Method for dyeing keratin materials comprising wash-free application of dyes having low water content and comprising C1-C6 alkoxysilanes, pigments and solvents

Abstract

The invention relates to a method for dyeing keratin materials, in particular human hair, comprising the following steps in the specified sequence: (1) providing a dye (F) containing, relative to the total weight of the dye (F): (F1) one or more organic C1-C6 alkoxysilanes and / or condensation products thereof, (F2) at least one pigment, (F3) less than 25.0 wt% of water, (F4) at least one pigment, and (F5) less than 25.0 wt% of water; and (F4) at least one solvent different from water; (2) applying a dye (F) to the wetted or dried keratin material; (3) optionally applying a determined amount of water to the keratin material still loaded with the dye (F), wherein the weight of the amount of water applied in step (3) is at most twice the weight of the dye (F) applied in step (2); and (4) drying the keratin material without pre-washing off the dye (F).

Description

[0001] A method for dyeing keratin materials comprising the leave-on application of a low-water content dye comprising a C1-C6 alkoxysilane, a pigment and a solvent.

[0002] The present application relates to a method for dyeing keratin materials, in particular human hair, wherein a dye having a low water content and containing at least one C1-C6 alkoxysilane, a pigment and a solvent is applied to the keratin material as a leave-on product.

[0003] The modification of the shape and color of keratin materials, in particular human hair, is an important area of ​​modern cosmetics. To modify the color of hair, the person skilled in the art is familiar with various coloring systems, depending on the coloring requirements. Oxidation colorants are generally used for permanent, intense coloring with good fastness properties and good gray coverage. Such dyes contain oxidation dye precursors, so-called developer components, and coupler components, which together form the actual dye under the influence of the oxidizing agent hydrogen peroxide. Oxidation colorants are characterized by very long-lasting color results.

[0004] When direct dyes are used, the ready-made dye diffuses from the colorant into the hair fiber. The color obtained with direct dyes is less durable and washes out more quickly than with oxidative hair dyeing. Color with direct dyes typically remains on the hair for a period of 5 to 20 shampoos.

[0005] It is known that the use of colour pigments can produce short-term colour changes on the hair and / or skin. Colour pigments are generally understood to mean insoluble colouring substances. These pigments are not dissolved in the colouring preparation in the form of small particles and are only deposited from the outside on the hair fibre and / or skin surface. Therefore, they can usually be removed again without residue by washing several times with a detergent containing a surfactant. Various products of this type are available on the market under the name of self-help hair dye cream (hair mascara).

[0006] If the user wishes a particularly long-lasting coloring, the use of oxidative colorants is currently the only option. However, despite numerous attempts at optimization, unpleasant ammonia or amine odors cannot be completely avoided in oxidative hair coloring. The hair damage still associated with the use of oxidative colorants also has an adverse effect on the user's hair. Therefore, the search for alternative high-performance coloring methods is a constant challenge.

[0007] EP 2168633 B1 is concerned with the task of producing permanent hair dyes using pigments. The document teaches that when a combination of pigments, organosilicon compounds, hydrophobic polymers and solvents is used, particularly shampoo-resistant colors can be produced on the hair. For example, 3-aminopropyltriethoxysilane is used as the organosilicon compound.

[0008] In the dyeing method of EP 2168633B1, organosilicon compounds of the silane class are used, wherein the molecular structure of these silanes includes at least one hydroxyl group and / or a hydrolyzable group. Due to the presence of hydroxyl groups or hydrolyzable groups, silanes are reactive substances that hydrolyze or oligomerize or polymerize in the presence of water. When applied to keratin materials, the oligomerization or polymerization of the silanes triggered by the presence of water ultimately leads to the formation of a film that fixes the dyeing compound, thereby producing a very durable color.

[0009] However, by more closely examining the dyeing methods disclosed in EP 2168633 B1, it was found that the colors produced on the hair using these agents or methods still need to be improved. In particular, the color intensity and the wear of the hair color still need to be optimized, and the durability, especially the wash fastness of these colors needs to be further improved.

[0010] The object of the present invention is to find a method for dyeing keratin materials such as hair, with which the pigments known from the prior art can be fixed to the hair in an extremely durable manner. The dye should have very good storage stability and the user should have to perform as few steps as possible when applying the agent. Furthermore, the application should be as sustainable as possible and use as little water as possible. Furthermore, the color intensity, the durability, in particular the wash fastness of the color, should be improved.

[0011] Surprisingly, it has now been found that the above objects can be achieved with excellent results if a dye (F) having a low water content and containing one or more organic C1-C6 alkoxysilanes (F1), at least one pigment (F2), less than 25.0% by weight of water (F3) and at least one solvent other than water (F4) is applied to a keratin material in a dyeing process. Here, a key aspect of the invention is that the dye (F) is not washed off, but the keratin material in which the dye (F) is still present is dried. The work leading to the present invention surprisingly showed that this dyeing process is not only more efficient, with the user consuming less water when applying the dye, but also that the keratin material dyed in this way can also be dyed more intensely, with the colors obtained having better durability, in particular better wash fastnesses.

[0012] The present invention relates to a method for dyeing keratin materials, in particular human hair, comprising the following steps in the specified order:

[0013] (1) providing a dye (F), wherein the dye (F) contains, based on the total weight of the dye (F):

[0014] (F1) one or more organic C1-C6 alkoxysilanes and / or condensation products thereof,

[0015] (F2) at least one pigment,

[0016] (F3) less than 25.0 wt% water, and

[0017] (F4) at least one solvent other than water,

[0018] (2) applying the dye (F) to the wet or dry keratin material,

[0019] (3) optionally applying a specified amount of water to the keratin material still coated with the dye (F), wherein the weight of the amount of water applied in step (3) is at most twice the weight of the dye (F) applied in step (2), and

[0020] (4) Drying the keratin material without previously washing off the dye (F).

[0021] Keratin materials

[0022] Keratin materials are understood to mean hair, skin and nails (such as fingernails and / or toenails). In addition, wool, fur and feathers also belong to the definition of keratin materials.

[0023] Keratin materials are preferably understood to mean human hair, human skin and human nails, in particular fingernails and toenails. Keratin materials are very particularly preferably understood to mean human hair.

[0024] Dyes for dyeing keratin materials (F)

[0025] In step (1) of the method according to the present invention, a dye (F) is provided. The dye (F) is characterized in that it contains, based on the total weight of the dye (F):

[0026] (F1) one or more organic C1-C6 alkoxysilanes and / or condensation products thereof,

[0027] (F2) at least one pigment,

[0028] (F3) less than 25.0 wt% water, and

[0029] (F4) at least one solvent other than water.

[0030] In the context of the present invention, the term "colorant" is used for coloring keratin materials, in particular hair, by using pigments. In the dyeing process, the above-mentioned pigment (F2) is deposited on the surface of the keratin material in a particularly uniform and smooth film. This film is formed in situ by oligomerization or polymerization of the organic C1-C6 alkoxysilane (F1) and comprises the pigment (F2).

[0031] Organic C1-C6 alkoxysilane (F1) and / or its condensation product

[0032] As a first type of material essential to the present invention, the dye (F) contains one or more organic C1-C6 alkoxysilanes (F1) and / or condensation products thereof.

[0033] The organic C1-C6 alkoxysilane (F1) contained in the dye (F) is a reactive compound. Organic silicon compounds, which are also referred to as organic silicon compounds (organosilicon compounds) alternatively, are compounds with direct silicon-carbon bonds (Si-C) or in which carbon is connected to a silicon atom via an oxygen, nitrogen or sulfur atom. The organic C1-C6 alkoxysilane according to the present invention is a compound containing 1 to 3 silicon atoms. Particularly preferably, the organic C1-C6 alkoxysilane contains one or two silicon atoms.

[0034] According to IUPAC rules, the name "silane" refers to a substance group of compounds based on a silicon skeleton and hydrogen. In the case of organosilanes, the hydrogen atoms are completely or partially replaced by organic groups such as (substituted) alkyl and / or alkoxy groups. Some of the hydrogen atoms in organosilanes can also be replaced by hydroxyl groups.

[0035] The organic C1-C6 alkoxysilane includes at least one C1-C6 alkoxy group directly bonded to the silicon atom. The alkoxy group is reactive and can first be hydrolyzed in the presence of water and then condensed with another organic C1-C6 alkoxysilane (or its hydrolyzate). The C1-C6 alkoxy group is preferably an ethoxy group or a methoxy group. For example, if the hydrolyzable group is an ethoxy group, the organic silicon compound preferably contains the structural unit R'R"R"'Si-O-CH2-CH3. Here, the R', R" and R"' functional groups represent the three remaining free valences of the silicon atom.

[0036] Particularly good results are obtained when the dye (F) according to the invention contains at least one first organic C1-C6-alkoxysilane (F1) of the formula (I).

[0037] In a particularly preferred embodiment, the process according to the invention is characterized in that the dye (F) contains at least one organic C1-C6-alkoxysilane (F1) of the formula (I) and / or a condensation product thereof,

[0038] R1R2N-L-Si(OR3) a (R4) b (I)

[0039] in

[0040] - R1 and R2 independently represent a hydrogen atom or a C1-C6 alkyl group,

[0041] -L represents a straight chain or branched divalent C1-C 20Alkylene,

[0042] - R3 and R4 independently represent a C1-C6 alkyl group,

[0043] -a represents an integer from 1 to 3, and

[0044] -b means the integer 3-a.

[0045] The substituents R1, R2, R3, R4 and L in the compound of formula (I) are explained below by way of example:

[0046] Examples of C1-C6 alkyl are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and tert-butyl, n-pentyl and n-hexyl. Propyl, ethyl and methyl are preferred alkyl groups. Examples of C2-C6 alkenyl are vinyl, allyl, but-2-enyl, but-3-enyl and isobutenyl; preferred C2-C6 alkenyl are vinyl and allyl. Preferred examples of hydroxy-C1-C6 alkyl are hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl and 6-hydroxyhexyl; 2-hydroxyethyl is particularly preferred. Examples of amino-C1-C6 alkyl are aminomethyl, 2-aminoethyl, 3-aminopropyl. 2-aminoethyl is particularly preferred. Straight-chain divalent C1-C 20 Examples of alkylene radicals are, for example, methylene (—CH2—), ethylene (—CH2—CH2—), propylene (—CH2—CH2—CH2—) and butylene (CH2—CH2—CH2—CH2—). Particular preference is given to propylene (—CH2—CH2—CH2—). Starting from a chain length of 3 C atoms, the divalent alkylene radical can also be branched. Branched divalent C3-C 20 Examples of alkylene groups are (-CH2-CH(CH3)-) and (-CH2-CH(CH3)-CH2-).

[0047] In the organosilicon compound of formula (I)

[0048] R1R2N-L-Si(OR3) a (R) b (I)

[0049] The radicals R1 and R2 independently of one another represent a hydrogen atom or a C1-C6-alkyl radical. Very particularly preferably, the radicals R1 and R2 both represent a hydrogen atom.

[0050] Indicates a straight-chain or branched divalent C1-C 20 The structural unit of the alkylene group or the linking group -L- is located in the middle of the organosilicon compound.

[0051] Preferably, -L- represents a linear divalent C1-C 20Alkylene. Further preferably, -L- represents a straight-chain divalent C1-C6 alkylene. Particularly preferably, -L- represents a methylene (-CH2-), ethylene (-CH2-CH2-), propylene (-CH2-CH2-CH2-) or butylene (-CH2-CH2-CH2-CH2-). Very particularly preferably, L represents a propylene (-CH2-CH2-CH2-).

[0052] The organosilicon compounds of formula (I) according to the present invention each carry a silicon-containing group -Si(OR3) at one end. a (R4) b .

[0053] R1R2N-L-Si(OR3) a (R4) b (I)

[0054] In the terminal structural unit -Si(OR3) a (R4) b In the above, the functional group R3 represents a hydrogen atom or a C1-C6 alkyl group, and the functional group R4 represents a C1-C6 alkyl group. Particularly preferably, R3 and R4 independently represent a methyl group or an ethyl group.

[0055] In this case, a represents an integer from 1 to 3, and b represents the integer 3-a. If a represents the number 3, b is equal to 0. If a represents the number 2, b is equal to 1. If a represents the number 1, b is equal to 2.

[0056] Colors with optimal washing fastnesses are obtained when the agent according to the invention contains at least one first organosilicon compound (a1) of the formula (I) in which the functional groups R3 and R4 independently of one another represent a methyl or ethyl group.

[0057] Furthermore, colors with optimal washing fastness are obtained when the agent according to the invention contains at least one first organosilicon compound (a1) of formula (I) in which the functional group a represents the number 3. In this case, the group b represents the number 0.

[0058] In a further preferred embodiment, the agent according to the invention is characterized in that it contains at least one first organosilicon compound (a1) of the formula (I),

[0059] in

[0060] - R3, R4 independently represent methyl or ethyl, and

[0061] -a represents the number 3, and

[0062] -b means the number 0.

[0063] In a further preferred embodiment, the agent according to the invention is characterized in that it contains at least one first organosilicon compound (a1) of the formula (I),

[0064] R1R2N-L-Si(OR3) a (R4) b (I)

[0065] in

[0066] -R1 and R2 both represent hydrogen atoms, and

[0067] -L represents a straight-chain divalent C1-C6 alkylene group, preferably a propylene group (-CH2-CH2-CH2-) or a vinylene group (-CH2-CH2-),

[0068] - R3, R4 independently represent methyl or ethyl, and

[0069] -a represents the number 3, and

[0070] -b means the number 0.

[0071] Particularly suitable organosilicon compounds of the formula (I) for achieving the objects according to the invention are:

[0072] -(3-aminopropyl)triethoxysilane,

[0073]

[0074] -(3-aminopropyl)trimethoxysilane,

[0075]

[0076] -1-(3-aminopropyl)silanetriol

[0077]

[0078] -(2-aminoethyl)triethoxysilane,

[0079]

[0080] -(2-aminoethyl)trimethoxysilane,

[0081]

[0082] -1-(2-aminoethyl)silanetriol

[0083]

[0084] -(3-dimethylaminopropyl)triethoxysilane,

[0085]

[0086] -(3-dimethylaminopropyl)trimethoxysilane,

[0087]

[0088] -1-(3-Dimethylaminopropyl)silanetriol

[0089]

[0090] -(2-dimethylaminoethyl)triethoxysilane,

[0091]

[0092] -(2-dimethylaminoethyl)trimethoxysilane, and / or

[0093]

[0094] -1-(2-Dimethylaminoethyl)silanetriol

[0095]

[0096] In a further preferred embodiment, the process according to the invention is characterized in that the dye (F) contains at least one organic C1-C6 alkoxysilane (F1) selected from the group consisting of (3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane, (2-aminoethyl)trimethoxysilane, (2-aminoethyl)triethoxysilane, (3-dimethylaminopropyl)trimethoxysilane, (3-dimethylaminopropyl)triethoxysilane, (2-dimethylaminoethyl)trimethoxysilane, (2-dimethylaminoethyl)triethoxysilane and condensation products thereof. It is particularly preferred if the dye contains (3-aminopropyl)triethoxysilane and / or condensation products thereof.

[0097] The organic C1-C6 alkoxysilane of formula (I) is commercially available. For example, (3-aminopropyl)trimethoxysilane can be purchased from Sigma-Aldrich. (3-aminopropyl)triethoxysilane can be purchased from Sigma-Aldrich.

[0098] In order to obtain colors with particularly good rubbing fastness and particularly high washing fastness, it has proven to be particularly advantageous if the dyes (F) according to the invention contain, in addition to or as an alternative to the organic C1-C6-alkoxysilane of the formula (I), at least one organic C1-C6-alkoxysilane of the formula (II): k (R7) m (II).

[0099] The organic C1-C6 alkoxysilane of formula (II) may also be referred to as silane of the alkylalkoxysilane type or alkylhydroxysilane type.

[0100] R5Si(OR6) k (R7) m (II)

[0101] in

[0102] -R5 means C1-C 12 alkyl,

[0103] -R6 represents a hydrogen atom or a C1-C6 alkyl group,

[0104] -R7 represents a C1-C6 alkyl group,

[0105] -k represents an integer from 1 to 3, and

[0106] -m means integer 3-k.

[0107] In a further preferred embodiment, the process according to the invention is characterized in that the dye contains at least one organic C1-C6-alkoxysilane (F1) of the formula (II),

[0108] R5Si(OR6) k (R7) m (II)

[0109] in

[0110] -R5 means C1-C 12 alkyl,

[0111] -R6 represents a hydrogen atom or a C1-C6 alkyl group,

[0112] -R7 represents a C1-C6 alkyl group,

[0113] -k represents an integer from 1 to 3, and

[0114] -m means integer 3-k.

[0115] In a further preferred embodiment, the dye (F) used in the process according to the invention is characterized in that, in addition to the organic C1-C6-alkoxysilane of the formula (I), it contains at least one further organic C1-C6-alkoxysilane of the formula (II)

[0116] R5Si(OR6) k (R7) m (II)

[0117] in

[0118] -R5 means C1-C 12 alkyl,

[0119] -R6 represents a hydrogen atom or a C1-C6 alkyl group,

[0120] -R7 represents a C1-C6 alkyl group,

[0121] -k represents an integer from 1 to 3, and

[0122] -m means integer 3-k.

[0123] In the organic C1-C6 alkoxysilane of formula (II), the group R5 represents a C1-C 12 Alkyl. The C1-C 12 The alkyl group is saturated and may be straight chain or branched. R5 preferably represents a straight chain C1-C8 alkyl group. Preferably, R5 represents a methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl or n-dodecyl group. Particularly preferably, R5 represents a methyl, ethyl or n-octyl group.

[0124] In the organosilicon compound of formula (II), the functional group R6 represents a hydrogen atom or a C1-C6 alkyl group. Particularly preferably, R6 represents a methyl group or an ethyl group.

[0125] In the organosilicon compound of formula (II), the functional group R7 represents a C1-C6 alkyl group. Particularly preferably, R7 represents a methyl group or an ethyl group.

[0126] In addition, k represents an integer from 1 to 3, and m represents an integer 3-k. If k represents the number 3, m is equal to 0. If k represents the number 2, m is equal to 1. If k represents the number 1, m is equal to 2.

[0127] Colors with optimal wash fastnesses are obtained when dyes (F) containing at least one organic C1-C6 alkoxysilane of formula (II) in which the functional group k represents the number 3 are used in the process. In this case, the group m represents the number 0.

[0128] Particularly suitable organosilicon compounds of the formula (II) for achieving the objects according to the invention are:

[0129] -methyltrimethoxysilane,

[0130]

[0131] -methyltriethoxysilane,

[0132]

[0133] -ethyltrimethoxysilane,

[0134]

[0135] -ethyltriethoxysilane,

[0136]

[0137] -n-Hexyltrimethoxysilane

[0138] -n-Hexyltriethoxysilane

[0139] -Octyltrimethoxysilane

[0140] -n-Octyltriethoxysilane

[0141] - n-dodecyltrimethoxysilane, and / or

[0142] -n-dodecyltriethoxysilane.

[0143]

[0144] In a further preferred embodiment, the process according to the invention is characterized in that the dye (F) contains at least one organic C1-C6 alkoxysilane (F1) selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane and condensation products thereof.

[0145] In order to achieve the objects according to the invention, further particularly suitable organosilicon compounds are:

[0146] -vinyltrimethoxysilane, and

[0147] -vinyltriethoxysilane.

[0148] In a particularly preferred embodiment, the dye (F) according to the invention is characterized in that it contains at least one first organic C1-C6 alkoxysilane of formula (I) selected from the group consisting of (3-aminopropyl)triethoxysilane and (3-aminopropyl)trimethoxysilane, and additionally at least one second organic C1-C6 alkoxysilane of formula (II) selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane and hexyltriethoxysilane.

[0149] The above organic C1-C6 alkoxysilanes are reactive compounds. In order to achieve particularly good dyeing results, it is particularly advantageous to use an organic C1-C6 alkoxysilane of formula (I) and / or (II) within a certain amount range in the dye (F).

[0150] In this context, it has been found to be preferred if the dye (F) according to the invention contains a total amount of 0.1 to 30.0 wt. %, preferably 0.5 to 20.0 wt. %, more preferably 5.0 to 15.0 wt. %, very particularly preferably 6.0 to 12.5 wt. % of one or more organic C1-C6 alkoxysilanes (F1) and / or condensation products thereof, based on the total weight of the dye.

[0151] Therefore, in a further very particularly preferred embodiment, the process according to the invention is characterized in that the dye (F) contains a total amount of 0.1 to 30.0 wt.-%, preferably 0.5 to 20.0 wt.-%, more preferably 5.0 to 15.0 wt.-%, very particularly preferably 6.0 to 12.5 wt.-% of one or more organic C1-C6 alkoxysilanes (F1) and / or condensation products thereof, based on the total weight of the dye (F).

[0152] Oligomers or condensates of organic silicon compounds

[0153] The organo C1-C6-alkoxysilanes (F1) according to the invention, in particular those of the formula (I) and / or (II), are reactive compounds which can undergo hydrolysis and condensation reactions with water.

[0154] The reaction of organic C1-C6 alkoxysilane with water can occur in various ways. Once the C1-C6 alkoxysilane is in contact with water by mixing, the reaction begins. Once the C1-C6 alkoxysilane and water are in contact, an exothermic hydrolysis reaction occurs according to the following scheme (reaction scheme using the example of 3-aminopropyltriethoxysilane):

[0155]

[0156] Depending on the number of hydrolyzable C1-C6 alkoxy groups per silane molecule, multiple hydrolysis reactions can also occur per C1-C6 alkoxysilane used:

[0157]

[0158] Example hydrolysis using methyltrimethoxysilane:

[0159]

[0160] Depending on the amount of water used, multiple hydrolysis reactions can also occur per C1-C6 alkoxysilane:

[0161]

[0162] The condensation of the partially (or partially completely) hydrolyzed C1-C6 alkoxysilane occurs after the hydrolysis, or almost simultaneously with the hydrolysis. The precondensation can be carried out, for example, according to the following scheme:

[0163]

[0164] Both partially hydrolyzed and fully hydrolyzed C1-C6 alkoxysilanes can participate in the condensation reaction with unreacted, partially hydrolyzed or fully hydrolyzed C1-C6 alkoxysilanes.

[0165] Possible condensation reactions are, for example (shown on the basis of a mixture of (3-aminopropyl)triethoxysilane and methyltrimethoxysilane):

[0166]

[0167]

[0168] In the above reaction schemes given by way of example, a condensation to form dimers is shown in each case, but a further condensation to oligomers having a plurality of silane atoms is also possible and preferred.

[0169] This hydrolysis or condensation reaction starts already in the presence of a very small amount of water, and therefore the oligomers and / or condensation products of the above-mentioned organosilicon compounds are also included in the present invention.

[0170] Pigment (F2)

[0171] As a second essential component, the dye (F) applied in the process according to the invention contains at least one pigment (F2).

[0172] Pigments within the meaning of the present invention are understood to mean coloring compounds having a solubility in water of less than 0.5 g / L, preferably less than 0.1 g / L, even more preferably less than 0.05 g / L at 20° C. Water solubility can be determined, for example, by the following method: 0.5 g of pigment is weighed into a beaker. A stirring rod is added. Then 1 liter of distilled water is added. The mixture is heated to 20° C. and stirred for 1 hour with a magnetic stirrer. If undissolved components of the pigment are still visible in the mixture after this period of time, the solubility of the pigment is less than 0.5 g / L. If the pigment-water mixture cannot be visually assessed due to the high strength of the pigment that can be finely dispersed, the mixture is filtered. If a portion of the undissolved pigment remains on the filter paper, the solubility of the pigment is less than 0.5 g / L.

[0173] Suitable pigments or color pigments may be of inorganic and / or organic origin.

[0174] In a preferred embodiment, the process according to the invention is characterized in that the dye (F) contains at least one pigment (F2) selected from inorganic pigments, organic pigments and / or metallic pigments.

[0175] Preferred color pigments are selected from synthetic or natural inorganic pigments. Inorganic color pigments of natural origin can be produced, for example, by chalk, ochre, umber, green earth, cooked ochre or graphite. In addition, black pigments such as black iron oxide, color pigments such as ultramarine or red iron oxide, and fluorescent or phosphorescent pigments can be used as inorganic color pigments.

[0176] Colored metal oxides, hydroxides and oxide hydrates, mixed-phase pigments, sulfur-containing silicates, silicates, metal sulfides, complex metal cyanides, metal sulfates, chromates and / or molybdates are particularly suitable. Particularly preferred color pigments are black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and brown iron oxides (CI 77491), manganese violet (CI 77742), ultramarine (sodium aluminum sulfosilicate, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI 77289), iron blue (ferric ferrocyanide, CI 77510) and / or cochineal (carmine).

[0177] Color pigments that are likewise particularly preferred according to the invention are colored pearlescent pigments. These pigments are usually based on mica and may be coated with one or more metal oxides. Mica is a phyllosilicate. The most important representatives of these silicates are muscovite, phlogopite, paragonite, biotite, lepidolite and pearl mica. In order to produce pearlescent pigments in combination with metal oxides, the mica, primarily muscovite or phlogopite, is coated with the metal oxide.

[0178] As an alternative to natural mica, synthetic mica coated with one or more metal oxides can also be used as pearlescent pigments. Particularly preferred pearlescent pigments are based on natural or synthetic mica and are coated with one or more of the abovementioned metal oxides. The color of the respective pigment can be varied by varying the layer thickness of the metal oxide.

[0179] In a further preferred embodiment, the agent according to the invention is characterized in that it contains at least one pigment selected from colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, complex metal cyanides, metal sulfates, bronze pigments and / or mica-based colored pigments coated with at least one metal oxide and / or metal oxychloride.

[0180] In another preferred embodiment, the dye (F) according to the invention is characterized in that it contains at least one pigment (F2) selected from the following group: mica-based pigments coated with one or more metal oxides (the metal oxides are selected from titanium dioxide (CI77891), black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and / or brown iron oxide (CI77491, CI 77499), manganese violet (CI 77742), ultramarine (sodium aluminum sulphosilicate, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI 77289), chromium oxide (CI 77288) and / or iron blue (ferric ferrocyanide, CI 77510).

[0181] Examples of particularly suitable color pigments are commercially available, for example, under the trade names and Purchased from Merck, and Purchased from Sensient, Purchased from Eckart Cosmetic Colors, Purchased from Sunstar Company.

[0182] A very particularly preferred trade name is The color pigments are, for example:

[0183] Colorona Copper, Merck, Mica, CI 77491 (Iron Oxides)

[0184] Colorona Passion Orange, Merck, Mica, CI 77491 (Iron Oxides), Alumina

[0185] Colorona Patina Silver, Merck, Mica, CI 77499 (Iron Oxides), CI 77891 (Titanium Dioxide)

[0186] Colorona RY, Merck, CI 77891 (titanium dioxide), mica, CI 75470 (carmine)

[0187] Colorona Oriental Beige, Merck, Mica, CI 77891 (Titanium Dioxide), CI 77491 (Iron Oxides)

[0188] Colorona Dark Blue, Merck, Mica, Titanium Dioxide, Ferric Ferrocyanide

[0189] Colorona Chameleon, Merck, CI 77491 (Iron Oxides), Mica

[0190] Colorona Aborigine Amber, Merck, Mica, CI 77499 (Iron Oxides), CI 77891 (Titanium Dioxide)

[0191] Colorona Blackstar Blue, Merck, CI 77499 (Iron Oxides), Mica

[0192] Colorona Patagonian Purple, Merck, Mica, CI 77491 (Iron Oxides), CI 77891 (Titanium Dioxide), CI 77510 (Ferric Ferrocyanide)

[0193] Colorona Red Brown, Merck, Mica, CI 77491 (Iron Oxides), CI 77891 (Titanium Dioxide)

[0194] Colorona Russet, Merck, CI 77491 (Titanium Dioxide), Mica, CI 77891 (Iron Oxides)

[0195] Colorona Imperial Red, Merck, Mica, Titanium Dioxide (CI 77891), D&C Red No. 30 (CI73360)

[0196] Colorona Majestic Green, Merck, CI 77891 (titanium dioxide), mica, CI 77288 (chromium oxide green)

[0197] Colorona Light Blue, Merck, Mica, Titanium Dioxide (CI 77891), Ferric Ferrocyanide (CI77510)

[0198] Colorona Red Gold, Merck, Mica, CI 77891 (Titanium Dioxide), CI 77491 (Iron Oxides)

[0199] Colorona Gold Plus MP 25, Merck, Mica, Titanium Dioxide (CI 77891), Iron Oxides (CI77491)

[0200] Colorona Carmine Red, Merck, Mica, Titanium Dioxide, Carmine

[0201] Colorona Blackstar Green, Merck, Mica, CI 77499 (Iron Oxides)

[0202] Colorona Bordeaux, Merck, Mica, CI 77491 (Iron Oxides)

[0203] Colorona Bronze, Merck, Mica, CI 77491 (Iron Oxides)

[0204] Colorona Bronze Fine, Merck, Mica, CI 77491 (Iron Oxides)

[0205] Colorona Fine Gold MP 20, Merck, Mica, CI 77891 (Titanium Dioxide), CI 77491 (Iron Oxides)

[0206] Colorona Sienna Fine, Merck, CI 77491 (Iron Oxides), Mica

[0207] Colorona Sienna, Merck, Mica, CI 77491 (Iron Oxides)

[0208] Colorona Precious Gold, Merck, Mica, CI 77891 (Titanium Dioxide), Silica, CI77491 (Iron Oxides), Tin Oxide

[0209] Colorona Sun Gold Sparkle MP 29, Merck, Mica, Titanium Dioxide, Iron Oxides, Mica, CI77891, CI 77491 (EU)

[0210] Colorona Mica Black, Merck, CI 77499 (Iron Oxides), Mica, CI 77891 (Titanium Dioxide)

[0211] Colorona Bright Gold, Merck, Mica, CI 77891 (Titanium Dioxide), CI 77491 (Iron Oxides)

[0212] Colorona Blackstar Gold, Merck, Mica, CI 77499 (Iron Oxides)

[0213] Another particularly preferred trade name is The color pigments are, for example:

[0214] Xirona Golden Sky, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide

[0215] Xirona Caribbean Blue, Merck, Mica, CI 77891 (Titanium Dioxide), Silica, Tin Oxide

[0216] Xirona Kiwi Rose, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide

[0217] Xirona Magic Mauve, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide.

[0218] In addition, a particularly preferred trade name is The color pigments are, for example:

[0219] Unipure Red LC 381EM, Sensient CI 77491 (Iron Oxide), Silica

[0220] Unipure Black LC 989EM, Sensient, CI 77499 (Iron Oxides), Silica

[0221] Unipure Yellow LC 182EM, Sensient, CI 77492 (Iron Oxides), Silica

[0222] In a further embodiment, the dyes (F) according to the invention may also contain one or more organic pigments.

[0223] The organic pigments according to the invention are corresponding insoluble organic dyes or lakes which can be selected, for example, from nitroso, nitro, azo, xanthene, anthraquinone, isoindolinone, isoindolinone, quinacridone, pyrenone, perylene, diketopyrrolopyrrole, indigo, thioindido, dioxazine and / or triarylmethane compounds.

[0224] Particularly suitable organic pigments may include, for example, carmine, quinacridone, phthalocyanine, sorghum red, blue pigments with color index numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100 or CI 74160, yellow pigments with color index numbers CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000 or CI 47005, green pigments with color index numbers CI 61565, CI 61570 or CI 74260, orange pigments with color index numbers CI 11725, CI 15510, CI 45370 or CI 71105, and CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 and / or CI 75470.

[0225] In another particularly preferred embodiment, the dye (F) according to the invention is characterized in that it contains at least one organic pigment (F2) selected from the group consisting of carmine, quinacridone, phthalocyanine, sorghum red, blue pigments with color indexes CI 42090, CI 69800, CI 69825, CI 73000, CI 74100 or CI 74160, yellow pigments with color indexes CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000 or CI 47005, green pigments with color indexes CI 61565, CI 61570 or CI 74260, green pigments with color indexes CI 11725, CI 15510, CI 45370 or CI 45371. CI 71105, and the red pigments with color index numbers CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 and / or CI 75470.

[0226] Organic pigments can also be lakes. The term lake within the meaning of the present invention is understood to mean particles comprising a dye-absorbing layer, wherein the unit consisting of particles and dye is insoluble under the above conditions. The particles can be, for example, an inorganic substrate, which can be aluminum, silicon dioxide, calcium borosilicate, calcium aluminum borosilicate or aluminum.

[0227] For example, alizarin lake can be used as the lake.

[0228] For dyeing keratin materials, pigments of specific shapes can also be used in the dye (F). For example, pigments based on lamellar and / or lenticular substrate platelets can be used. In addition, coloring based on substrate platelets including vacuum metallized pigments is also possible.

[0229] In a further embodiment, the process according to the invention can be characterized in that the dye (F) also contains one or more dyeing compounds selected from pigments based on lamellar substrate flakes, pigments based on lenticular substrate flakes, and vacuum metallization pigments.

[0230] The average thickness of this type of substrate flakes is at most 50nm, preferably less than 30nm, particularly preferably at most 25nm, for example at most 20nm. The average thickness of the substrate flakes is at least 1nm, preferably at least 2.5nm, particularly preferably at least 5nm, for example at least 10nm. The preferred range of the thickness of the substrate flakes is 2.5 to 50nm, 5 to 50nm, 10 to 50nm; 2.5 to 30nm, 5 to 30nm, 10 to 30nm; 2.5 to 25nm, 5 to 25nm, 10 to 25nm, 2.5 to 20nm, 5 to 20nm and 10 to 20nm. Preferably, each substrate flake has a thickness as uniform as possible.

[0231] Due to the low thickness of the substrate flakes, the pigments have a particularly high covering power.

[0232] The substrate flakes are integrally constructed. In this context, integral means composed of a single independent unit, without cracks, delaminations or inclusions, although structural changes may occur within the substrate flakes. The substrate flakes are preferably uniformly constructed, i.e., there are no concentration gradients within the flakes. In particular, the substrate flakes are not layered and have no particles distributed therein.

[0233] The size of the substrate flakes can be matched to the respective application, in particular to the desired effect on keratin materials. Typically, the average maximum diameter of the substrate flakes is about 2 to 200 μm, in particular about 5 to 100 μm.

[0234] In a preferred embodiment, the shape factor (aspect ratio) represented by the ratio of the average size to the average thickness is at least 80, preferably at least 200, more preferably at least 500, and particularly preferably greater than 750. In this case, the average size of the uncoated substrate piece is understood to mean the d50 value of the uncoated substrate piece. Unless otherwise stated, the d50 values ​​are determined using a Sympatec Helos model apparatus with QUIXEL wet dispersion. For the preparation of the samples, the samples to be investigated are pre-dispersed in isopropanol for 3 minutes.

[0235] The substrate tablets may be composed of any material that can be formed into tablet form.

[0236] They can be of natural origin, but can also be produced synthetically. Materials from which the substrate platelets can be constructed are, for example, metals and metal alloys, metal oxides (preferably aluminum oxide), inorganic compounds and minerals such as mica and (semi)precious stones, and plastic materials. Preferably, the substrate platelets are made of a metal (alloy).

[0237] Any metal suitable for metallic luster pigments is suitable as the metal. Such metals are especially iron and steel, and all air-resistant and water-resistant (semi)metals such as platinum, zinc, chromium, molybdenum and silicon, and their alloys such as aluminum bronze and brass. Preferred metals are aluminum, copper, silver and gold. Preferred substrate flakes are aluminum flakes and brass flakes, particularly preferably substrate flakes made of aluminum.

[0238] The lamellar substrate flakes are characterized by irregularly structured edges and are also called "corn flakes" due to their appearance.

[0239] Due to their irregular structure, pigments based on lamellar substrate platelets produce a high proportion of scattered light. In addition, pigments based on lamellar substrate platelets cannot completely cover the existing color of the keratin material and can achieve, for example, effects similar to natural graying.

[0240] Lenticular (= lens-shaped) substrate platelets have essentially regular, rounded edges and are also referred to as “silver dollars” due to their appearance. Due to their regular structure, the proportion of reflected light predominates in the case of pigments based on lenticular substrate platelets.

[0241] Vacuum metallized pigment (VMP) can be obtained, for example, by releasing metal, metal alloy or metal oxide from the corresponding film of application. These pigments are characterized by the particularly small thickness of the substrate flakes in the range of 5 to 50nm and the particularly smooth surface of increased reflectivity. In the context of the application, the substrate sheet included in the pigment metallized in vacuum is also referred to as VMP substrate sheet. For example, the VMP substrate sheet of aluminum can be obtained by releasing aluminum from the metallized film.

[0242] The substrate platelets made of metal or metal alloy may be passivated, for example by anodization (oxide layer) or chromating.

[0243] Uncoated lamellar, lenticular and / or VPM substrate platelets, in particular those made of metal or metal alloys, highly reflect incident light and produce light-dark flashes, but no color impression.

[0244] For example, color impressions can be produced by optical interference effects. Such pigments can be based on substrate sheets that are coated on at least one side. These exhibit interference effects by superimposing different refracted and reflected light beams.

[0245] Therefore, preferred pigments are pigments based on coated lamellar substrate flakes. The substrate flakes preferably have at least one coating B of a high-refractive metal oxide with a coating thickness of at least 50 nm. Coating A is preferably still between coating B and the surface of the substrate flake. Optionally, another coating C is on layer B, which is different from the underlying layer B.

[0246] The suitable material of coating A, B and C is all can be applied on the material of substrate sheet with film-like and permanent mode, and in the case of coating A and B, has required optical property.Usually, the coating of a part on substrate sheet surface is enough to obtain the pigment with gloss effect.Therefore, for example, can only apply the upper side and / or the lower side of substrate sheet, omit the side.Preferably, the whole surface (comprising the side surface) of the substrate sheet of optional passivation is covered by coating B.Therefore substrate sheet is wrapped up by coating B fully.This improves the optical property of pigment and increases the mechanical and chemical resilience of pigment.More than also be applicable to layer A, and if exist, preferably also be applicable to layer C.

[0247] Although a plurality of coating layers A, B and / or C may always be present, the coated substrate sheets preferably each have only one coating layer A, B and C (if present).

[0248] Coating B comprises at least one highly refractive metal oxide. The refractive index of the highly refractive material is at least 1.9, preferably at least 2.0, more preferably at least 2.4. Coating B preferably comprises at least 95 wt%, particularly preferably at least 99 wt% of one or more highly refractive metal oxides.

[0249] The thickness of the coating B is at least 50 nm. The thickness of the coating B is preferably not more than 400 nm, particularly preferably at most 300 nm.

[0250] Highly refractive metal oxides suitable for coating B are preferably selectively light absorbing (i.e., colored) metal oxides, such as iron (III) oxide (α- and γ-Fe2O3, red), cobalt (II) oxide (blue), chromium (III) oxide (green), titanium (III) oxide (blue, usually mixed with titanium oxynitride and titanium nitride) and vanadium (V) oxide (orange), and mixtures thereof. Colorless highly refractive oxides such as titanium dioxide and / or zirconium oxide are also suitable.

[0251] Coating B may contain selectively absorbing dyes, preferably in amounts of 0.001 to 5% by weight, particularly preferably 0.01 to 1% by weight, based in each case on the total amount of coating B. Organic and inorganic dyes which can be stably incorporated into metal oxide coatings are suitable.

[0252] The coating A preferably has at least one low-refractive metal oxide and / or metal oxide hydrate. Preferably, the coating A comprises at least 95 wt %, particularly preferably at least 99 wt %, of a low-refractive metal oxide (hydrate). The refractive index of the low-refractive material is at most 1.8, preferably at most 1.6.

[0253] Low-refractive metal oxides suitable for coating A include, for example, silicon (di) oxide, silicon oxide hydrate, aluminum oxide, aluminum oxide hydrate, boron oxide, germanium oxide, manganese oxide, magnesium oxide and mixtures thereof, preferably silicon dioxide. The thickness of coating A is preferably 1 to 100 nm, particularly preferably 5 to 50 nm, particularly preferably 5 to 20 nm.

[0254] The distance between the surface of the substrate sheet and the inner surface of the coating B is preferably at most 100 nm, particularly preferably at most 50 nm, particularly preferably at most 20 nm. Because the thickness of the coating A and therefore the distance between the surface of the substrate sheet and the coating B is within the above range, it can be ensured that the pigment has a high covering power.

[0255] If the pigment based on lamellar substrate platelets has only one layer A, it is preferred that the pigment has lamellar substrate platelets made of aluminum and a silicon dioxide layer A. If the pigment based on lamellar substrate platelets has a layer A and a layer B, it is preferred that the pigment comprises lamellar substrate platelets made of aluminum, a silicon dioxide layer A and an iron oxide layer B.

[0256] According to a preferred embodiment, the pigment has a further metal oxide (hydrate) coating C which is different from the underlying coating B. Suitable metal oxides are, for example, silicon (di) oxide, silicon oxide hydrate, aluminum oxide, aluminum oxide hydrate, zinc oxide, tin oxide, titanium dioxide, zirconium oxide, iron (III) oxide and chromium (III) oxide. Silicon dioxide is preferred.

[0257] The thickness of the coating C is preferably 10 to 500 nm, particularly preferably 50 to 300 nm. By providing a coating C, for example based on TiO2, better interference can be achieved while maintaining a high covering power.

[0258] Layers A and C are used in particular for corrosion protection and chemical and physical stabilization. Layers A and C particularly preferably contain silicon dioxide or aluminum oxide applied by the sol-gel method. The method comprises dispersing an uncoated layered substrate sheet or a layered substrate sheet already coated with layer A and / or layer B in a solution of a metal alkoxide (such as tetraethyl orthosilicate or aluminum triisopropoxide) (usually in a solution of an organic solvent or a solution of a mixture of an organic solvent and water containing at least 50 wt % of an organic solvent such as a C1 to C4 alcohol), and adding a weak base or acid to hydrolyze the metal alkoxide, thereby forming a metal oxide film on the surface of the (coated) substrate sheet.

[0259] For example, layer B can be produced by hydrolytic decomposition of one or more organometallic compounds and / or by precipitation of one or more dissolved metal salts and optionally subsequent post-treatment (eg conversion of the formed hydroxide-containing layer into an oxide layer by tempering).

[0260] Although each of the coating layers A, B and / or C may contain a mixture of two or more metal oxides (hydrates), each of the coating layers preferably contains a metal oxide (hydrate).

[0261] The thickness of the pigment based on the coated lamellar or lenticular substrate flakes or the pigment based on the coated VMP substrate flakes is preferably 70 to 500 nm, particularly preferably 100 to 400 nm, especially preferably 150 to 320 nm, for example 180 to 290 nm. Due to the small thickness of the substrate flakes, the pigment has a particularly high covering power. In particular, because the thickness of the uncoated substrate flakes is low and because the thickness of the coatings A and C (if present) is set to the minimum possible value, a small thickness of the coated substrate flakes is achieved. The thickness of the coating B determines the color impression of the pigment.

[0262] Depending on the structure of the layer A, B or C, the adhesion and wear resistance of the pigment based on the coated substrate sheet in the keratin material can be significantly improved by further modifying the outermost layer with organic compounds such as silanes, phosphates, titanates, borates or carboxylic acids. The organic compound is bound to the surface of the outermost layer, preferably the surface of the layer A, B or C containing the metal oxide. The outermost layer means the layer that is spatially farthest from the lamellar substrate sheet. The organic compound is preferably a functional silane compound that can be bound to the layer A, B or C containing the metal oxide. These can be monofunctional or difunctional compounds. Examples of the bifunctional organic compound include methacryloxyacryltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-acryloxyethyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane, 2-acryloxyethyltriethoxysilane, 3-methacryloxypropyltri(methoxyethoxy)silane, 3-methacryloxypropyltri(butoxyethoxy) ... Acyloxypropyl tri(propoxy)silane, 3-methacryloxypropyl tri(butoxy)silane, 3-acryloxypropyl tri(methoxyethoxy)silane, 3-acryloxypropyl tri(butoxyethoxy)silane, 3-acryloxypropyl tri(butoxy)silane, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl ethyl dichlorosilane, vinyl methyl diacetoxysilane, vinyl methyl dichlorosilane, vinyl methyl diethoxysilane, vinyl triacetoxysilane, vinyl trichlorosilane, phenyl vinyl diethoxysilane or phenyl allyl dichlorosilane. In addition, it can be modified with monofunctional silanes, especially alkyl silanes or aryl silanes. This has only one functional group, which can be covalently bonded to the pigment surface (i.e. the outermost metal oxide layer) based on the coated layered substrate platelets, or, when not completely covered, to the metal surface. The hydrocarbon functional group of the silane is away from the pigment. According to the type and property of the hydrocarbon functional group of silane, different degrees of pigment hydrophobicity are achieved. The example of this silane is hexadecyl trimethoxy silane, propyl trimethoxy silane etc. Particularly preferably, the pigment of the aluminum substrate sheet based on silicon dioxide coating is surface modified with monofunctional silane. Octyl trimethoxy silane, octyl triethoxy silane, hexadecyl trimethoxy silane and hexadecyl triethoxy silane are particularly preferred. Due to the surface characteristics / hydrophobization of the change, the improvement in adhesion, wear resistance and orientation can be achieved in application.

[0263] Suitable pigments based on lamellar substrate flakes include, for example, the VISIONAIRE series of pigments from Eckart.

[0264] Pigments based on lenticular substrate platelets may be referred to, for example, as Gorgeous is commercially available from Schlenk Metallic Pigments GmbH.

[0265] Pigments based on substrate flakes including vacuum metallized pigments may be referred to, for example, as Marvelous or Aurous is commercially available from Schlenk Metallic Pigments GmbH.

[0266] Due to their excellent light and temperature resistance, the use of the above-mentioned pigments in the dyes (F) of the process according to the invention is very particularly preferred. It is further preferred if the pigments used have a certain particle size. Therefore, according to the invention, if the average particle size D of at least one pigment is 50 The average particle size D is advantageously 1.0 to 50 μm, preferably 5.0 to 45 μm, preferably 10 to 40 μm, and in particular 14 to 30 μm. 50 It can be determined, for example, using dynamic light scattering (DLS).

[0267] One or more pigments can preferably be used in an amount of 0.1 to 20.0% by weight, preferably 0.2 to 10.0% by weight, based in each case on the total weight of the dye (F).

[0268] In a further particularly preferred embodiment, the process according to the invention is characterized in that the dye (F) contains one or more pigments (F2) in a total amount of 0.1 to 20.0 wt. %, preferably 0.2 to 10.0 wt. %, based on the total weight of the dye (F).

[0269] Water content of dye (F)

[0270] Another characteristic of the dye (F) is the water content (F3), which must be lower than 25 wt%. The dye (F) thus contains less than 25.0 wt% of water relative to its total weight.

[0271] The low water content of the dye (F) ensures the storage stability of the dye (F) and also ensures that the organic C1-C6-alkoxysilane is still present in reactive form and has not yet fully polymerized. If the complete crosslinking of the organic C1-C6-alkoxysilane takes place only after the dye (F) has been applied to the keratin material, the film formed during the crosslinking is characterized by particularly high robustness and resistance. If the dye (F) contains less than 25.0 wt. % of water, a robust film is already obtained. It has proven to be preferred to even further reduce the water content of the dye (F).

[0272] Particularly preferably, the dye (F) is produced with such a low water content that the water content of the dye (F) is in the range of 0 to 20.0 wt.-%, preferably 0.1 to 10.0 wt.-%, more preferably 0.1 to 5.0 wt.-%, particularly preferably 0.5 to 3.0 wt.-% of water (F3), based on the total weight of the dye (F).

[0273] In a further particularly preferred embodiment, the process according to the invention is characterized in that the dye (F) contains 0 to 20.0 wt.-%, preferably 0.1 to 10.0 wt.-%, more preferably 0.1 to 5.0 wt.-%, particularly preferably 0.5 to 3.0 wt.-% of water (F3), based on the total weight of the dye (F).

[0274] Solvent (F4) in dye (F)

[0275] As a fourth component essential to the present invention, the dye (F) contains at least one solvent (F4) other than water. Solvent is an established term used in chemistry for substances that are liquid at room temperature (20° C.) and are capable of dissolving other chemical substances. One or more solvents (F4) ensure fine dispersion of the pigment (F2) and provide uniform mixing of the pigment (F2) and the C1-C6 alkoxysilane (F1). At the same time, the addition of at least one solvent also improves the storage stability of the dye (F).

[0276] Since the dye (F) is manufactured with a low water content, the solvent (F4) together with water or alone preferably forms the cosmetic carrier and is therefore preferably the main component of the dye (F).

[0277] Suitable solvents may be, for example, compounds selected from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, dipropylene glycol, diethylene glycol monoethyl ether, glycerol, phenoxyethanol, benzyl alcohol, poly C1-C6 alkylene glycol, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate and glycerol carbonate.

[0278] In a further particularly preferred embodiment, the process according to the invention is characterized in that the dye (F) contains at least one solvent (F4) other than water, which is selected from ethanol, isopropanol, 1,2-propylene glycol, 1,3-propylene glycol, ethylene glycol, 1,2-butylene glycol, dipropylene glycol, diethylene glycol monoethyl ether, glycerol, phenoxyethanol, benzyl alcohol, poly-C1-C6 alkylene glycols, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate and glycerol carbonate.

[0279] In a further specifically very particularly preferred embodiment, the process according to the invention is characterized in that the dye (F) contains at least one solvent (F4) other than water which is selected from ethanol and isopropanol.

[0280] The CAS number for ethanol is 64-17-5. Isopropyl alcohol is also known as 2-propanol and has a CAS number of 67-63-0. Alternatively, 1,2-propylene glycol is also known as 1,2-propanediol and has CAS numbers of 57-55-6 [(RS)-1,2-dihydroxypropane], 4254-14-2 [(R)-1,2-dihydroxypropane] and 4254-153 [(S)-1,2-dihydroxypropane]. 1,3-propylene glycol is also known as 1,3-dihydroxypropane or 1,3-propanediol and has a CAS number of 504-63-2. Ethylene glycol is also alternatively known as 1,2-ethanediol and has a CAS number of 107-21-1. 1,2-Butanediol (1,2-butylene glycol) may also be known as 1,2-butanediol and has CAS numbers of 584-03-2 (racemate), 40348-66-1 ((R)-enantiomer) and 73522-17-5 ((S)-enantiomer).

[0281] Dipropylene glycol (or oxydipropylene glycol) forms a group of substances derived from glycol ethers. The group of dipropylene glycols includes 2,2'-oxydi-1-propanol with CAS number 108-61-2, 1,1'-oxydi-2-propanol with CAS number 110-98-5 and 2-(2-hydroxypropoxy)-1-propanol with CAS number 106-62-7. The mixture of these three isomers has CAS number 25265-71-8.

[0282] Diethylene glycol monoethyl ether may alternatively also be referred to as ethoxydiglycol or ethyldiglycol or 2-(2-ethoxyethoxy)ethanol and has a CAS number of 111-90-0.

[0283] Glycerin may also be alternatively referred to as 1,2,3-propanetriol, and has a CAS number of 56-81-5. Phenoxyethanol has a CAS number of 122-99-6.

[0284] Benzyl alcohol may also be alternatively referred to as benzyl alcohol and has a CAS number of 100-51-6.

[0285] Suitable poly-C1-C6 alkylene glycols include in particular polyethylene glycols such as those described by formula (AG):

[0286]

[0287] Therein, x represents an integer of 1 to 1000, preferably 1 to 100, particularly preferably 2 to 50.

[0288] Alkylene glycols of formula (AG) are protic substances having at least one hydroxyl group and, due to the recurring -CH2-CH2-O- units, can also be referred to as polyethylene glycols when x is a value of at least 2. In the alkylene glycols (a1) of formula (AG), x is an integer from 1 to 10,000. In the context of the work leading to the present invention, it has been found that these polyethylene glycols exhibit particularly advantageous suitability for improving the fastness properties of dyeing agents on the one hand and also for optimally adjusting the viscosity of the agents on the other hand.

[0289] Polyethylene glycols with molecular weights between 200 g / mol and 400 g / mol are non-volatile liquids at room temperature. The melting range of PEG600 is 17 to 22°C and therefore has a pasty consistency. In the case of molecular weights above 3000 g / mol, PEG is a solid substance and is commercially available as flakes or powders.

[0290] For example, a very particularly preferred low molecular weight polyethylene glycol is PEG-8. PEG-8 comprises on average 8 ethylene glycol units (x1=8), has an average molecular weight of 400 g / mol, and has the CAS number 25322-68-3. PEG-8 is also alternatively known as PEG 400 and is commercially available, for example, from APS.

[0291] Further very suitable low molecular weight polyethylene glycols are, for example, PEG-6, PEG-7, PEG-9 and PEG-10.

[0292] Another very suitable polyethylene glycol is, for example, PEG-32. PEG-32 comprises 32 ethylene glycol units (x1=32), has an average molar mass of 1500 g / mol, and has the CAS number 25322-68-3. PEG-32 is also alternatively known as PEG 1500 and is commercially available, for example, from Clariant.

[0293] Dimethyl carbonate is also alternatively referred to as dimethyl carbonate, and has a CAS number of 616-38-6. Diethyl carbonate is also alternatively referred to as diethyl carbonate, and has a CAS number of 105-58-8.

[0294] Ethylene carbonate is also known as 1,3-dioxolane-2-one. Ethylene carbonate corresponds to the compound of formula (I) in which R1 and R2 represent hydrogen and n is 0. The CAS number of ethylene carbonate is 96-49-1.

[0295] Propylene carbonate is also alternatively referred to as 4-methyl-1,3-dioxolane-2-one. Propylene carbonate corresponds to the compound of formula (I) wherein R1 is methyl, R2 is hydrogen and n is 0. The CAS numbers of propylene carbonate are 108-32-7 [(RS)-4-methyl-1,3-dioxolane-2-one], 51260-39-0 [(S)-4-methyl-1,3-dioxolane-2-one] and 16606-55-6 [(R)-4-methyl-1,3-dioxolane-2-one]. The present invention encompasses all of the above stereoisomers.

[0296] According to the invention, butylene carbonate is understood to mean 1,2-butylene carbonate, which is also alternatively called 4-ethyl-1,3-dioxolane-2-one and has the CAS number 4437-85-8. Butylene carbonate corresponds to the compound of formula (I) in which R1 is an ethyl group, R2 is a hydrogen atom and n is 0.

[0297] Glycerol carbonate is alternatively also known as 4-hydroxymethyl-1,3-dioxolane-2-one and has the CAS number 931-40-8. Glycerol carbonate corresponds to the compound of formula (I) in which R1 represents a hydroxymethyl group, R2 represents a hydrogen atom and n represents the number 0.

[0298] In a preferred embodiment, the one or more solvents (F4) constitute the cosmetic carrier of the agent and are therefore preferably used as the main component in the dye (F). In this context, main component refers to the component used in an amount that exceeds all other ingredients.

[0299] When used as main components, it may be advantageous to select one or more solvents (F4) in a correspondingly high amount. Thus, for example, the dye (F) may contain a total amount of 20 to 95 wt.-%, preferably 30 to 85 wt.-%, more preferably 40 to 80 wt.-%, very particularly preferably 45 to 75 wt.-% of one or more solvents (F4) other than water, based on the total weight of the dye (F).

[0300] In a further particularly preferred embodiment, the process according to the invention is characterized in that the dye (F) contains one or more solvents other than water (F4) in a total amount of 20 to 95 wt.-%, preferably 30 to 85 wt.-%, more preferably 40 to 80 wt.-%, very particularly preferably 45 to 75 wt.-%, based on the total weight of the dye (F).

[0301] Fatty components in dyes (F5)

[0302] As a further optional component, the dye can additionally contain at least one fatty component (F5) which is liquid at 20° C. Similar to the solvent (F4), the liquid fatty component (F5) can also ensure a fine dispersion of the pigment (F2) and provide a uniform mixing with the silane (F1). At the same time, the addition of the fatty component (F5) can further improve the storage stability of the agent.

[0303] "Fat components" in the context of the present invention are understood to be organic compounds whose solubility in water at room temperature (22° C.) and atmospheric pressure (760 mmHg) is less than 1 wt %, preferably less than 0.1 wt %. Fat components that are liquid at 20° C. have a melting point below 20° C. (measured at atmospheric pressure (760 mmHg)).

[0304] The definition of the fat component also explicitly includes only uncharged (ie nonionic) compounds. The fat component has at least one saturated or unsaturated alkyl group with at least 8 C atoms. The molecular weight of the fat component is at most 5,000 g / mol, preferably at most 2,500 g / mol, particularly preferably at most 1,000 g / mol. The fat component is a polyoxyalkylated or polyglycerolated compound.

[0305] Linear or cyclic silicone oils, hydrocarbon oils, liquid fatty acid triglycerides, liquid fatty alcohols and ester oils may be mentioned as particularly suitable fat components, with the proviso that the melting point of each compound of the abovementioned substance classes is below 20°C.

[0306] In the sense of the present invention, only nonionic substances are explicitly regarded as fat components. Charged compounds such as fatty acids and their salts are not to be understood as fat components.

[0307] In a further particularly preferred embodiment, the process according to the invention is characterized in that the dye (F) contains at least one fatty component (F5) which is liquid at 20° C. and is selected from linear or cyclic silicone oils, hydrocarbon oils, liquid fatty acid triglycerides, liquid fatty alcohols, ester oils and mixtures thereof.

[0308] Silicone oils may also be referred to as oligoalkylsiloxanes and polyalkylsiloxanes that are liquid at 20°C, i.e., the melting point of the silicone oil is below 20°C (at atmospheric pressure (760 mmHg)). Preferred linear silicone oils are oligoalkylsiloxanes of general formula (V):

[0309]

[0310] Therein, z represents an integer from 0 to 10,000, preferably an integer from 0 to 1,000, more preferably an integer from 0 to 100, very particularly preferably an integer from 0 to 10.

[0311] Very particularly preferred linear oligoalkylsiloxanes are, for example:

[0312] -Hexamethyldisiloxane

[0313]

[0314] -Octamethyltrisiloxane

[0315]

[0316] -Decamethyltetrasiloxane

[0317]

[0318] Hexamethyldisiloxane has the CAS number 107-46-0 and is commercially available from, for example, Sigma-Aldrich.

[0319] Octamethyltrisiloxane has the CAS number 107-51-7 and is also commercially available from Sigma-Aldrich.

[0320] Decamethyltetrasiloxane has the CAS number 141-62-8 and is also commercially available from Sigma-Aldrich.

[0321] Another particularly suitable silicone oil is commercially available, for example, under the trade name Dimethicone Fluid 5 cSt from Clearco. The common name of this silicone oil is polydimethylsiloxane, CAS number 63148-62-9. This substance is a clear, colorless and odorless liquid low viscosity oil.

[0322] Another particularly suitable silicone oil is commercially available from Dow Corning under the trade name Xiameter PMX 200 (1.5 cSt). This oil is also a dimethicone or polydimethylsiloxane having the CAS number 63148-62-9.

[0323] Preferred cyclic oligoalkylsiloxanes are compounds of formula (VI)

[0324]

[0325] Therein y represents an integer from 1 to 5. z preferably represents the number 1, 2 or 3.

[0326] Very particularly preferred cyclic oligoalkylsiloxanes are, for example:

[0327] -Hexamethylcyclotrisiloxane

[0328] -Octamethylcyclotetrasiloxane

[0329] -Decamethylcyclopentasiloxane

[0330] In a further preferred embodiment, the agent according to the invention is characterized in that it contains as fatty component (c) at least one silicone oil of the formula (V) and / or (VI),

[0331]

[0332] wherein z represents an integer from 0 to 10,000, preferably an integer from 0 to 1,000, more preferably an integer from 0 to 100, very particularly preferably an integer from 0 to 10,

[0333]

[0334] wherein y represents an integer of 1 to 5, preferably an integer of 1 to 3.

[0335] In a further preferred embodiment, the agent according to the invention is characterized in that it contains at least one oligoalkylsiloxane (c) selected from the group consisting of hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane and / or decamethylcyclopentasiloxane.

[0336] In contrast to reactive organosilicon compounds, in particular silanes of formula (I) and (II), oligoalkylsiloxanes contain only dialkylsilyl groups (in particular dimethylsilyl groups) and trialkylsilyl groups (in particular trimethylsilyl groups) which are linked to one another via oxygen atoms. Oligoalkylsiloxanes are therefore not themselves reactive compounds within the meaning of the present invention and do not have any hydrolyzable groups.

[0337] Hydrocarbon oils are also particularly suitable fat components which are liquid at 20°C.

[0338] Hydrocarbons are compounds with 8 to 80 C atoms which contain only carbon and hydrogen atoms. In this context, aliphatic hydrocarbons such as mineral oil, liquid paraffin oil (e.g. liquid paraffin or paraffinum perliquidum), isoparaffin oil and polydecene are particularly preferred. The hydrocarbons according to the invention are also characterized in that their melting point at atmospheric pressure is below 20°C.

[0339] Liquid fatty acid triglycerides are also particularly suitable fat components which are liquid at 20°C.

[0340] For C 12 -C 30 Fatty acid triglycerides, in the context of the present invention, are triesters of the trivalent alcohol glycerol, which are understood to have 3 equivalents of fatty acids. Both structurally identical and different fatty acids within the triglyceride molecule can participate in ester formation, provided that the melting point of the fatty acid triglyceride is below 20°C.

[0341] According to the invention, fatty acids are understood to be saturated or unsaturated, unbranched or branched, unsubstituted or substituted C 12 -C 30 Carboxylic acid. Unsaturated fatty acids can be monounsaturated or polyunsaturated fatty acids. For unsaturated fatty acids, their CC double bonds can have cis or trans configurations.

[0342] Fatty acid triglycerides are characterized by a particular suitability in which, starting from glycerol, at least one of the ester groups is formed by a fatty acid selected from the group consisting of dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), lignoceric acid (lignoceric acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), petroselinic acid [(Z)-6-octadecenoic acid], palmitoleic acid [(9Z)-hexadec-9-enoic acid], oleic acid [(9Z)-octadec-9-enoic acid], elaidic acid [(9E)-decadecanoic acid] Octadeca-9-enoic acid], erucic acid [(13Z)-docosa-13-enoic acid], linoleic acid [(9Z,12Z)-octadeca-9,12-dienoic acid, linolenic acid [(9Z,12Z,15Z)-octadeca-9,12,15-trienoic acid, elaeolic acid [(9Z,11E,13E)-octadeca-9,11,3-trienoic acid], arachidonic acid [(5Z,8Z,11Z,14Z)-eicosane-5,8,11,14-tetraenoic acid] and / or nervonic acid [(15Z)-eicosane-15-enoic acid].

[0343] Therefore, another particularly preferred embodiment is an agent for dyeing keratin materials, characterized in that it contains as fat component (c) which is liquid at 20° C. naturally occurring fatty acid triglycerides and / or a mixture of naturally occurring fatty acid triglycerides contained in soybean oil, peanut oil, olive oil, sunflower oil, macadamia oil, moringa oil, almond oil, marula oil and / or optionally hydrogenated castor oil.

[0344] Liquid fatty alcohols are also particularly suitable fat components which are liquid at 20°C.

[0345] Preferred linear unsaturated fatty alcohols are (9Z)-octadeca-9-en-1-ol (oleyl alcohol), (9E)-octadeca-9-en-1-ol (elaidol), (9Z,12Z)-octadeca-9,12-dien-1-ol (linoleyl alcohol), (9Z,12Z,Z)-octadeca-9,12,15-trien-1-ol (linolenyl alcohol), gadoleol ((9Z)-eicos-9-en-1-ol), arachidonic acid ((5Z,8Z,11Z,14Z)-eicos-5,8,11,14-tetraen-1-ol), erucic acid ((13Z)-docosa-13-en-1-ol) and / or basil alcohol ((13E)-docosaen-1-ol). An example of a branched liquid fatty alcohol is 2-octyldodecanol.

[0346] Ester oils are also particularly suitable fat components which are liquid at 20°C.

[0347] Ester oil should be understood as C 12 -C 30 Fatty acids and aliphatic C1-C 24 Esters of alcohols. In other words, the ester oils according to the invention are characterized in that their melting point at standard pressure (1013 mbar) is below 20°C.

[0348] When the composition contains at least one selected from C 12 -C 24 Fatty acids and aliphatic monovalent C1-C 24 When post-treatments of ester oils of monoesters of alcohols are applied to previously dyed hair, particularly strong improvements in hair feel are achieved.

[0349] In a further very particularly preferred embodiment, the process according to the invention is characterized in that the post-treatment agent contains at least one fatty component (N-3) selected from esters consisting of C 12 -C 30 Fatty acids and aliphatic monovalent C1-C 24 Alcohol composition.

[0350] In C 12 -C 30 In the fatty acid group, C 12 -C 24 Fatty acids are particularly suitable. C 12 -C 24Examples of fatty acids are caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, eleostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and technical mixtures thereof. Examples of fatty alcohol components in ester oils are isopropanol, hexanol, octanol, 2-ethylhexyl alcohol, decanol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmityl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidic alcohol, petroselinic acid, linoleyl alcohol, linoleyl alcohol, eleostearyl alcohol, arachidic acid, gadoleyl alcohol, behenyl alcohol, erucic acid and basilic acid and technical mixtures thereof.

[0351] These C 12 -C 24 Fatty acids are synthesized by C1-C 24 The aliphatic alcohol is reacted to esterify, and the aliphatic alcohol is particularly preferably a monohydric alcohol, so that the esterification produces a monoester.

[0352] Aliphatic C1-C 24 The alcohols may be straight-chain or branched, saturated or mono- or polyunsaturated.

[0353] For example, an alcohol selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, n-pentanol, 2-ethylhexanol, n-hexanol, n-octanol, n-decanol and n-dodecanol can be used as the C1-C2 alcohol. 24 Aliphatic saturated alcohol.

[0354] Monovalent unsaturated C1-C 24 Examples of alcohols are oleyl alcohol (octadec-9-en-1-ol), oleyl alcohol (octadec-9-en-1-ol), oleyl alcohol (octadec-9-en-1-ol), palmitoleyl alcohol (cis-9-hexadecen-1-ol), anti-oleyl alcohol (trans-9-octadecen-1-ol) and cis-11-octadecen-1-ol.

[0355] To form an ester, select C 12 -C 24 Fatty acids and C1-C 12 Alcohol, so that the ester formed by esterification of the two reactants is an ester oil, ie its melting point at 1013 mbar is below 20°C.

[0356] Some ester oils according to the present invention can be used in the form of commercial raw materials, which are mixtures of esters obtained from fatty acids of different chain lengths and / or alcohols of different chain lengths. These raw materials can have a melting range. For these raw materials, a melting point below 20°C means that the melting process starts at a temperature below 20°C.

[0357] For example, if an ester oil in the form of a specific raw material can be used in a reagent, wherein the melting range of the raw material is from 16 to 27° C., then the raw material contains at least one ester oil having a melting point below 20° C. Such an ester oil is therefore according to the invention.

[0358] Particularly preferred according to the invention is 2-ethylhexyl palmitate ( 24) Isopropyl myristate ( IPM), C16-18 Alkyl Isononanoate ( SN), 2-ethylhexyl stearate ( 868), Cetyl Oleate, Tricaprylin, Coconut Fatty Alcohol Caprate / Caprylate ( LC), n-butyl stearate, oleyl erucate ( J 600), isopropyl palmitate ( IPP), oleyl oleate Hexyl laurate ( A), di-n-butyl adipate ( B), Cetearyl Isononanoate ( SN) and decyl oleate ( V).

[0359] Most particularly preferably, the ester oil (N-3) is selected from isopropyl myristate, 2-ethylhexyl palmitate, C16-18 alkyl isononanoate, 2-ethylhexyl stearate, cetyl oleate, coconut fatty alcohol caprate, coconut fatty alcohol caprylate, n-butyl stearate, oleyl erucate, isopropyl palmitate, oleyl oleate, hexyl laurate, cetearyl isononanoate and decyl oleate.

[0360] Alternatively, isopropyl myristate is also known as isopropyl myristate, with a CAS number of 110-27-0. Isopropyl myristate is a colorless, odorless liquid with a melting point of 0-1°C.

[0361] 2-Ethylhexyl palmitate is also alternatively referred to as 2-ethylhexyl palmitate, with a CAS number of 29806-73-3. 2-Ethylhexyl palmitate is a branched saturated ester oil of palmitic acid and ethylhexyl alcohol. 2-Ethylhexyl palmitate exists at room temperature as a clear, colorless liquid with a slightly greasy odor.

[0362] C16-18 Alkyl Isononanoate is also alternatively known as Cetearyl Isononanoate; the CAS numbers for this ester are 84878-33-1 and 84878-34-2. 16-18 Alkyl ester is a transparent slightly yellow liquid. At 20°C, isononanoic acid C 16-18 The viscosity of the alkyl esters is 19-22 mPas.

[0363] 2-Ethylhexyl stearate is also alternatively referred to as ethylhexyl stearate, with the CAS number 91031-48-0. 2-Ethylhexyl stearate is in the form of a transparent, slightly yellow, low-viscosity oil. At 20° C., 2-Ethylhexyl stearate has a viscosity of 14-16 mPas and is therefore an oil at room temperature.

[0364] The CAS number of cetyl oleate is 22393-86-8.

[0365] The CAS number of coconut fatty alcohol caprylate / caprate is 95912-86-0. It is C8-C 10 Fatty acids and C 12 -C 18 A mixture of fatty alcohols, present as a yellow liquid with a melting point of 10°C.

[0366] n-Butyl stearate is also known as butyl stearate, CAS No. 85408-76-0 (C 16-18 ) and 123-95-5(C 18 ). n-Butyl stearate is a pale yellow liquid and begins to melt at 16°C.

[0367] The CAS number of oleyl erucate is 17673-56-2. Oleyl erucate is a yellow liquid. At 20°C, the viscosity of oleyl erucate is 40-50 mpas, so it is an oil at room temperature.

[0368] Isopropyl palmitate is also alternatively known as propan-2-yl hexadecanoate, CAS number 142-91-6. The melting point of isopropyl palmitate is 13.5°C.

[0369] Alternatively, oleyl oleate is also known as cis-9,10-octadecenyl-cis-9,10-octadecanoate or oleyl oleate, with a CAS number of 3687-45-4. Oleyl oleate is a transparent slightly yellow oil with a viscosity of 25-30 mPas at 20°C and is an oil at room temperature.

[0370] Hexyl laurate is also alternatively known as hexyl laurate, CAS number 34316-64-8. Hexyl laurate is a clear, slightly yellow, odorless oil at room temperature. At 20°C, hexyl laurate has a viscosity of 5-7 mpas and is therefore an oil at room temperature.

[0371] Cetearyl Isononanoate is also known alternatively as Isononanoate C 16-18 Alkyl esters, CAS No. 84878-33-1 and 84878-34-2. Cetearyl isononanoate is a pale yellow liquid with a melting point of 16-22°C.

[0372] Decyl oleate is also alternatively referred to as decyl oleate, CAS number 3687-46-5. Decyl oleate is a slightly yellow liquid with a viscosity of 15-20 mPas at 20° C. Therefore, decyl oleate is an oil at room temperature.

[0373] Preferably, one or more fatty components (F5) which are liquid at 20° C. are used in a certain amount range in the agents according to the invention. Particularly good results are achieved when the dye (F) contains a total amount of 1.0 to 99 wt.-%, preferably 5.0 to 60.0 wt.-%, more preferably 10.0 to 30.0 wt.-%, very particularly preferably 15.0 to 25.0 wt.-% of one or more fatty components (c) which are liquid at 20° C., based on the total weight of the dye (F).

[0374] In a further particularly preferred embodiment, the process according to the invention is characterized in that the dye (F) contains a total amount of 1.0 to 99 wt.-%, preferably 5.0 to 60.0 wt.-%, more preferably 10.0 to 30.0 wt.-%, very particularly preferably 15.0 to 25.0 wt.-%, of one or more fat components (F5) which are liquid at 20° C., based on the total weight of the dye (F).

[0375] Other optional components of the dye (F)

[0376] In addition to the essential components (F1), (F2), (F3) and (F4) and the optional component (F5), the dye (F) may optionally contain further components.

[0377] The dye (F) may therefore also contain other active ingredients, auxiliaries and additives, such as cationic, nonionic, amphoteric, zwitterionic and / or anionic surfactants, thickening polymers, film-forming polymers, structurants (such as glucose, maleic acid and lactic acid), hair conditioning compounds (such as phospholipids, for example lecithin and cephalin); perfume oils, dimethyl isosorbide and cyclodextrins; active fiber structure improvers, in particular mono-, disaccharides and oligosaccharides, such as glucose, galactose, fructose and lactose; dyes for coloring the product; active anti-dandruff ingredients, such as piroctone olamine, omadine zinc and climbazole; amino acids and oligopeptides; animal and / or vegetable protein hydrolysates, and their fatty acid condensation products or in the form of optionally anionically or cationically modified derivatives; light stabilizers and UV blockers; Active ingredients, such as panthenol, pantothenic acid, pantolactone, allantoin, pyrrolidone carboxylic acid and its salts and bisabolol; polyphenols, in particular hydroxycinnamic acid, 6,7-dihydroxycoumarin, hydroxybenzoic acid, catechins, tannins, leucocyanidins, anthocyanidins, flavanones, flavonoids and flavonols; ceramides or pseudoceramides; vitamins, provitamins and vitamin precursors; plant extracts; fats and waxes, such as fatty alcohols, beeswax, montan wax and paraffin; swelling and osmotic agents, such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidine, urea and primary, secondary and tertiary phosphates; opacifiers, such as latex, styrene / PVP and styrene / acrylamide copolymers; pearlescent agents, such as ethylene glycol monostearate and ethylene glycol distearate and PEG-3 distearate; and propellants, such as propane-butane mixtures, N2O, dimethyl ether, CO2 and air.

[0378] Those skilled in the art select these additional substances according to the desired properties of the reagent. Regarding other optional components and the usage amounts of the components, explicit reference is made to the relevant manuals known to those skilled in the art. The usage amounts of the additional active ingredients and adjuvants in the formulations according to the present invention are preferably generally 0.0001 to 25 wt%, particularly 0.0005 to 15 wt%, relative to the total weight of the specific reagent.

[0379] Steps of dyeing method

[0380] The method according to the invention comprises the following steps in the specified order:

[0381] (1) providing the above-mentioned dye (F),

[0382] (2) applying the dye (F) to the wet or dry keratin material,

[0383] (3) optionally applying a specified amount of water to the keratin material still coated with the dye (F), wherein the weight of the amount of water applied in step (3) is at most twice the weight of the dye (F) applied in step (2), and

[0384] (4) Drying the keratin material without previously washing off the dye (F).

[0385] In one embodiment, the dye (F) according to the present invention in the above-mentioned form can be directly provided as is and applied to keratin materials or hair. In this form, the dye (F) according to the present invention is also a ready-to-use agent and can be provided, for example, in a bottle, container, tube or jar. The greatest advantage of this form of application is that the form of application is convenient and simple, because the user can easily take out the dye from the bottle or container providing the dye (F) and apply it to the keratin material. For this embodiment, it is not necessary to mix, vibrate and / or homogenize with one or more other components or compositions.

[0386] In addition, however, dye (F) can also be first prepared in or before step (1) of the method. This production can be carried out, for example, by mixing a silane blend containing one or more organic C1-C6 alkoxysilanes (F1) with another reagent containing a pigment (F2). In this case, water (F3) and solvent (F4) can be present in the silane blend and / or the reagent containing the pigment. In this embodiment, components (F1) to (F4) can be present in at least two containers manufactured separately and can be combined or mixed together during the preparation of dye (F). Even if this embodiment means more effort for the user, it may be preferred to improve the storage stability of C1-C6 alkoxysilane (F1), avoid premature aggregation between silane (F1) and pigment (F2) or prevent undesirable interaction between silane (F1) and solvent (F4).

[0387] In the second step of the method according to the invention, the dye (F) is applied to the wet or dry keratin material. The application or application can be carried out, for example, with the aid of a small brush, a brush or a nozzle, or the user can operate with gloved hands.

[0388] In one embodiment, the dye can be applied to dry keratin materials or hair. In this case, due to the amount of water (F3) contained in the dye (F) itself, hydrolysis and condensation of the organic C1-C6 alkoxysilane occur.

[0389] When the dye (F) is applied to previously wetted or towel-dried hair, particularly good intense and durable colors can be obtained. Since the dye (F) itself has a low water content or is anhydrous, the additional amount of water in the hair supports the condensation of the organic C1-C6 alkoxysilane directly on the keratin surface. In this way, a particularly uniform and resistant coating is formed, which tightly wraps around the hair fiber and is formed directly to the area where the film is to be located.

[0390] Wet or towel-dried hair is understood to be hair that has been thoroughly wetted with water in a sink or shower and then squeezed and dried with a towel (e.g., for 30 seconds). Thus, wet or towel-dried hair is no longer dripping, but is still damp.

[0391] In a further very particularly preferred embodiment, the process according to the invention is characterized in that

[0392] (2) The dye (F) is applied to the keratin material which has been wetted shortly before the application.

[0393] The keratin material, such as the hair, which is moistened shortly before application is moistened within a period of at most 30 minutes, preferably at most 10 minutes, before application.

[0394] In step 3 of the process, a specified amount of water is optionally applied to the keratin material still coated with the dye (F), wherein the weight of the amount of water applied in step (3) is at most twice the weight of the dye (F) applied in step (2).

[0395] Step (3) of the method according to the invention is optional and can be carried out, for example, if the dye (F) is applied to the dry keratin material in step (2), or if the amount of water present in the wet keratin material is not sufficient to completely crosslink or condense the organic C1-C6 alkoxysilane. Thus, the additional application of a specified amount of water in step (3) can initiate post-condensation or post-crosslinking of the organic C1-C6 alkoxysilane. This post-crosslinking ensures further hardening of the film or coating.

[0396] However, in step (3), the dye (F) should not be washed out, i.e. the additional amount of water applied to the hair coated in the dye (F) should be large enough so that the C1-C6 alkoxysilane can come into contact with a sufficient amount of water but the dye (F) is not washed out or does not run off the hair fiber. As shown in the work leading to the present invention, this is the case when the weight of the amount of water applied in step (3) is at most twice the weight of the dye (F) applied in step (2).

[0397] Here, the amount of water and the amount of dye (F) are to be understood as amounts by weight. Thus, if 50 g of dye (F) are applied to the hair / keratin material in step (2), then at most 100 g of water may be applied to the hair / keratin material in step (3).

[0398] In step (3), a specified amount of water can be distributed on the keratin material and mixed with the dye (F), which is also still on the keratin material. This mixing can be assisted by rubbing with the hands or a small brush.

[0399] It is particularly preferred if step (3) is carried out. Therefore, very particular is a method comprising the steps of,

[0400] (2) applying the dye (F) to the wet keratin material, and

[0401] (3) applying a specified amount of water to the keratin material still coated with the dye (F),

[0402] The total amount of water used for moistening the material in step (2) and for application to the keratin material in step (3) is at most twice the weight of dye (F) applied in step (2).

[0403] Also particularly preferred is a method comprising the steps,

[0404] (2) applying the dye (F) to the wet keratin material, and

[0405] (3) applying a specified amount of water to the keratin material still coated with the dye (F),

[0406] The total amount of water used for moistening the material in step (2) and for application to the keratin material in step (3) is precisely at most twice the weight of dye (F) applied in step (2).

[0407] Thus, if 50 g of dye (F) are applied to the hair / keratin material in step (2), up to 50 g of water may be applied to the hair / keratin material in step (3) together with up to exactly the same amount of water.

[0408] There may be a period of time between steps (2) and (3) (if step (3) is carried out) of a few seconds to 60 minutes, preferably 30 seconds to 30 minutes.

[0409] After step (3), the keratin material is dried in step (4) without previously washing out the dye (F).

[0410] During drying, the water (F3) and solvent (F4) present in the dye evaporate or vaporize, and the film formed by condensation of the C1-C6-alkoxysilane solidifies. Drying can be carried out in air or under the influence of heat, for example with the aid of a heating hood or a hair dryer.

[0411] Between steps (3) and (4) there may be (if step (3) is carried out) a period of a few seconds to 60 minutes, preferably 30 seconds to 30 minutes. If the keratin material is dried in air, step (4) begins immediately after step (3).

[0412] If step (3) is not carried out, there may be a period of time of a few seconds to 60 minutes, preferably 30 seconds to 30 minutes, between steps (2) and (4). If the keratin material is dried in air, step (4) begins immediately after step (2).

[0413] The drying of the keratin material or hair which takes place in step (4) can be accelerated by a heat treatment. Heat treatment is understood to mean that the keratin material is brought into contact with a heating device or such a heating device is applied to the keratin material. Furthermore, the keratin material can also be brought into contact with warm / hot air for the heat treatment. For example, a hair dryer, a hair dryer, a heat hood, a hair straightener, a curling iron or an infrared lamp can be used as a device.

[0414] In a particularly preferred embodiment, the method according to the invention is characterized in that the heat treatment is carried out by application of a hair dryer, a hair dryer, a heat hood, a hair straightener, a curling iron or infrared lamps.

[0415] It has also been found that the treatment temperature during the heat treatment is preferably from 40° C. to 210° C., preferably from 50° C. to 190° C., more preferably from 50° C. to 170° C., even more preferably from 50° C. to 150° C., very particularly preferably from 50° C. to 100° C. In other words, it has been found that it is particularly preferred if the heat treatment is carried out using an apparatus which is heated to a temperature of from 40° C. to 210° C., preferably from 50° C. to 190° C., more preferably from 50° C. to 170° C., even more preferably from 50° C. to 150° C., very particularly preferably from 50° C. to 100° C.

[0416] In a further very particularly preferred embodiment, the process according to the invention is characterized in that

[0417] (4) Drying the keratin material at a temperature of 40 to 210° C., preferably 45 to 190° C., more preferably 45 to 170° C., even more preferably 45 to 150° C., very particularly preferably 45 to 100° C., without previously washing out the dye (F).

[0418] For example, the keratin material or the hair can thus be treated with a hair dryer blowing warm or hot air onto the keratin material. The air is very particularly preferably at 50 to 100° C. Alternatively, the keratin material or the hair is held under an infrared lamp, which is particularly preferably set to a temperature of 50 to 100° C. For the purpose of the heat treatment, the hair can also be pressed between two corresponding temperature-controlled plates of a hair straightener, which plates can be moved simultaneously along the fibers. The plates of the hair straightener can be set to a temperature of, for example, up to 210° C.

[0419] The heat treatment can conveniently be carried out until the keratin material still coated with the dye (F) has become dry to the touch or completely dry.

[0420] After or before step (4), the method according to the invention may also optionally include further steps. For example, further work has shown that the durability of the color obtained, in particular the wash fastness, can be further improved if the keratin material has been tempered in high humidity air after or before step (4). Contact with humid air causes the film or coating produced on the keratin material to become more resistant. Particularly good results are obtained when the colored keratin material or the colored dried keratin material is tempered in air with a relative humidity of 40% to 99%, preferably 50% to 95%, more preferably 60% to 95%, particularly preferably 70% to 95% (measured at 20° C. and a pressure of 11013.25 hPa).

[0421] In a further embodiment, a method comprising the following steps before or after step (4) is particularly preferred:

[0422] The keratin material is brought into contact with air having a relative humidity of 40% to 99%, preferably 50% to 95%, more preferably 60% to 95%, particularly preferably 70% to 95% (measured at 20° C. and a pressure of 11013.25 hPa).

[0423] Air humidity (or simply humidity) refers to the proportion of water vapor in the gas mixture in the air. Therefore, liquid water (such as raindrops, fog droplets) or ice do not count as air humidity. Depending on the temperature and pressure, a given volume of air can only contain a certain maximum amount of water vapor. This maximum amount of water vapor in the air is called the saturation amount of water vapor. Relative air humidity is the most common measure of air humidity, which in this case is 100%. Usually, the relative air humidity expressed as a percentage (%) indicates the weight ratio of the current water vapor content to the maximum possible water vapor content at the current temperature and pressure.

[0424] For example, at normal pressure (1013.25 hPa), the saturation amount of water vapor in the air is (corresponding to 100% relative air humidity):

[0425] temperature Saturation -30℃ <![CDATA[0.5g / m 3 <!-- 29 -->]]> -20℃ <![CDATA[1.0g / m 3 ]]> -15℃ <![CDATA[1.4g / m 3 ]]> -10℃ <![CDATA[2.2g / m 3 ]]> -5℃ <![CDATA[3.2g / m 3 ]]> 0℃ <![CDATA[4.9g / m 3 ]]> 5℃ <![CDATA[6.8g / m 3 ]]> 10℃ <![CDATA[9.4g / m 3 ]]> 15℃ <![CDATA[12.8g / m 3 ]]> 20℃ <![CDATA[17.3g / m 3 ]]> 20℃ <![CDATA[23.1g / m 3 ]]> 30℃ <![CDATA[30.4g / m 3 ]]>

[0426] At relative air humidity below 100%, the amount of water vapor in the air decreases accordingly (measured at normal pressure of 1013.25 hPa).

[0427]

[0428] Various measuring devices for measuring air humidity are known in the prior art and are commercially available.

[0429] For example, a PCE-MMK1 hygrometer from "PCE Instruments" can be used to measure relative and absolute air humidity. Air humidity can also be measured with a Bosch PTD thermal detector from "Bosch Home and Garden".

[0430] Bringing the keratin material into contact with air, or in other words treating, resting or storing the keratin material in air with a correspondingly high humidity level, can be done, for example, by keeping the person in a climate chamber or by using a steam hood or climate hood. Steam hoods are commercially available and widely used in the hairdressing industry. Example

[0431] 1. Preparation

[0432] Production of silane blends

[0433] In a 500 ml round bottom flask, 25 g of ethanol (anhydrous) and 49.7 g of methyltriethoxysilane were stirred and mixed together. The mixture was further stirred and heated to 50°C.

[0434] Then, 6.8 g of 1% aqueous sulfuric acid solution was added dropwise over a period of about 5 minutes. The temperature of the reaction mixture was raised to 62° C. and lowered to 55° C. after the addition was complete. Stirring was continued for another 20 minutes. Afterwards, 18.6 g of (3-aminopropyl) triethoxysilane was added dropwise over a period of about 5 minutes. After all additions were made, the mixture was stirred at 50° C. for another 45 minutes and then poured into an airtight glass container.

[0435] The silane blend produced in this way was incorporated into the following dye (F) (all amounts are in wt % unless otherwise stated):

[0436]

[0437] 2. Apply

[0438] Dyes (FI) to (FIV) were applied to hair tresses (Kerling Euronatur hair, white and Kerling 9-0, approximately 5 cm in length) using the following method:

[0439]

[0440] 3. Measurement of washing fastness

[0441] The dye was applied as described in point 2. After drying and resting, the tresses were visually assessed under fluorescent light. 0HW is the color result obtained directly after dyeing. To measure the wash fastness, the tresses were then washed 4 and 8 times, respectively (4HW, 8HW).

[0442] For each shampooing, commercially available shampoo (0.25 g shampoo Schauma 7 The shampoo was then rinsed off under running warm water for 1 minute and the hair tresses were dried. The above process corresponds to shampooing. This process was repeated for each additional shampooing. After the corresponding number of shampooings, the tresses were again visually evaluated under fluorescent light.

[0443] Color intensity: ++++ Very high+++ High++ Medium+ Low

[0444] The following color results are obtained:

[0445]

[0446]

[0447]

[0448]

[0449]

[0450]

[0451]

[0452] When the dyes (FI) to (FIV) are used in the leave-in dyeing process according to the invention, colors with improved color intensity and improved wash fastness can be obtained on different types of hair tresses.

Claims

1. A method for dyeing keratin materials, in particular human hair, comprising the following steps in the specified order: (1) providing a dye (F), wherein the dye (F) contains, based on the total weight of the dye (F): (F1) one or more organic C1-C6 alkoxysilanes and / or condensation products thereof, (F2) at least one pigment, (F3) less than 25.0 wt% water, and (F4) at least one solvent other than water, (2) applying the dye (F) to a wet or dry keratin material, (3) optionally applying a specified amount of water to the keratin material still coated with the dye (F), wherein the weight of the amount of water applied in step (3) is at most twice the weight of the dye (F) applied in step (2), and (4) Drying the keratin material without previously washing off the dye (F).

2. The method according to claim 1, characterized in that The dye (F) contains at least one organic C1-C6 alkoxysilane (F1) of formula (I) and / or a condensation product thereof, R1R2N-L-Si(OR3) a (R4) b (I), in - R1 and R2 independently represent a hydrogen atom or a C1-C6 alkyl group, -L represents a straight chain or branched divalent C1-C 20 Alkylene, - R3 and R4 independently represent a C1-C6 alkyl group, -a represents an integer from 1 to 3, and -b means the integer 3-a.

3. The method according to claim 1 or 2, characterized in that The dye (F) contains at least one organic C1-C6 alkoxysilane (F1) selected from the following group: (3-aminopropyl)trimethoxysilane, (3-aminopropyl)-triethoxysilane, (2-aminoethyl)trimethoxysilane, (2-aminoethyl)triethoxysilane, (3-dimethylaminopropyl)trimethoxysilane, (3-dimethylaminopropyl)triethoxysilane, (2-dimethylaminoethyl)trimethoxysilane, (2-dimethylaminoethyl)triethoxysilane and condensation products thereof.

4. The method according to any one of claims 1 to 3, characterized in that The dye contains at least one organic C1-C6 alkoxysilane (F1) of formula (II): <h2 style=";text-align:left;direction:ltr">R5Si(OR6)<h2 style=";text-align:left;direction:ltr"> k <h2 style=";text-align:left;direction:ltr"> (R7)<h2 style=";text-align:left;direction:ltr"> m <h2 style=";text-align:left;direction:ltr"> (II) in -R5 means C1-C 12 alkyl, -R6 represents a hydrogen atom or a C1-C6 alkyl group, -R7 represents a C1-C6 alkyl group, -k represents an integer from 1 to 3, and -m means integer 3-k.

5. The method according to any one of claims 1 to 4, characterized in that The dye (F) contains at least one organic C1-C6 alkoxysilane (F1) selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane and condensation products thereof.

6. The method according to any one of claims 1 to 5, characterized in that The dye (F) contains a total amount of 0.1 to 30.0 wt. %, preferably 0.5 to 20.0 wt. %, more preferably 5.0 to 15.0 wt. %, very particularly preferably 6.0 to 12.5 wt. %, based on the total weight of the dye (F).

7. The reagent according to any one of claims 1 to 6, characterized in that The dye (F) contains at least one pigment (F2) selected from inorganic pigments, organic pigments and / or metal pigments.

8. The method according to any one of claims 1 to 7, characterized in that The dye (F) contains 0 to 20.0 wt %, preferably 0.1 to 10.0 wt %, more preferably 0.1 to 5.0 wt %, particularly preferably 0.5 to 3.0 wt % of water (F3), based on the total weight of the dye (F).

9. The method according to any one of claims 1 to 8, characterized in that The dye (F) contains at least one solvent (F4) other than water, and the solvent (F4) is selected from ethanol, isopropanol, 1,2-propylene glycol, 1,3-propylene glycol, ethylene glycol, 1,2-butylene glycol, dipropylene glycol, diethylene glycol monoethyl ether, glycerol, phenoxyethanol, benzyl alcohol, poly C1-C6 alkylene glycol, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate and glycerol carbonate, preferably selected from ethanol and isopropanol.

10. The method according to any one of claims 1 to 9, characterized in that The dye (F) contains one or more solvents other than water (F4) in a total amount of 20 to 95 wt %, preferably 30 to 85 wt %, more preferably 40 to 80 wt %, very particularly preferably 45 to 75 wt %, based on the total weight of the dye (F).

11. The method according to any one of claims 1 to 10, characterized in that The dye (F) contains at least one fatty component (F5) which is liquid at 20° C. and is selected from linear or cyclic silicone oils, hydrocarbon oils, liquid fatty acid triglycerides, liquid fatty alcohols, ester oils and mixtures thereof.

12. The method according to any one of claims 1 to 11, characterized in that The dye (F) contains one or more fatty components (F5) which are liquid at 20° C. in a total amount of 1.0 to 99 wt %, preferably 5.0 to 60.0 wt %, more preferably 10.0 to 30.0 wt %, very particularly preferably 15.0 to 25.0 wt %, based on the total weight of the dye (F).

13. The method according to any one of claims 1 to 12, characterized by the following steps: (2) The dye (F) is applied to a keratin material which has been moistened shortly before the application.

14. The method according to any one of claims 1 to 13, comprising: (2) applying the dye (F) to the wet keratin material, and (3) applying a specified amount of water to the keratin material still coated with the dye (F), The total amount of water used for wetting the keratin material in step (2) and for application thereto in step (3) is at most twice the weight of the dye (F) applied in step (2).

15. The method according to any one of claims 1 to 14, comprising: (4) Drying the keratin material at a temperature of 40 to 210° C., preferably 45 to 190° C., more preferably 45 to 170° C., even more preferably 45 to 150° C., very particularly preferably 45 to 100° C., without previously washing off the dye (F).

16. The method according to any one of claims 1 to 15, comprising, before or after step (4), contacting the keratin material with air having a relative humidity of 40% to 99%, preferably 50% to 95%, more preferably 60% to 95%, particularly preferably 70% to 95% (measured at 20° C. and a pressure of 11013.25 hPa).

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