic Ci-Ce alkoxysilane and / or its hydrolysis and / or condensation products, at least one polysaccharide, and at least one solvent other than water. The agent is further characterized in that it contains less than 10% water by weight.

[0005] Further aspects of the present application are methods for treating keratinous fibers, in which an agent of the first invention is applied to keratinous fibers and optionally rinsed off after a dwell time. In this process, the agent is brought into contact with a defined quantity of water during or shortly before application.

[0006] Altering the shape and color of keratin fibers, especially hair, is an important area of ​​modern cosmetics. Depending on the desired color, professionals are familiar with various dyeing systems for changing hair color. For permanent, intense colorations with good colorfastness and gray coverage, oxidation dyes are typically used. These dyes usually contain oxidation dye precursors, so-called developer components and coupler components, which react with oxidizing agents such as hydrogen peroxide to form the actual dyes. Oxidation dyes are characterized by very long-lasting color results.

[0007] When using direct dyes, pre-formed pigments diffuse from the dye into the hair fiber. Compared to oxidative hair coloring, dyes produced with direct dyes are less durable and wash out more quickly. Dyes made with direct dyes typically remain on the hair for between 5 and 20 washes.

[0008] For temporary color changes to hair and / or skin, the use of color pigments is well-known. Color pigments are generally understood to be insoluble, coloring substances. These are present in the coloring formulation in the form of small particles and are simply deposited on the hair fibers and / or skin surface. Therefore, they can usually be removed completely after a few washes with surfactant-containing cleansers. Various products of this type are available on the market under the name "hair mascara."

[0009] If a user desires particularly long-lasting color, the use of oxidative dyes has so far been their only option. However, despite numerous optimization attempts, an unpleasant ammonia or amine odor cannot be completely avoided with oxidative hair coloring. The hair damage still associated with the use of oxidative dyes also has a detrimental effect on the user's hair. Therefore, the search for alternative, high-performance dyes and coloring methods remains a challenge. Currently, there is a particular focus on coloring systems in which the color-giving compounds are integrated into a film deposited on the surface of the hair fiber, so that they can be removed completely and without altering the original hair color, if desired.

[0010] EP 2168633 B1 addresses the challenge of creating long-lasting hair colors using pigments. The document teaches that by using a combination of a pigment, an organic silicon compound, a film-forming polymer, and a solvent, it is possible to create hair colors that are particularly resistant to abrasion and / or shampooing.

[0011] The major advantage of the alkoxy silanes used in EP 2168633 B1 lies in the fact that the high reactivity of this class of compounds enables very fast coating. Excellent staining results can thus be achieved after very short application times of just a few minutes.

[0012] The coating formed by the Ci-Ce alkoxysilanes can be used to immobilize dyes applied simultaneously with the silanes in a film on the surface of the keratin fibers. Further studies have shown that the silanes can also be applied to the already dyed keratin fibers after dyeing, so that the coating forms on the already dyed keratin fibers and thus increases the residence time of the previously applied dyes on the keratin fibers.

[0013] In addition to the advantages described above, the high reactivity of alkoxysilanes also presents some disadvantages. The organic Ci-Ce alkoxysilanes used to form the coating are highly reactive compounds that undergo hydrolysis, oligomerization, and / or polymerization in the presence of water. It is important to adjust the rate of oligomerization or polymerization so that the coating can be applied within a timeframe acceptable to the user. Due to their high reactivity, organic alkoxysilanes cannot be formulated with large quantities of water, as a significant excess of water initiates immediate hydrolysis followed by polymerization. The polymerization that occurs when alkoxysilanes are stored in aqueous media manifests as a thickening or gelation of the aqueous preparation. This results in highly viscous, gel-like, or thickened preparations.Their gel-like consistency prevents them from being applied evenly to the keratin material. Furthermore, storing alkoxy silanes in the presence of high water levels leads to a loss of reactivity, making the formation of a durable and uniform coating on the keratin material impossible. However, the formation of a uniform coating is particularly important in dyeing and color protection processes.

[0014] For these reasons, it is necessary to store the organic alkoxy silanes in an anhydrous or low-water environment and to package the corresponding preparations in a separate container. The low-water preparations containing the alkoxy silanes can also be referred to as a "silane blend." To produce a hair treatment product (M), the "silane blend" is then incorporated into a cosmetic carrier, which, since the product should be low-water or anhydrous, is solvent-based. Alcohols such as ethanol, isopropanol, or longer-chain Cs-Cs alkanols or polyethylene glycols have proven to be particularly suitable solvents. Ethanol has proven to be especially effective.

[0015] For application to the keratin fibers, the agent (M), which contains the silane blend, must be brought into contact with a defined amount of water. The coating develops upon contact with water. This contact can be achieved, for example, by mixing the agent (M) with a defined amount of water or with another preparation containing a defined amount of water. This mixing process then produces the ready-to-use agent (AM), which is applied to the keratin fibers. Another option is to apply the agent (M) to previously moistened hair, so that contact with water occurs directly on the keratin fiber itself. Alternatively, the agent (M) can first be applied to the keratin fibers, and then a defined amount of water is applied to the fibers still covered with the agent (M).

[0016] In all these application methods of the agent (M) or the ready-to-use agent (AM) on the keratin fibers, the viscosity of the agent must fall within a specific range. The agent on the keratin fibers must not be too thin, otherwise it will drip off the fibers. However, it must also not be too thick, so that it spreads easily and quickly onto the keratin fibers and coats them evenly. Ideally, the low-water agent (M), which contains the silane blend, is itself relatively low in viscosity so that it mixes quickly and easily with the water or water-based composition when preparing the ready-to-use coating agent. Upon contact with the water, a specific viscosity should then develop in the ready-to-use agent (AM).

[0017] The low-water agent (M) containing the silane blend must also be stable during storage.

[0018] The objective of this application was to find a low-water or anhydrous agent (M) for treating keratinous fibers in which the reactive Ci-Ce alkoxysilanes could be stably incorporated. The agent should be storage-stable and contain a thickener that keeps the agent relatively low in viscosity in its solvent-based form, but thickens reliably during preparation of the ready-to-use agent or upon contact with water. In the ready-to-use agent, the water-initiated polymerization rate of the Ci-Ce alkoxysilanes should be adjusted such that the pot life of the agent, i.e., the period during which the Ci-Ce alkoxysilanes are still capable of polymerization and can form a coating, is at least 30 minutes. During application, the agent should enable the reproducible formation of a uniform coating.When applied to dyed keratin fibers, the product should also increase the color intensity and improve the wash fastness of the dyes.

[0019] Surprisingly, it has been found that this task can be fully solved if a substance (M) is used to treat the keratinous fibers which contains - based on its total weight - at least one organic Ci-Ce-alkoxysilane and / or its hydrolysis and / or condensation products (m1), at least one cellulose polymer (m2) as a thickener, at least one solvent other than water (m3) and less than 10 wt% water (m4).

[0020] A first object of the present invention is a means (M) for treating keratinous fibers, in particular human hair, comprising - based on the total weight of the means (M) -

[0021] (m1) at least one organic Ci-Ce alkoxysilane and / or its hydrolysis and / or condensation products, and

[0022] (m2) at least one polysaccharide, and

[0023] (m3) at least one solvent other than water, and

[0024] (m4) less than 10 wt.% water.

[0025] The work leading to this invention has surprisingly shown that the cellulose polymers (m2) are highly compatible with reactive Ci-Ce alkoxysilanes (m1) and, when formulated in a solvent-based (m3) and low-water (m4) system, yield a homogeneous and low-viscosity agent that can be reliably thickened upon contact with water and adjusted to the desired viscosity range without any undesirable reaction occurring between the thickener polymer and the Ci-Ce alkoxysilane during storage. The ready-to-use agent (AM) obtained upon mixing with water or an aqueous formulation was clear, did not form lumps, and, when applied to dyed hair, was able to both increase the intensity of the coloration and improve its wash fastness.The fact that the polysaccharides, unlike a large number of other thickener polymers tested, possess this performance profile was surprising and unforeseeable for the expert.

[0026] Keratinous fibers

[0027] Keratinous fibers include hair, but also wool, fur, and feathers. Human hair is particularly well-regarded as a keratinous fiber.

[0028] Agents for treating keratinous fibers

[0029] For the purposes of this application, the term "agent for treating keratinous fibers" is understood to mean the application of the agent (M) itself to dry or moist, and particularly preferably moistened, keratinous fibers. The agent (M) may also be converted into a ready-to-use agent (AM) by mixing it with water or a water-based preparation, which is then applied to the keratinous fibers.

[0030] The treatment of keratin fibers particularly preferably refers to the application of a treatment to dyed keratin fibers in order to increase the color intensity of the dyed fibers and / or to improve their wash fastness.

[0031] However, treatment can also refer to a coating that is intended to style, care for and / or protect the keratin fibers or hair.

[0032] The treatment is particularly well-suited to the application of the agent to dyed keratin fibers that have previously been dyed with a direct dye and / or a pigment. This application forms an undyed coating on the surface of the fibers, which prevents the dyes from washing out and thus increases the wash fastness of the dyes.

[0033] The treatment of keratinous fibers can also be understood as dyeing the fibers. For this purpose, the agent can additionally contain at least one coloring compound. Organic Ci-Cs alkoxysilanes: As the first essential component (m1) of the invention, the agent (M) according to the invention contains at least one organic Ci-Ce alkoxysilane and / or its hydrolysis and / or condensation products.

[0034] As reactive compounds, the organic Ci-Ce-alkoxysilanes oligomerize or condense, thus forming a film or coating on the surface of the keratin fibers.

[0035] Organic silicon compounds, also alternatively referred to as organosilicon compounds, are compounds that either have a direct silicon-carbon bond (Si-C) or in which the carbon is linked to the silicon atom via an oxygen, nitrogen, or sulfur atom. The organic silicon compounds according to the invention are compounds containing one to three silicon atoms. Particularly preferably, the organic silicon compounds contain one or two silicon atoms.

[0036] According to IUPAC rules, the term silane refers to a group of chemical compounds based on a silicon backbone and hydrogen. In organic silanes, the hydrogen atoms are wholly or partially replaced by organic groups such as (substituted) alkyl groups and / or alkoxy groups. In organic silanes, some of the hydrogen atoms may also be replaced by hydroxyl groups.

[0037] In an organic Ci-Ce alkoxysilane, at least one Ci-Ce alkoxy group is directly bonded to the silicon atom. The Ci-Ce alkoxy group(s) is, in particular, an ethoxy group or a methoxy group. If, for example, the hydrolyzable group is an ethoxy group, the organic silicon compound preferably contains a structural unit R'R"R"'Si-O-CH2-CH3. The substituents R', R" and R"' represent the three remaining free valences of the silicon atom.

[0038] Particularly stable films can be produced using Ci-Ce alkoxy silanes of formula (I) and / or their hydrolysis and / or condensation products,

[0039] RiR2N-L-Si(OR3) a (R4)b (I) where Ri, R2 independently represent a hydrogen atom or a Ci-Ce alkyl group, L represents a linear or branched divalent Ci-C2o alkylene group, R3, R4 independently represent a Ci-Ce alkyl group, a represents an integer from 1 to 3, and b represents the integer 3 - a.

[0040] In a further particularly preferred embodiment, a composition (M) according to the invention is characterized in that it contains at least one Ci-Ce-alkoxy-silane (m1) of formula (S-I) and / or its hydrolysis and / or condensation products.

[0041] RiR2N-L-Si(OR3) a (R4)b (Sl), wherein

[0042] Ri, R2 independently of each other stand for a hydrogen atom or a Ci-Ce alkyl group,

[0043] L stands for a linear or branched, divalent Ci-C2o alkylene group,

[0044] R3 and R4 independently represent a Ci-Ce alkyl group, a represents an integer from 1 to 3, and b represents the integer 3 - a.

[0045] The substituents Ri, R2, R3, R4 and L in the compounds of formula (I) are explained below by way of example:

[0046] Examples of a C2-Ce alkyl group are methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, n-pentyl, and n-hexyl. Propyl, ethyl, and methyl are preferred alkyl groups. Examples of a C2-Ce alkenyl group are vinyl, allyl, but-2-enyl, but-3-enyl, and isobutenyl; vinyl and allyl are preferred C2-Ce alkenyl groups.

[0047] Examples of linear divalent Ci-C2o alkylene groups include the methylene group (-CH2-), the ethylene group (-CH2-CH2-), the propylene group (-CH2-CH2-CH2-), and the butylene group (-CH2-CH2-CH2-CH2-). The propylene group (-CH2-CH2-CH2-) is particularly preferred. From a chain length of 3 carbon atoms, divalent alkylene groups can also be branched. Examples of branched, divalent C3-C2o alkylene groups are (-CH2-CH(CH3)-) and (-CH2-CH(CH3)-CH2-).

[0048] In the organic silicon compounds of formula (I)

[0049] RiR2N-L-Si(OR3) a (R4)b (I), the substituents Ri and R2 independently represent a hydrogen atom or a Ci-Ce alkyl group. Most preferentially, the substituents Ri and R2 both represent a hydrogen atom.

[0050] In the middle part of the organic silicon compound is the structural unit or linker -L- which stands for a linear or branched, divalent Ci-C2o alkylene group.

[0051] A divalent Ci-C2o alkylene group can alternatively be described as a divalent or dicovalent C1-C2o alkylene group, meaning that each group L can form two bonds. One bond is from the amino group RIR2N to the linker L, and the second bond is between the linker L and the silicon atom. Preferably, -L- represents a linear, divalent Ci-C2o alkylene group. More preferably, -L- represents a linear divalent Ci-Ce alkylene group. Particularly preferably, -L- represents a methylene group (-CH2-), an ethylene group (-CH2-CH2-), a propylene group (-CH2-CH2-CH2-), or a butylene group (-CH2-CH2-CH2-CH2-). Most preferably, L represents a propylene group (-CH2-CH2-CH2-).

[0052] The linear propylene group (-CH2-CH2-CH2-) can alternatively be called the propane-1,3-diyl group.

[0053] The organic silicon compounds of formula (I)

[0054] RiR2N-L-Si(OR3) a (R4)b (I), each carry the silicon-containing group -Si(OR3)a(R4)b at one end.

[0055] In the terminal structural unit -Si(OR3)a(R4)b, the R3 group represents a hydrogen atom or a Ci-Ce alkyl group, and the R4 group represents a Ci-Ce alkyl group. Particularly preferably, R3 and R4 independently represent a methyl group or an ethyl group.

[0056] Here, 'a' represents an integer from 1 to 3, and 'b' represents the integer 3 - 'a'. If 'a' represents the number 3, then 'b' equals 0. If 'a' represents the number 2, then 'b' equals 1. If 'a' represents the number 1, then 'b' equals 2.

[0057] Particularly resistant films could be produced if the agent (M) contains at least one organic silicon compound (m1) of formula (I) in which the residues R3, R4 independently stand for a methyl group or for an ethyl group.

[0058] When applied to dyed keratinous fibers, the intensity and wash fastness of the dyes could be greatly increased, especially when the agent (M) contains at least one organic silicon compound (m1) of formula (I) in which the residues R3, R4 independently represent a methyl group or an ethyl group.

[0059] Furthermore, dyes with the best wash fastness were obtained when the agent contained at least one organic silicon compound (m1) of formula (I), in which the residue a represents the number 3. In this case, the residue b represents the number 0.

[0060] In a further preferred embodiment, the agent (M) according to the invention is characterized in that it contains at least one organic silicon compound (m1) of formula (I), wherein R3, R4 independently represent a methyl group or an ethyl group and

[0061] - a stands for the number 3 and

[0062] - b represents the number 0.

[0063] In a further preferred embodiment, a composition according to the invention is characterized in that it contains at least one organic Ci-Ce-alkoxysilane (m1) of formula (I), RiR2N-L-Si(OR3) a (R4)b (I), wherein

[0064] - Ri, R2 both stand for a hydrogen atom, and

[0065] - L represents a linear, divalent Ci-Ce alkylene group, preferably a propylene group (-CH2-CH2-CH2-) or an ethylene group (-CH2-CH2-),

[0066] - R3 represents a hydrogen atom, an ethyl group or a methyl group,

[0067] - R4 represents a methyl group or an ethyl group,

[0068] - a stands for the number 3 and

[0069] - b represents the number 0, and / or its hydrolysis and / or condensation products.

[0070] Organic silicon compounds of formula (I) that are particularly suitable for solving the problem set out in the invention are

[0071] - (3-Aminopropyl)triethoxysilane

[0072] - (3-Aminopropyl)trimethoxysilane

[0073] - 1-(3-Aminopropyl)silanetriol

[0074] - (2-Aminoethyl)triethoxysilane

[0075] - (2-Aminoethyl)trimethoxysilane

[0076] - (3-Dimethylaminopropyl)triethoxysilane

[0077] - (3-Dimethylaminopropyl)trimethoxysilane

[0078]

[0079] - (2- D i met hy la min oethy l)t riet h oxys i la n .

[0080] - (2-Dimethylaminoethyl)trimethoxysilane and

[0081] 1-(2-Dimethylaminoethyl)silanetriol

[0082] In a further preferred embodiment, a composition (M) according to the invention is characterized in that it contains at least one organic Ci-Ce-alkoxysilane selected from the group consisting of

[0083] - (3-Aminopropyl)triethoxysilane

[0084] - (3-Aminopropyl)trimethoxysilane

[0085] - 1-(3-Aminopropyl)silanetriol - (2-Aminoethyl)triethoxysilane

[0086] - (2-Aminoethyl)trimethoxysilane

[0087] - 1-(2-Aminoethyl)silanetriol

[0088] - (3-Dimethylaminopropyl)triethoxysilane

[0089] - (3-Dimethylaminopropyl)trimethoxysilane

[0090] - 1 -(3-Dimethylaminopropyl)silanetriol

[0091] - (2-Dimethylaminoethyl)triethoxysilane

[0092] - (2-Dimethylaminoethyl)trimethoxysilane

[0093] - 1-(2-Dimethylaminoethyl)silanetriol and / or the hydrolysis and / or condensation products of the aforementioned compounds.

[0094] The aforementioned organic silicon compounds of formula (I) are commercially available. (3-Aminopropyl)trimethoxysilane, for example, can be purchased from Sigma-Aldrich. (3-Aminopropyl)triethoxysilane is also commercially available from Sigma-Aldrich.

[0095] In further experiments, it has also proven to be particularly advantageous if the agent contains at least one organic Ci-Ce-alkoxysilane (m1) of formula 1.

[0096] R5Si(OR6)k(R7)m (II), where

[0097] - R5 represents a Ci-Cia alkyl group,

[0098] - Re stands for a hydrogen atom or a Ci-Ce alkyl group,

[0099] - R7 stands for a Ci-Ce alkyl group

[0100] - k represents an integer from 1 to 3, and

[0101] - m represents the integer 3 - k stands for.

[0102] The organic silicon compounds of formula (II) can also be referred to as silanes of the alkyl-alkoxy-silane type.

[0103] If Re represents a hydrogen atom, the group directly bonded to the silicon atom is an OH group. If k equals three and the Re group represents a hydrogen atom in all three units, the silane is an alkyl trihydroxysilane, which can alternatively be called an alkylsilane triol. Alkylsilane triols are the complete hydrolysis products of the corresponding alkoxysilanes.

[0104] Organic Ci-Ce-alkoxysilanes of formula (II) are preferred

[0105] R5Si(ORe)k(R7)m (II), where - Rs represents a Ci-Cia alkyl group,

[0106] - Re stands for a Ci-Ce alkyl group,

[0107] - R7 stands for a Ci-Ce alkyl group

[0108] - k represents an integer from 1 to 3, and

[0109] - m represents the integer 3 - k, and / or their hydrolysis and / or condensation products.

[0110] In a further particularly preferred embodiment, a composition (M) according to the invention is characterized in that it contains at least one Ci-Ce-alkoxy-silane (m1) of formula (S-Il) and / or its hydrolysis and / or condensation products.

[0111] R5Si(OR6)k(R7)m (S-Il), where

[0112] - R5 represents a Ci-Cia alkyl group,

[0113] - Re stands for a Ci-Ce alkyl group,

[0114] - R7 stands for a Ci-Ce alkyl group

[0115] - k represents an integer from 1 to 3, and

[0116] - m represents the integer 3 - k stands for.

[0117] In the organic silicon compounds of formula (II), the group R5 represents a C1-C18 alkyl group. This Ci-Cie alkyl group is saturated and can be linear or branched. Preferably, R9 represents a linear Ci-Cis alkyl group. Preferably, R5 represents a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, an n-dodecyl group, or an n-octyldecyl group. Particularly preferably, R9 represents a methyl group, an ethyl group, an n-hexyl group, or an n-octyl group.

[0118] In the organic silicon compounds of form (II), the residue Re represents a hydrogen atom or a Ci-Ce alkyl group. Particularly preferably, Re represents a methyl group or an ethyl group.

[0119] In the organic silicon compounds of form (II), the residue R7 represents a Ci-Ce alkyl group. R7 particularly preferably represents a methyl group or an ethyl group.

[0120] Furthermore, k represents an integer from 1 to 3, and m represents the integer 3 - k. If k represents the number 3, then m equals 0. If k represents the number 2, then m equals 1. If k represents the number 1, then m equals 2.

[0121] Particularly stable films, improved color intensities, and especially good wash fastness were achieved when at least one organic Ci-Ce-alkoxysilane of formula (II) was used in the mean (M), in which the residue k represents the number 3. In this case, the residue m represents the number 0.

[0122] Organic silicon compounds of formula (II) are particularly suitable for solving the problem set out in the invention.

[0123] - Methyltrimethoxysilane

[0124] - Ethyltrimethoxysilane - n-Hexyltrimethoxysilane

[0125] - n-Octyltriethoxysilane

[0126] - n-Dodecyltrimethoxysilane and / or

[0127]

[0128] - n-Dodecyltriethoxysilane.

[0129] In a further preferred embodiment, a composition (M) according to the invention is characterized in that it contains at least one organic silicon compound of formula (II) selected from the group consisting of

[0130] - Methyltrimethoxysilane

[0131] - Methyltriethoxysilane

[0132] - Ethyltrimethoxysilane

[0133] - Ethyltriethoxysilane

[0134] - Propyltrimethoxysilane

[0135] - Propyltriethoxysilane

[0136] - Hexyltrimethoxysilane

[0137] - Hexyltriethoxysilane

[0138] - Octyltrimethoxysilane

[0139] - Octyltriethoxysilane

[0140] - Dodecyltrimethoxysilane

[0141] - Dodecyltriethoxysilane

[0142] - Octadecyltrimethoxysilane and / or

[0143] - Octadecyltriethoxysilane.

[0144] Particularly robust films were obtained when a combination of organic Ci-Ce alkoxysilanes of formulas (I) and (II) or the particularly preferred representatives of these groups was used in the composition (M). In a further particularly preferred embodiment, a composition (M) according to the invention is characterized in that it contains

[0145] - at least one first Ci-Ce-alkoxy-silane (m1) selected from the group consisting of (3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane, (2-aminoethyl)trimethoxysilane, (2-aminoethyl)triethoxysilane, (3-dimethyl-aminopropyl)trimethoxysilane, (3-dimethylaminopropyl)triethoxysilane, (2-dimethylaminoethyl)trimethoxysilane, (2-dimethylaminoethyl)triethoxysilane and / or their hydrolysis and / or condensation products, and

[0146] - at least one second Ci-Ce-alkoxy-silane (m1) selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane and / or their hydrolysis and / or condensation products.

[0147] In this context, it has proven preferable if the agent (M) - based on the total weight of the agent (M) - contains one or more organic Ci-Ce-alkoxysilanes (m1) and / or their hydrolysis and / or condensation products in a total amount of 0.1 to 50.0 wt.%, preferably 5.0 to 45 wt.%, more preferably 15.0 to 40 wt.% and most preferably 20.0 to 35.0 wt.%.

[0148] In a further particularly preferred embodiment, a composition according to the invention is characterized in that it contains – based on the total weight of the composition (M) – one or more organic Ci-Ce-alkoxysilanes (m1) and / or their hydrolysis and / or condensation products in a total amount of 0.1 to 50.0 wt.%, preferably 5.0 to 45 wt.%, more preferably 15.0 to 40 wt.% and most preferably 20.0 to 35.0 wt.%.

[0149] Hydrolysis and / or condensation products of organic Ci-Ce alkoxysilanes

[0150] Even the addition of small amounts of water leads to hydrolysis of organic Ci-Ce alkoxysilanes with at least one hydrolyzable group (the respective alkoxy group). The hydrolysis products and / or organic silicon compounds with at least one hydroxyl group can react with each other in a condensation reaction. For this reason, both the organic Ci-Ce alkoxysilanes with at least one hydrolyzable group and their hydrolysis and / or condensation products may be present in the respective product. When using silanes with at least one hydroxyl group, both the organic silicon compounds with at least one hydroxyl group and silanes with multiple hydroxyl groups, as well as their condensation products, may be present in the product.

[0151] A condensation product is defined as a product formed by the reaction of at least two organic silicon compounds, each containing at least one hydroxyl group or hydrolyzable group per molecule, with the elimination of water and / or an alkanol. Condensation products can be, for example, dimers, trimers, or oligomers, in equilibrium with the monomers. Depending on the amount of water used or consumed in the hydrolysis, the equilibrium shifts from the monomeric organic silicon compounds to the condensation product.

[0152] Particularly good results were obtained when organic Ci-Ce alkoxysilanes of formula (I) and / or (II) were used in the process. Since, as previously described, hydrolysis / condensation begins even in trace amounts of moisture, the hydrolysis and / or condensation products of the organic alkoxysilanes (I) and / or (II) are also included in this embodiment.

[0153] The organic Ci-Ce alkoxy silanes, especially those of formula (I) and / or (II), are reactive compounds that can undergo hydrolysis and condensation reactions with water.

[0154] The reaction of organic Ci-Ce alkoxy silanes with water can occur via various pathways. The reaction begins as soon as the Ci-Ce alkoxy silanes come into contact with water through mixing. Once Ci-Ce alkoxy silanes and water come into contact, an exothermic hydrolysis reaction takes place according to the following scheme (reaction scheme using 3-aminopropyltriethoxysilane as an example):

[0155] Depending on the number of hydrolyzable Ci-Ce-alkoxy groups per silane molecule, the hydrolysis reaction can also occur multiple times per Ci-Ce-alkoxy-silane used: or

[0156] Hydrolysis using methyltrimethoxysilane as an example:

[0157] Ome Ome

[0158] CH3— Si— OMe + H2O CH3— si — OH + MeOH

[0159] Ome Ome

[0160] Depending on the amount of water used, the hydrolysis reaction can also occur multiple times per Ci-Ce-alkoxy-silane used:

[0161] Ome OH

[0162] CH3— Si I— Ome + 2 H2O CH3— SI— OH + 2 MeOH

[0163] Ome Ome or

[0164] Following hydrolysis, or almost simultaneously with hydrolysis, the partially (or in some cases completely) hydrolyzed Ci-Ce-alkoxy silanes undergo condensation. The pre-condensation can proceed, for example, according to the following scheme:

[0165] OH OH Ome OH

[0166] H3C-SI— OMe + H3C— Si— OMe ► MeO— Si— O— Si— OMe + MeOH

[0167] Ome Ome CH 3 CH3 Both partially hydrolyzed and fully hydrolyzed Ci-Ce-alkoxysilanes can participate in the condensation reaction, undergoing condensation with unreacted, partially or fully hydrolyzed Ci-Ce-alkoxysilanes.

[0168] Possible condensation reactions include (shown using the mixture of (3-aminopropyl)triethoxysilane and methyltrimethoxysilane): and / or

[0169] In the above exemplary reaction schemes, the condensation to a dimer is shown in each case, however further condensations to oligomers with several silane atoms are also possible and preferred.

[0170] This hydrolysis or condensation reaction begins even in the presence of very small amounts of water; therefore, the oligomers and / or condensation products of the aforementioned organic silicon compounds are also included in this invention.

[0171] For the purposes of the application, condensation products of organic Ci-Ce-alkoxysilanes are understood to be condensates that are formed by the reaction of the organic Ci-Ce-alkoxysilanes with each other.

[0172] Polysaccharides (m2)

[0173] As the second essential component (m2) of the invention, the agent according to the invention contains at least one polysaccharide.

[0174] The polysaccharide(s) (m2) have proven to be particularly compatible with the organic Ci-Ce alkoxysilane(s) (m1). The joint incorporation of (m1) and (m2) into a low-water, solvent-based system results in a homogeneous and storage-stable agent (M) that can be stored for extended periods without undesirable reactions between (m1) and (m2). The agent (M) is low in viscosity and clear, but thickens reliably upon contact with water or an aqueous preparation, ensuring thorough mixing of the two compositions. The ready-to-use agent produced in this manner is also homogeneous and clear.Furthermore, the reactivity of the silanes in the ready-to-use product is maintained long enough that, even in whole-head application, the ready-to-use product can be applied comfortably and without haste to the entire head without the silanes losing their reactivity too quickly.

[0175] Polysaccharides (or complex carbohydrates) are carbohydrates in which a large number of monosaccharides (simple sugars) are linked via a glycosidic bond. Polysaccharides belong to the class of polymers and are biopolymers. According to the invention, the polysaccharide(s) can be cationic, nonionic, and / or anionic.

[0176] Suitable polysaccharides include, for example, cellulose, guar gum, glycogen, starch, pectins, callose and / or chitin.

[0177] The effects described above could be achieved with cationic and / or non-ionic polysaccharides, but especially with cationic polysaccharides.

[0178] In a further particularly preferred embodiment, a means (M) according to the invention is characterized in that it contains at least one polysaccharide (m2) from the group consisting of cationic, non-ionic and / or anionic polysaccharides, preferably from the group consisting of cationic and non-ionic polysaccharides, and most preferably from the group consisting of cationic polysaccharides.

[0179] Cationic polymers are defined as polymers that have a group in their main and / or side chain which can be either temporarily or permanently cationic. According to the invention, polymers that possess a cationic group regardless of the pH of the compound are referred to as "permanently cationic." These are generally polymers containing a quaternary nitrogen atom, for example, in the form of an ammonium group. Quaternary ammonium groups are preferred cationic groups. In particular, polymers in which the quaternary ammonium group is bound to a polysaccharide main chain via an optionally substituted Ci to C4 hydrocarbon group have proven to be especially suitable.

[0180] Other cationic polymers according to the invention are the so-called "temporarily cationic" polymers. These polymers typically contain an amino group which, at certain pH values, exists as a quaternary ammonium group and is therefore cationic. In a further, particularly preferred embodiment, a composition (M) according to the invention is characterized in that it contains at least one cationic polysaccharide (m2) from the group consisting of cationic celluloses, cationic guar, and / or cationic starches, and most preferably selected from the group consisting of cationic celluloses.

[0181] For the purposes of the present invention, cationic celluloses are understood to be cellulose derivatives which have been synthetically modified by reaction with one or more reagents such that they carry cationic charges or a large excess of cationic charges.

[0182] Cellulose is the main component of plant cell walls. It is unbranched and consists of several hundred to tens of thousands of β-D-glucose molecules (β-1,4-glycosidic bonds) or cellobiose units. The average molar mass is 50,000–500,000 g / mol. The average degree of polymerization (DP) of cellulose can be determined by various physical measurements. Viscosity measurements are most commonly used to determine the degree of polymerization, yielding characteristic values ​​depending on the biological origin.

[0183] Quaternated hydroxyethylcelluloses have proven particularly suitable for solving the problem described in the invention. Hydroxyethylcelluloses are celluloses in which the hydroxyl groups on the glucose units are substituted at one or more positions by (poly)hydroxyethyl groups. Hydroxyethylcelluloses therefore possess at least one structural unit of formula (a), (b) and / or (c).

[0184]

[0185] In structural units (a), (b) and (c) each n can independently assume an integer from 1 to 50, preferably from 1 to 20. The positions marked with an asterisk represent the linkage point to the next glucose unit.

[0186] To introduce the cationic charge(s), the hydroxyethylcellulose is now quaternized, i.e., a quaternary tetraalkylammonium group - which may optionally carry further substituents or heteroatoms - is introduced by chemical reaction with a reagent.

[0187] In a further particularly preferred embodiment, a composition according to the invention is characterized in that it contains at least one quaternized hydroxyethylcellulose as the cationic cellulose (m2).

[0188] It is particularly advantageous if the quaternized hydroxyethylcelluloses contain one or more

[0189] Structural units of formula (d) carry, where X can represent chloride, bromide, acetate, or methyl sulfate. The position of group (d) marked with an asterisk is preferably bound via a hydroxyl group of the hydroxyethylcellulose (i.e., the hydrogen atom on a hydroxyl group of the hydroxyethylcellulose is replaced by the group (d)).

[0190] In a further particularly preferred embodiment, a means according to the invention is characterized in that it contains a cationic cellulose (m2) with at least one structural unit of the general formula (I),

[0191] where

[0192] Z1 and / or Z2 either represent a hydrogen atom or a group Y, n independently in each of the groupings Y stands for an integer from 0 to 20,

[0193] X stands for chloride, bromide, acetate or methyl sulfate, provided that at least one of the groups Z1 and / or Z2 stands for a group Y.

[0194] Preferably, n represents an integer of at least 1.

[0195] In a further particularly preferred embodiment, a means according to the invention is characterized in that it contains a cationic cellulose (m2) with at least one structural unit of the general formula (I), where Z1 and / or Z2 represent either a hydrogen atom or a group Y, n independently in each of the groupings Y stands for an integer from 1 to 20,

[0196] X stands for chloride, bromide, acetate or methyl sulfate, provided that at least one of the groups Z1 and / or Z2 stands for a group Y.

[0197] The best results were obtained when polyquaternium-10 was used as the cationic cellulose (m2).

[0198] Polyquaternium-10 is also known as "Cellulose 2-hydroxyethyl 2-[2-hydroxy-3-(trimethylammonio)-propoxy]ethyl 2-hydroxy-3-(trimethylammonio)propyl ether chloride" and has the CAS number 81859-24-7. The compound is commercially available, for example, under the trade name Antistatic 10 from 3V Sigma and under the trade name JR 400 from Shanghai Jida meticulous Chemical Industry.

[0199] In a further particularly preferred embodiment, a composition according to the invention is characterized in that it contains polyquaternium-10 as the cationic cellulose (m2).

[0200] Polyquaternium-4 is also a particularly suitable cationic cellulose. It is a copolymer of hydroxyethylcellulose and dimethyl diallyl ammonium chloride and is likewise a highly preferred cationic polymer. Polyquaternium-4 is assigned the CAS number 92183-41-0.

[0201] Polyquaternium-24 is a quaternary ammonium salt of hydroxyethylcellulose reacted with a lauryldimethylammonium-substituted epoxide, which bears the CAS number 107987-23-5. Polyquaternium-24 is also a highly preferred cationic polymer.

[0202] Preferably, the composition according to the invention can also contain at least one cationic guar as a polysaccharide (m2). Guar, which can alternatively also be called guar flour, guar gum, or guar gum, bears the CAS number 9000-30-0. Guar is a polysaccharide obtained from the seed of the guar bean and consists of D-mannopyranose units linked together in a chain-like fashion via beta-1,4-glycosidic bonds. Every second mannopyranose unit carries alpha-D-galcotpyranosyl residues via a 1,6-linkage.

[0203] Guar is preferably cationically modified. Guar hydroxypropyltrimonium chloride, for example, can be used as a particularly suitable cationic guar derivative.

[0204] Particularly preferred guar derivatives are the cationic hydroxyalkyl guar derivatives, preferably cationic hydroxyethyltrimethylammonium guar and / or cationic hydroxypropyltrimethylammonium guar with average molecular weights of 300,000 to 2,500,000 Daltons. Especially preferred are the cationic guar polymers known under the INCI name Guar Hydroxypropyltrimonium Chloride with a molecular weight (average weight) of 900,000 to 3,600,000 Daltons, preferably of 300,000 to 2,500,000 Daltons.

[0205] The cationic charge density of these guar polymers is preferably at least 0.5 meq / g, more preferably at least 0.6 meq / g, and particularly at least 0.8 meq / g. Their nitrogen content is preferably in the range of 1.1 to 1.6 wt.% (based on their total weight).

[0206] Suitable cationic guar compounds are marketed, for example, under the trade name Jaguar® and have the INCI name Guar Hydroxypropyltrimonium Chloride. Furthermore, particularly suitable cationic guar compounds are also available from Hercules under the name N-Hance®. Additional cationic guar compounds are marketed by BASF SE under the name Cosmedia®. A preferred cationic guar compound is the product AquaCat® from Hercules. This raw material is a pre-dissolved cationic guar compound.

[0207] The agent according to the invention can also contain at least one cationic starch as a polysaccharide (m2).

[0208] Cationic starch derivatives are cationic derivatives of starch. The term starch refers to polysaccharides that are produced on an industrial scale from potatoes, tapioca, cereals, or corn.

[0209] Starch is a polysaccharide consisting primarily of alpha-D-glucose units. Starch molecules are made up of alpha-D-glucose molecules linked together by glycosidic bonds. The term "starch" here encompasses amylose, which consists of linear chains with a helical structure where the alpha-D-glucose units are linked only by alpha-1,4-glycosidic bonds. The term "starch" also includes amylopectin, which comprises highly branched structures with both alpha-1,6-glycosidic and alpha-1,4-glycodiditic linkages.

[0210] These starch derivatives are modified according to the usual methods known and described in the literature, and finally cationic and starch derivatives are produced from them.

[0211] The degree of substitution for the cationic substitution of starch can, for example, range between 0.01 and 5.0. A degree of substitution of 0.1 to 3.0 is preferred. Degrees of substitution of 0.1 to 2.0 are particularly preferred. The molecular weights of the cationic starch derivatives according to the invention range between 100,000 and 50,000,000 Daltons. Preferably, the starch derivatives according to the invention have a molecular weight of 100,000 to 25,000,000 Daltons, and most preferably, a molecular weight of 100,000 to 20,000,000 Daltons.

[0212] Suitable cationic starch derivatives are available, for example, from Ondeo Nalco under the trade names Starch HP CI 25, Sensomer CI 50, Starch CI 50 A 40, Starch Cl 25 MO, Starch Cl 25 TA, Starch HP Cl 25, and Starch HP Cl 50. Naturally, all other cationic starch derivatives that meet at least the requirements regarding the degree of substitution or molecular weight are also suitable cationic starch derivatives within the meaning of the present invention.

[0213] Very good results were also obtained when at least one non-ionic cellulose was used as the polysaccharide (m2).

[0214] Cellulose is composed of β-1,4-glycosidically linked D-glucopyranose units. In the solid state, crystalline regions alternate with those of lower order (amorphous regions) within cellulose. Natural and manufacturing-related impurities, such as the presence of carboxyl groups, are typically in the range of less than 1%. According to the invention, cellulose itself is therefore not considered an anionic polysaccharide.

[0215] A cellulose suitable for use according to the invention preferably has a degree of polymerization (DP), i.e., a chain length of glucopyranose units, of 10 to approximately 8000. In particular, so-called microcrystalline cellulose can also exhibit advantageous effects in this regard. Microcrystalline cellulose is obtained by partial alkaline or acidic hydrolysis of celluloses, in which only the amorphous regions of the semi-crystalline cellulose are attacked and completely dissolved. This initially results in microfine cellulose, which is disaggregated into microcrystalline cellulose in aqueous suspension under mechanical stress. The degree of polymerization remaining after hydrolysis (also leveling-off polymerization = LODP) of the microcrystalline cellulose is in the range of approximately 30–400. Preferred celluloses are therefore microcrystalline celluloses and have a degree of polymerization of 30 to 400.

[0216] For the purposes of this invention, a nonionic cellulose also includes a nonionic derivative of a cellulose, i.e., the cellulose can be modified with substituents by reaction with a chemical agent and / or bear further uncharged chemical functional groups. Within the scope of the present invention, the nonionic cellulose derivatives and the definition of nonionic celluloses are included.

[0217] Particularly preferred are non-ionic celluloses, for example, selected from the group consisting of hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, hydroxybutyl methylcellulose, hydroxyethyl ethylcellulose, hydroxypropyl methyl cellulose, methyl ethylcellulose and ethylcellulose.

[0218] In a further particularly preferred embodiment, a composition (M) according to the invention is characterized in that it contains at least one non-ionic polysaccharide (m2) from the group consisting of 2-hydroxypropyl cellulose, 3-hydroxypropyl cellulose, 2-hydroxypropyl methyl cellulose, 3-hydroxypropyl methyl cellulose and / or 2-hydroxyethyl cellulose, particularly preferably from the group consisting of 2-hydroxypropyl cellulose and 3-hydroxypropyl cellulose.

[0219] Particularly well suited to solving the problem according to the invention are the non-ionic celluloses from the group of cellulose ethers, in particular from the group consisting of hydroxyethylcellulose, hydroxypropylcellulose and hydroxypropyl methylcellulose.

[0220] These are sold, for example, under the trademarks Culminal® and Benecel® and Natrosol® types by companies such as Aqualon, Hercules or Ashland.

[0221] A hydroxypropylcellulose with a molecular weight of 30,000 to 50,000 g / mol, which is sold, for example, under the trade name Nisso Sl® by the company Lehmann & Voss, Hamburg, is also particularly suitable.

[0222] To achieve sufficient thickening performance, the polysaccharides (m2) are preferably used in specific quantity ranges in the compound (M). A particularly stable compound (M) with very good thickening properties upon mixing with water was obtained when the compound (M) contained one or more polysaccharides (m2) in a total amount of 0.1 to 12.0 wt.%, preferably 0.4 to 8.5 wt.%, more preferably 0.8 to 7.0 wt.%, and most preferably 2.0 to 5.0 wt.%, based on the total weight of the compound (M). In a further particularly preferred embodiment, a composition (M) according to the invention is characterized in that it contains - based on its total weight - one or more polysaccharides (m2) in a total amount of 0.1 to 12.0 wt.%, preferably 0.4 to 8.5 wt.%, more preferably 0.8 to 7.0 wt.% and most preferably 2.0 to 5.0 wt.%.

[0223] In a further particularly preferred embodiment, a composition (M) according to the invention is characterized in that it contains - based on its total weight - one or more cationic celluloses and / or cellulose derivatives (m2) in a total amount of 0.1 to 12.0 wt.%, preferably 0.4 to 8.5 wt.%, more preferably 0.8 to 7.0 wt.% and most preferably 2.0 to 5.0 wt.%.

[0224] In a further particularly preferred embodiment, a composition (M) according to the invention is characterized in that it contains - based on its total weight - one or more cationic guars and / or guar derivatives (m2) in a total amount of 0.1 to 12.0 wt.%, preferably 0.4 to 8.5 wt.%, more preferably 0.8 to 7.0 wt.% and most preferably 2.0 to 5.0 wt.%.

[0225] In a further particularly preferred embodiment, a composition (M) according to the invention is characterized in that it contains - based on its total weight - one or more non-ionic celluloses and / or cellulose derivatives (m2) in a total amount of 0.1 to 12.0 wt.%, preferably 0.4 to 8.5 wt.%, more preferably 0.8 to 7.0 wt.% and most preferably 2.0 to 5.0 wt.%.

[0226] Solvent average (M)

[0227] Since the agent (M) according to the invention is low in water or anhydrous, the cosmetic carrier of the agent comprises at least one solvent (m3) other than water.

[0228] Compounds from the group consisting of ethanol, isopropanol, poly-Ci-Ce alkylene glycols, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, dipropylene glycol, ethanol, isopropanol, diethylene glycol monoethyl ether, glycerin, phenoxyethanol, and benzyl alcohol are particularly well-suited as cosmetic carriers. Ethanol and / or isopropanol have proven especially suitable. Ethanol is the most preferred.

[0229] In a further particularly preferred embodiment, a composition (M) according to the invention is characterized in that it contains one or more solvents (m3) other than water from the group consisting of ethanol, isopropanol, poly-Ci-Ce alkylene glycols, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, dipropylene glycol, diethylene glycol monoethyl ether, glycerol, phenoxyethanol and benzyl alcohol, most preferably ethanol. Ethanol has the CAS number 64-17-5. Isopropanol has the CAS number 67-63-0.

[0230] 1,2-Propylene glycol is also alternatively known as 1,2-propanediol and has the CAS numbers 57-55-6 [(RS)-1,2-dihydroxypropane], 4254-14-2 [(R)-1,2-dihydroxypropane] and 4254-153 [(S)-1,2-dihydroxypropane]. Ethylene glycol is also alternatively known as 1,2-ethanediol and has the CAS number 107-21-1. Glycerol is also alternatively known as 1,2,3-propanetriol and has the CAS number 56-81-5. Phenoxyethanol has the CAS number 122-99-6.

[0231] All of the solvents described above are commercially available from various chemical suppliers such as Aldrich or Fluka.

[0232] Other suitable solvents include alkylene glycols of formula (AG) where x represents an integer from 1 to 10000, preferably an integer from 2 to 800, further preferably an integer from 3 to 600, even more preferably an integer from 3 to 400, and most especially preferably an integer from 4 to 200.

[0233] In a further particularly preferred embodiment, a method according to the invention is therefore characterized in that the agent (a) contains one or more alkylene glycols (a4) of formula (AG),

[0234] (AG), where x represents an integer from 1 to 10000, preferably an integer from 2 to 800, more preferably an integer from 3 to 600, even more preferably an integer from 3 to 400, and most preferably an integer from 4 to 200. The alkylene glycols of formula (AG) are protic substances with at least one hydroxyl group, which, due to their repeating unit -CH2-CH2-O-, provided that x represents a value of at least 2, can also be referred to as polyalkylene glycols or polyethylene glycols. In the alkylene glycols of formula (AG), x represents an integer from 1 to 10000. In the course of the work leading to this invention, it has been found that these polyethylene glycols are particularly well suited to improving the fastness properties of the dyes and also to optimally adjusting the viscosity of the dyes.

[0235] Depending on their chain length, polyethylene glycols are liquid or solid, water-soluble polymers. Polyethylene glycols with a molecular weight between 200 g / mol and 400 g / mol are non-volatile liquids at room temperature. PEG 600 has a melting range of 17 to 22 °C and thus a paste-like consistency. At molecular weights above 3000 g / mol, PEGs are solid substances and are commercially available as flakes or powder.

[0236] The use of low molecular weight alkylene glycols (or polyethylene glycols) has proven particularly suitable for solving the problem described in the invention. In the case of low molecular weight alkylene glycols (or polyethylene glycols) as defined in the present invention, x represents an integer from 1 to 100, preferably an integer from 1 to 80, more preferably an integer from 2 to 60, even more preferably an integer from 3 to 40, even more preferably an integer from 4 to 20, and most preferably an integer from 6 to 15.

[0237] In a further particularly preferred embodiment, a means according to the invention is characterized in that it contains at least one alkylene glycol of formula (AG-1), where x1 represents an integer from 1 to 100, preferably an integer from 1 to 80, further preferably an integer from 2 to 60, still more preferably an integer from 3 to 40, still more preferably an integer from 4 to 20 and most especially preferably an integer from 6 to 15.

[0238] One particularly preferred low-molecular-weight polyethylene glycol is, for example, PEG-8. PEG-8 comprises, on average, 8 ethylene glycol units (x1 = 8), has an average molecular weight of 400 g / mol, and bears the CAS number 25322-68-3. PEG-8 is also alternatively referred to as PEG 400 and is commercially available, for example, from the company APS.

[0239] Other suitable low molecular weight polyethylene glycols include PEG-6, PEG-7, PEG-9 and PEG-10.

[0240] Another suitable polyethylene glycol is, for example, PEG-32. PEG-32 comprises 32 ethylene glycol units (x1 = 32), has an average molecular weight of 1500 g / mol, and bears the CAS number 25322-68-3. PEG-32 is also alternatively known as PEG 1500 and can be purchased commercially, for example, from the company Clariant.

[0241] The solvent(s) other than water (m3) are preferably used in the compound (M) in specific quantity ranges. Good results were obtained when the compound (M) – based on the total weight of the compound (M) – contained one or more solvents other than water in a total amount of 10.0 to 99.0 wt.%, preferably 30.0 to 95.0 wt.%, more preferably 50.0 to 90.0 wt.%, even more preferably 55.0 to 85.0 wt.%, and most preferably 60.0 to 80.0 wt.%.

[0242] In a further particularly preferred embodiment, a composition (M) according to the invention is characterized in that it contains – based on the total weight of the composition (M) – one or more solvents (m3) other than water in a total amount of 10.0 to 99.0 wt.%, preferably 30.0 to 95.0 wt.%, more preferably 50.0 to 90.0 wt.%, even more preferably 55.0 to 85.0 wt.% and most preferably 60.0 to 80.0 wt.%.

[0243] In a further particularly preferred embodiment, a composition (M) according to the invention is characterized in that it contains - based on the total weight of the composition (M) - 10.0 to 99.0 wt.%, preferably 30.0 to 95.0 wt.%, more preferably 50.0 to 90.0 wt.%, even more preferably 55.0 to 85.0 wt.% and most preferably 60.0 to 80.0 wt.% ethanol (m3).

[0244] Average water content (m4) (M)

[0245] The low water content of the agent (M) is one of the factors that ensures its storage stability and allows the organic Ci-Ce alkoxysilanes to remain in a reactive form and not yet fully polymerized. If complete crosslinking of the organic Ci-Ce alkoxysilanes occurs only during or after application of the agent (M) to the keratin fibers, the resulting film is characterized by particularly high robustness and resistance. Robust films are already obtained when the respective agent (M) contains less than 10.0 wt% water. However, further reduction of the water content in the agent (M) has proven advantageous.

[0246] Particularly preferably, the coating agent (M) is formulated with such low water content that the water content of the agent (M) - based on the total weight of the agent (M) - is in the range of 0 to 7.5 wt.%, preferably 0.0 to 5.0 wt.%, more preferably 0.0 to 4.0 wt.% and most preferably 0.1 to 2.5 wt.% water (m4).

[0247] In a further particularly preferred embodiment, a means (M) according to the invention is characterized in that it contains - based on the total weight of the means (M) - 0 to 7.5 wt.%, preferably 0.0 to 5.0 wt.%, more preferably 0.0 to 4.0 wt.% and most preferably 0.1 to 2.5 wt.% water (m4).

[0248] The range of 0.1 to 2.5 wt% water means that the product contains as little water as possible, or that the amount of water that may be introduced into the product (M) by other ingredients contained in the product (M) does not exceed 2.5 wt%.

[0249] Methods for treating keratinous fibers

[0250] The agent (M) described above of the first invention is used for treating keratinous fibers, in particular human hair.

[0251] The composition (M), which contains the organic Ci-Ce-alkoxysilane(s) (m1), is formulated to be low in water or anhydrous (m4). Therefore, water must be added to the composition (M) during application to achieve the final hydrolysis or condensation of the organic Ci-Ce-alkoxysilane(s). Preferably, the amount of water added is defined.

[0252] The addition of water can be accomplished in various ways. In a particularly preferred embodiment, the agent (M) can be applied to the keratinous fibers, which have been moistened shortly before application.

[0253] Since the product (M) itself is low in water or anhydrous, the remaining water in the hair supports the condensation of the organic Ci-Ce-alkoxysilanes directly on the surface of the keratin. In this way, a particularly uniform and resistant coating forms, which tightly envelops the hair fiber and is created precisely where the film is intended to be.

[0254] Dry keratinous fibers, especially dry hair, are understood to be material that has not undergone any additional treatment immediately before the dyeing process (i.e., up to three hours before the dyeing process) and has not been moistened with water or with water / shampoo.

[0255] The term "dampened" or "towel-dried" hair refers to hair that has been thoroughly wetted with water at the sink or in the shower, then squeezed dry and rubbed with a towel (e.g., for 30 seconds). Damp hair, which can also be described as damp or towel-dried, is therefore no longer dripping wet, but still moist.

[0256] Example: The user thoroughly wets their hair under the tap by completely saturating it with water. Then they dry their hair with a dry towel for 30 seconds.

[0257] A second subject matter of the present application is therefore a method for treating keratinous fibers, in particular human hair, comprising applying an agent (M), as disclosed in detail in the description of the first subject matter of the invention, to moist keratinous fibers and optionally rinsing off the agent after an exposure time.

[0258] Preferably, the keratinous fibers are moistened shortly before application of the agent (M), for example 10 seconds to 20 minutes before its application, preferably 10 seconds to 5 minutes before its application.

[0259] The product (M) can be applied, for example, by distributing or distributing and massaging it onto the keratinous material (or hair) using a gloved hand, a brush, an applicator bottle, or an applicator. Following application to the keratinous fibers or hair, the product (M) can be massaged in. This massaging can be done, for example, by mechanically rubbing or scrubbing the hair with a gloved hand.

[0260] In a further embodiment, the agent (M) can be converted into its ready-to-use agent (AM) by mixing it with water or a water-containing composition. The preparation of the application mixture preferably takes place shortly before application, for example, 10 seconds to 20 minutes before application. Particularly preferably, the ready-to-use agent (AM) is applied directly to the keratinous fibers after its preparation.

[0261] Another subject matter of the present application is therefore a method for treating keratinous fibers, in particular human hair, comprising (1) the production of a ready-to-use agent (AM) by mixing an agent (M), as disclosed in detail in the description of the first subject matter of the invention, with water or with an aqueous formulation (A), and

[0262] (2) the application of the ready-to-use agent (AM) produced in step (1) to dry or moist keratinous fibers, and

[0263] (3) if necessary, rinsing the agent out of the keratinous fibers.

[0264] The agent (M) and water can be mixed, for example, in a weight ratio of 3:1 to 1:3, preferably 2:1 to 1:2, more preferably 1.5:1 to 1:1.5 and most preferably 1.2:1 to 1:1.2.

[0265] For example, with a weight ratio of 1.2:1, 120 g of the agent (M) are mixed with 100 g of water.

[0266] For example, with a weight ratio of 1 :1 ,2, 100 g of the agent (M) is mixed with 120 g of water.

[0267] The aqueous formulation (A) preferably contains water as its main component, but may also contain other ingredients. For example, an aqueous formulation (A) may contain 98% by weight water and 2% by weight of other components. At a mixing ratio of 1.2:1, 120 g of the product (A) are then mixed with 102.04 g of the aqueous formulation (A).

[0268] Particularly preferred is the preparation of the ready-to-use agent (AM) in step (1) by mixing the agent (M) with water (which may be tap water or distilled water).

[0269] The amount of water in the ready-to-use product (WMP) influences the extent and rate of condensation of the Ci-Ce alkoxysilanes. Therefore, the water content in the ready-to-use product (WMP) also affects the pot life, i.e., the period during which the Ci-Ce alkoxysilanes remain reactive and condensation occurs. For a period of up to 30 minutes, which is typically required for full-head application of a product to the hair, a water content of 25.0 to 98.0 wt%, preferably 30.0 to 80.0 wt%, more preferably 35.0 to 70.0 wt%, and most preferably 40 to 65 wt% has proven to be particularly suitable.At this water content, the ready-to-use product remained reactive for at least 30 minutes and still formed a homogeneous and closed film on the keratin fibers even if the user allowed the ready-to-use product to stand for 30 minutes after its preparation before applying it to the hair.

[0270] In a further particularly preferred embodiment, a method according to the invention is characterized in that the ready-to-use agent (AM) – based on the total weight of the ready-to-use agent (AM) – has a water content of 25.0 to 98.0 wt.%, preferably 30.0 to 80.0 wt.%, more preferably 35.0 to 70.0 wt.% and most preferably 40 to 65 wt.%.

[0271] The ready-to-use product (AM) can be applied to dry or previously moistened keratin fibers. Application can be carried out, for example, by spreading or spreading and massaging the product (M) onto the keratin material (or hair) using a gloved hand, a brush, an applicator bottle, or an applicator. Following application to the keratin fibers or hair, the product (M) can be further massaged in. This can be done, for example, by mechanically rubbing or scrubbing the hair with a gloved hand.

[0272] Leave-on or rinse-off application of the product (M)

[0273] After application and, if necessary, a short exposure time, the product (M) (or the ready-to-use product (AM) if the product (M) was mixed with water before application) can be rinsed out of the keratin fibers. Rinsing can be done with water only or with water and the aid of a shampoo. This form of application can also be referred to as a rinse-off application.

[0274] In another embodiment, however, it is also possible not to rinse off the agent (M), but rather to dry the keratin fibers still coated with the agent (M) (or the keratin fibers coated with the diluted agent (M)) without washing. Without washing off the agent (M), the film formed on the keratin fibers can continue to condense or harden for some time. Since particularly resistant films can be obtained in this way, this embodiment is especially preferred. This form of application can also be referred to as a leave-on application.

[0275] In a further particularly preferred embodiment, a method according to the invention is therefore characterized by the drying of the keratinous fibers without prior washing out of the agent (M).

[0276] During drying, the water (M) and solvent(s) present in the medium or in the keratin fibers evaporate, and the film formed by the condensation of the Ci-Ce-alkoxysilanes hardens. Drying can be carried out either in air or under heat, for example using a heat cap or a hairdryer.

[0277] The time between the application of the agent (M) and the drying of the keratin fibers can range from a few seconds to 60 minutes, preferably from 30 seconds to 30 minutes. If the keratin fibers are dried in air, the drying process begins in principle immediately after the application of the agent (M), since the volatile components begin to evaporate during the contact time of the agent (M).

[0278] The drying of keratin fibers, or hair, can be accelerated by heat treatment. Heat treatment involves bringing the keratin fibers into contact with a heated device, or applying this heated device to or on the keratin fibers. Alternatively, the keratin fibers can also be exposed to warm / hot air for heat treatment. Examples of suitable devices include a hairdryer, a hair dryer, a heat cap, a flat iron, a curling iron, or an infrared lamp.

[0279] In a particularly preferred embodiment, a method according to the invention is characterized in that the heat treatment is carried out by using a hairdryer, a hair dryer, a heat cap, a flat iron, a curling iron or an infrared lamp.

[0280] Furthermore, it was found that it is preferred if the treatment temperature during the heat treatment is between 40 °C and 210 °C, preferably between 50 °C and 190 °C, more preferably between 50 °C and 170 °C, even more preferably between 50 °C and 150 °C, and most preferably between 50 °C and 100 °C. In other words, it has proven particularly preferred if the heat treatment is carried out with a device that is heated to a temperature of 40 °C to 210 °C, preferably between 50 °C and 190 °C, more preferably between 50 °C and 170 °C, even more preferably between 50 °C and 150 °C, and most preferably between 50 °C and 100 °C.

[0281] In a further particularly preferred embodiment, a method according to the invention is characterized in that the keratinous fibers still covered with the agent (M) or with the agent (AM) are dried, wherein the drying preferably takes place at a temperature of 40 °C to 210 °C, more preferably from 40 °C to 190 °C, more preferably from 45 °C to 170 °C, even more preferably from 45 °C to 100 °C and most preferably from 45 °C to 70 °C.

[0282] For example, the keratin fibers or hair can be treated with a hairdryer that blows warm or hot air onto them. Preferably, this air is between 50 and 100 °C. Alternatively, the keratin fibers or hair can be held under an infrared lamp, preferably set to a temperature of 50 to 100 °C. For heat treatment, hair can also be pressed between two appropriately heated plates of a flat iron, which can simultaneously be moved along the fiber. The plates of the flat iron can, for example, be set to a temperature of up to 210 °C. The heat treatment can advantageously be continued until the keratin fibers, still coated with the agent (M), are partially or completely dry.

[0283] Possible uses of the product

[0284] As previously described, the agent according to the invention is very well suited for treating keratin fibers and can be used for all purposes where a resistant coating of the keratin fibers improves the properties of the fibers. As already described, the application of the agent (M) has shown particular advantages when applied to dyed keratin fibers, since in this way the color intensity and also the wash fastness of the dyed keratin fibers could be improved.

[0285] The prior coloring of the keratinous fibers can be done, for example, with direct dyes and / or pigments, or an oxidative coloring can be carried out beforehand, in which the color is achieved with oxidation dye precursors and hydrogen peroxide as an oxidizing agent.

[0286] In a further particularly preferred embodiment, one of the previously described methods is therefore characterized in that it is a method for color protection of dyed keratinous fibers and that the agent (M) or the ready-to-use agent (AM) is applied to dyed keratinous fibers that have previously been dyed by applying at least one dye from the group consisting of oxidation dye precursors, direct dyes and / or pigments.

[0287] In a further particularly preferred embodiment, the agent (M) or the ready-to-use agent (AM) is applied to colored keratinous fibers that have previously been colored with a pigment and / or a direct dye.

[0288] Regarding the further embodiments of the methods according to the invention, what has been said about the means according to the invention applies mutatis mutandis.

[0289] Examples

[0290] The following formulations were produced (unless otherwise stated, all values ​​are in wt.%)

[0291] 1.1. Production and application of dyes

[0292] The following dye was produced (all values ​​are in wt.% unless otherwise stated):

[0293] Table 1

[0294] To remove any potentially adhering substances (moth powder, preservatives, etc.), strands of hair (Kerling Euronaturhaar white) were pre-washed with a commercially available shampoo, rinsed with water, and then dried. The cleaned strands were then stored for at least 72 hours.

[0295] For the dyeing process, each strand was immersed in the dye solution (F1) and left there for 10 minutes. The strand was then removed from the dye solution, excess liquid was wiped off, and the strand was dried using a standard hairdryer. The dyed strands were then colorimetrically measured. After drying, the strands were stored for 72 hours.

[0296] 1.2. Production of the agent (M) and the ready-to-use agent (AM)

[0297] Production of the silane blend

[0298] In a 500 ml round-bottom flask, 59.7 g of methyltriethoxysilane and 29.9 g of 3-aminopropyltriethoxysilane were mixed together with stirring. The headspace above this mixture was purged with argon. The reaction mixture was then heated to 50 °C, and 10.4 g of a 2.5% solution of sodium hydroxide in water were added dropwise while stirring. The mixture was stirred for a further 6 hours at 50 °C, then allowed to cool, and subsequently transferred to an airtight glass vessel.

[0299] The silane blend produced in this way was incorporated into the following agent (M) (all values, unless otherwise stated, are in wt.%): Table 2

[0300] The compound (M1) was mixed with distilled water in a 1:1 weight ratio (i.e., 50 g of the compound (M1) was mixed with 50 g of distilled water) and shaken thoroughly. The ready-to-use compound (AM1) was thus prepared.

[0301] 1.3. Application of the product (AM1) to strands of hair

[0302] The hair strands dyed and stored according to step 1 were briefly moistened with tap water. To do this, the strands were wetted under the tap, then excess water was squeezed out, and the strands were rubbed with a towel. The resulting towel-dried hair strands are no longer dripping wet but still retain some residual moisture. The ready-to-use sealant (AM1) was then applied to these strands (0.3 g (AM1) per 2 g strand).

[0303] To test the pot life of the ready-to-use product, the ready-to-use product (AM1) was applied to the keratin fibers immediately after mixing (0 minutes), as well as 15 minutes and 30 minutes after mixing. After application, the ready-to-use product (AM1) was worked into the strands by gentle massaging.

[0304] After a 15-minute application time, some of the strands were rinsed with water and then dried using a hairdryer (rinse-off application).

[0305] In another part of the strands, the product (AM1) was not washed out, but the strands still covered with the ready-to-use product (AM1) were dried using a standard hairdryer (leave-on application).

[0306] The strands were then measured again using colorimetric methods.

[0307] The dE value used to assess color intensity is derived from the L*a*b* color measurements taken on the respective strand as follows: dE = [ (Li - Lo) 2 + (ai - ao) 2 + (bi - bo) 2 ] 1 / 2

[0308] Lo, ao and bo = measured values ​​of the uncolored strand

[0309] Li, ai, and bi = measured values ​​of the dyed strand or measured values ​​of the dyed / sealed strand (directly after dyeing, 0 HW). The higher the dE value, the greater the color difference between the undyed and dyed strands. The higher the dE value, the greater the color intensity compared to the undyed strand.

[0310] Table 3: Color intensities compared to the uncolored strand - results after 0 hair washes

[0311] HW: Hair washes dE: Color intensity of the dyed strand (or dyed and sealed strand) in

[0312] Comparison to an uncolored strand: yes = ready-to-use sealant (AM1) was washed out (rinse-off application); no = ready-to-use sealant (AM1) was not washed out (leave-on application).

[0313] Pot-Live: ready-to-use sealant (AM1) was mixed with

[0314] Water left to stand for 0 minutes, 15 minutes or 30 minutes and then applied to the colored strand.

[0315] Sealing with the ready-to-use agent (AM1) (Table 3, rows 3 to 8) resulted in an increase in color intensity compared to staining without post-treatment (Table 3, row 2, comparison). This increase in color intensity was observed both when the agent (AM1) was washed out and when it was applied as a leave-on product.

[0316] Furthermore, it was demonstrated that the ready-to-use product (AM1) has a pot life of at least 30 minutes. This means that the ready-to-use product retains its reactivity for at least 30 minutes after mixing with water. Even when the product (AM1) was left to stand for 15 or 30 minutes after mixing with water before application to the hair strands, an increase in color intensity was still achieved.

[0317] 1.4. Measuring wash fastness

[0318] To measure colorfastness, the strands dyed according to section 1.3 were subjected to 12 manual hair washes (WW). For each wash, the strand was moistened, then a commercially available shampoo (Schauma 7 Herbs) was massaged into the strand for 25 seconds (0.25 g of shampoo per gram of hair). The strand was then rinsed with lukewarm tap water for 30 seconds and dried.

[0319] After 12 hair washes, the strands were measured again using colorimetric methods.

[0320] The dE value used to assess color intensity is derived from the L*a*b* color measurements taken on the respective strand as follows: dE = [ (Li - Lo) 2 + (ai - ao) 2 + (bi - bo) 2 ] 1 / 2

[0321] Lo, ao and bo = measured values ​​of the uncolored strand

[0322] Li, ai and bi = measured values ​​of the dyed (or dyed / sealed) and then 12-times washed strand

[0323] The higher the dE value, the greater the color difference between the undyed and the dyed (or dyed / sealed) and washed strand. The higher the dE value compared to the undyed hair, the higher the color intensity and therefore the colorfastness of the respective strand.

[0324] Table 4: Color intensities compared to the uncolored strand - results after 12

[0325] Hair washing

[0326] Even after 12 washes, the strands sealed with the ready-to-use product (AM1) (Table 4, rows 3 to 8) were still much more intensely colored compared to a strand that was washed after coloring but not sealed (Table 4, row 2). Sealing the colored strands with (AM1) therefore significantly improved the colorfastness of the dyed strands.

[0327] 1.5. Investigation of different thickeners

[0328] The following products (M) were produced (all values, unless otherwise stated, are in wt.%):

[0329] Table 5 To test the thickening performance, each of the agents (M1) to (M4) was mixed with water in a 1:1 weight ratio. The ready-to-use agents (AM1) to (AM4) were thus prepared. The viscosity and external appearance of the agents (M1) to (M4) and the ready-to-use agents (AM1) to (AM4) prepared from them were evaluated.

[0330] Table 6

[0331] The desired properties of the agent (M) and the ready-to-use agent (AM) could only be achieved by thickening with polyquaternium-10.

Claims

Patent claims 1. Agent (M) for treating keratinous fibers, especially human hair, containing - based on the total weight of the agent - (m1) at least one organic Ci-Ce alkoxysilane and / or its hydrolysis and / or condensation products, and (m2) at least one polysaccharide, and (m3) at least a solvent other than water, and (m4) less than 10 wt.% water.

2. Composition (M) according to claim, characterized in that it contains at least one Ci-Ce-alkoxy-silane (m1) of formula (Sl) and / or its hydrolysis and / or condensation products. RiR2N-L-Si(OR3) a (R4)b (Sl), wherein Ri, R2 independently of each other stand for a hydrogen atom or a Ci-Ce alkyl group, L represents a linear or branched divalent Ci-C2o alkylene group, R3 and R4 independently represent a Ci-Ce alkyl group, a represents an integer from 1 to 3, and b represents the integer 3 - a.

3. Composition (M) according to one of claims 1 to 2, characterized in that it contains at least one Ci-Ce-alkoxy-silane (m1) of formula (S-Il) and / or its hydrolysis and / or condensation products R5Si(OR6)k(R7)m (S-Il), where - Re stands for a Ci-Cis alkyl group, - Re stands for a Ci-Ce alkyl group, - R7 stands for a Ci-Ce alkyl group - k represents an integer from 1 to 3, and - m represents the integer 3 - k stands for.

4. Means (M) according to any one of claims 1 to 3, characterized in that it contains - at least one first Ci-Ce-alkoxy-silane (m1) selected from the group consisting of (3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane, (2-aminoethyl)trimethoxysilane, (2-aminoethyl)triethoxysilane, (3-dimethyl-aminopropyl)trimethoxysilane, (3-dimethylamino- propyl)triethoxysilane, (2-Dimethylaminoethyl)trimethoxysilane, (2-Dimethylaminoethyl)-triethoxysilane and / or their hydrolysis and / or condensation products, and - at least one second Ci-Ce-alkoxy-silane (m1) selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane and / or their hydrolysis and / or condensation products.

5. Composition (M) according to any one of claims 1 to 4, characterized in that it contains - based on the total weight of the composition (M) - one or more organic Ci-Ce-alkoxysilanes (m1) and / or their hydrolysis and / or condensation products in a total amount of 0.1 to 50.0 wt.%, preferably 5.0 to 45 wt.%, more preferably 15.0 to 40 wt.% and most preferably 20.0 to 35.0 wt.%.

6. Composition (M) according to any one of claims 1 to 5, characterized in that it contains at least one cationic polysaccharide (m2) from the group consisting of cationic celluloses, cationic guar and / or cationic starches, most preferably selected from the group consisting of cationic celluloses.

7. Composition (M) according to any one of claims 1 to 6, characterized in that it contains at least one non-ionic polysaccharide (m2) from the group consisting of 2-hydroxypropyl cellulose, 3-hydroxypropyl cellulose, 2-hydroxypropyl methyl cellulose and / or 3-hydroxypropyl methyl cellulose and 2-hydroxyethyl cellulose, particularly preferably from the group consisting of 2-hydroxypropyl cellulose and 3-hydroxypropyl cellulose.

8. Composition (M) according to any one of claims 1 to 7, characterized in that it contains - based on its total weight - one or more polysaccharides (m2) in a total amount of 0.1 to 12.0 wt.%, preferably 0.4 to 8.5 wt.%, more preferably 0.8 to 7.0 wt.% and most preferably 2.0 to 5.0 wt.%.

9. Composition (M) according to any one of claims 1 to 8, characterized in that it contains one or more solvents (m3) other than water from the group consisting of ethanol, isopropanol, poly-Ci-Ce alkylene glycols, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, dipropylene glycol, diethylene glycol monoethyl ether, glycerin, phenoxyethanol and benzyl alcohol, most preferably ethanol.

10. Composition (M) according to any one of claims 1 to 9, characterized in that it comprises – based on the total weight of the composition (M) – one or more solvents (m3) other than water in a total quantity of 10.0 to 99.0 wt.%, preferably from 30.0 to 95.0 wt.%, further preferably 50.0 to 90.0 wt.%, even more preferably 55.0 to 85.0 wt.% and most preferably 60.0 to 80.0 wt.%.

11. Composition according to any one of claims 1 to 10, characterized in that it contains - based on the total weight of the composition - 0 to 7.5 wt.%, preferably 0.0 to 5.0 wt.%, more preferably 0.0 to 4.0 wt.% and most preferably 0.1 to 2.5 wt.% water (m4).

12. Method for treating keratinous fibers, in particular human hair, comprising applying an agent (M) according to any one of claims 1 to 11 to moist keratinous fibers and optionally rinsing off the agent after an exposure time.

13. Method for treating keratinous fibers, especially human hair, comprising (1) the production of a ready-to-use agent (AM) by mixing an agent (M) as described in any one of claims 1 to 1 1 with water or with an aqueous formulation (A), and (2) the application of the ready-to-use agent produced in step (1) to dry or moist keratinous fibers, and (3) if necessary, rinsing the agent out of the keratinous fibers.

14. Method according to claim 13, characterized in that the ready-to-use agent (AM) - based on the total weight of the ready-to-use agent (AM) - has a water content of 25.0 to 98.0 wt.%, preferably of 30.0 to 80.0 wt.%, more preferably of 35.0 to 70.0 wt.% and most preferably of 40 to 65 wt.%.

15. Method according to one of claims 12 or 13, characterized in that the keratinous fibers still covered with the agent (M) or with the agent (AM) are dried, wherein the drying preferably takes place at a temperature of 40 °C to 210 °C, more preferably from 40 °C to 190 °C, more preferably from 45 °C to 170 °C, even more preferably from 45 °C to 100 °C and most preferably from 45 °C to 70 °C.

16. Method according to one of claims 12 to 15, characterized in that it is a method for color protection of dyed keratinous fibers and that the agent (M) or the ready-to-use agent (AM) is applied to dyed keratinous fibers which have previously been dyed by applying at least one dye from the group consisting of oxidation dye precursors, direct dyes and / or pigments.

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