Agent for dyeing keratinous materials, in particular human hair, comprising an aminosilicone and a metallic pigment of the platelet type

Abstract

The present invention relates to an agent for dyeing keratinous materials, in particular human hair, comprising (a1) at least one amino-functionalized silicone polymer and (a2) at least one platelet-type metallic pigment.

Description

[Technical field]

[0001] The present application relates to an agent for dyeing keratinous materials, in particular human hair, comprising at least one amino-functionalized silicone polymer and at least one metallic pigment of the platelet type.

[0002] Another subject of the present application is a method for dyeing keratinous materials, in particular human hair, in which the agent described above is applied to the keratinous materials and, if applicable, washed off after an exposure time of between 30 seconds and 45 minutes. [Background technology]

[0003] Changing the shape and color of keratinous materials, especially human hair, is an important area of ​​modern cosmetics. To change the color of hair, the skilled person is familiar with various dyeing systems depending on the dyeing requirements. Oxidation dyes are generally used for permanent and strong dyeing with good fastness and good coverage of gray. Such dyeing agents include oxidation dye precursors (known as developer and coupler components), which form the actual dye under the influence of an oxidizing agent, for example hydrogen peroxide. Oxidation dyes are characterized by a very long-lasting color finish.

[0004] When using direct dyes, the already formed dye diffuses from the dye into the hair fiber. Compared to oxidative hair dyes, the color obtained with direct dyes is less durable and washes out faster. The color with direct dyes usually remains in the hair for 5 to 20 washes.

[0005] The use of color pigments to briefly change the color of hair and / or skin is known. Color pigments are generally understood to mean insoluble dyeing substances. They are present undissolved in the dye preparation in the form of small particles and are only deposited externally on the hair fiber and / or on the skin surface. They can therefore be removed again, generally without leaving any residue, after several washes with surfactant-containing cleansers. Various products of this kind are commercially available under the name hair mascara.

[0006] If users wish to achieve a particularly long-lasting dyeing, the use of oxidation dyes has been the only option up to now. However, despite numerous optimization attempts, the unpleasant ammonia or amine odor cannot be completely avoided in oxidation dyeing. The residual hair damage associated with the use of oxidation dyes also has a detrimental effect on the user's hair. The search for alternative high-performance dyes and dyeing processes is therefore a continuing challenge. Recently, pigment-based dyeing systems have received particular attention.

[0007] In pigment-based dyes, the main challenge is to bond the pigment to the keratinous material uniformly and for as long as possible. Since the pigment cannot diffuse into the keratinous material, it is usually fixed to the keratinous material surface via various adhesive substances. Suitable fixing substances are, for example, polymeric compounds such as aminosilicones that form a layer or film on the keratinous material, in which the pigment is embedded. Depending on the strength or hydrophobicity of the dye layer, it can remain on the keratinous material even after several hair washings, thus forming a dye with improved wash fastness.

[0008] When used on hair, the main drawback that may be related to the formation of dyed film is that hair feel is impaired.In particular, when pigments or aminosilicones are used in large ranges, hair can feel heavy, oily, uncomfortable, sticky, and even stiff.Therefore, there is a great need for improvement in terms of finding pigment-based dyes that are long-lasting, coverable, and do not adversely affect hair feel. Summary of the Invention [Problem to be solved by the invention]

[0009] The object of the present invention is to provide a dyeing agent that allows the pigment to be fixed to the hair in a very durable manner.When this agent is used in a dyeing process, a particularly strong dyeing result with good washing fastness and excellent covering power must be achieved.At the same time, the hair after dyeing must have a pleasant, smooth and not heavy hair feel. [Means for solving the problem]

[0010] Surprisingly, it has been found that this aforementioned objective can be achieved in a remarkable manner when keratinous materials, in particular human hair, are dyed with an agent comprising at least one amino-functionalized silicone polymer and at least one metallic pigment of the platelet type.

[0011] The first subject of the present invention is (a1) at least one amino-functionalized silicone polymer, and (a2) at least one platelet-type metallic pigment The present invention relates to an agent for dyeing keratinous materials, in particular human hair, which comprises

[0012] Within the context of the research leading to the present invention, it was possible to discover that particularly good color results are obtained when platelet-type metallic pigments mixed with at least one aminosilicone are applied to keratinous materials, in particular human hair. The dyeings thus obtained are distinguished by a particularly high coverage and a uniform color result. If the platelet-type metallic pigment is selected from the corresponding bright metals, optically shining effects can also be produced, and the hair dyed with the pigment appears brighter compared to the original hair color. In this context, it turned out to be very particularly surprising that even after using higher concentrations of aminosilicone (a1) and platelet-type metallic pigment (a2), the hair still feels natural, smooth and not heavy. This made it possible to achieve a particularly uniform dyeing with high coverage while obtaining a natural hair feel.

[0013] Keratin Substances Keratinous materials are understood to mean hair, skin and nails (such as fingernails and / or toenails). Furthermore, wool, fur and feathers also fall within the definition of keratinous materials.

[0014] Keratinous materials are preferably understood to mean human hair, human skin and human nails, in particular fingernails and toenails. Keratinous materials are very particularly preferably understood to mean human hair.

[0015] Dyeing agent Within the scope of the present invention, the term "dye" is used for the coloring of keratinous materials, in particular hair, brought about by the use of pigments, whereby the pigments as coloring compounds are deposited on the surface of the keratinous materials in a particularly homogeneous and even film.

[0016] According to the present invention, the dyeing agent represents a ready-to-use agent. This ready-to-use agent can be, for example, filled into a container and applied in this form to keratin materials without further dilution, mixing or other method steps. However, for reasons of storage stability, it has been found to be very particularly preferable that ready-to-use cosmetics are prepared by the hairdresser or the user only immediately before use. To prepare a ready-to-use agent, it is possible, for example, to mix the amino-functionalized silicone polymer (a1) with the platelet-type metallic pigment (a2), and it is also possible that components (a1) and / or (a2) are provided in the form of a concentrate or are present separately in a suitable separate cosmetic carrier as an emulsion / dispersion. The agents can be mixed, for example, by stirring or shaking.

[0017] In other words, a first subject of the invention is an agent for dyeing keratinous materials, in particular human hair, said agent being preferably ready to use and comprising in a cosmetic carrier: (a1) at least one amino-functionalized silicone polymer, and (a2) at least one platelet-type metallic pigment Includes.

[0018] Amino-functionalized silicone polymers (a1) As a first essential component, the agent according to the invention comprises at least one amino-functionalized silicone polymer (a1), also called aminosilicone or amodimethicone.

[0019] Silicone polymers are generally macromolecules containing repeating organic units and having a molecular weight of at least 500 g / mol, preferably at least 1000 g / mol, more preferably at least 2500 g / mol, and even more preferably at least 5000 g / mol.

[0020] The maximum molecular weight of a silicone polymer depends on the degree of polymerization (number of polymerized monomers) and the batch size, and is also determined by the polymerization method. In the context of the present invention, the maximum molecular weight of a silicone polymer is 10 7 g / mol or less, preferably 10 6 g / mol or less, particularly preferably 10 5 It is preferably less than g / mol.

[0021] Silicone polymers contain multiple Si-O repeat units, where the Si atoms can carry organic residues, such as alkyl or substituted alkyl groups, and therefore silicone polymers are alternatively called polydimethylsiloxanes.

[0022] Corresponding to the high molecular weight of the silicone polymers, these are based on more than 10 Si-O repeat units, preferably more than 50 Si-O repeat units, particularly preferably more than 100 Si-O repeat units and very particularly preferably more than 500 Si-O repeat units.

[0023] Amino-functionalized silicone polymer is understood to mean functionalized silicone that has at least one structural unit with amino group.Amino-functionalized silicone polymer preferably has a plurality of structural units, each of which has at least one amino group.Amino group is understood to mean primary amino group, secondary amino group and tertiary amino group.All of these amino groups are protonated in acidic environment and exist in cationic form.

[0024] In principle, it was possible to achieve positive effects when the amino-functionalized silicone polymer (a1) had at least one primary amino group, at least one secondary amino group, and / or at least one tertiary amino group. However, dyeings with the highest color intensity were observed when amino-functionalized silicone polymers (a1) containing at least one secondary amino group were used in the agent.

[0025] In a very particularly preferred embodiment, the agent according to the invention comprises (a1) at least one amino-functionalized silicone polymer having at least one secondary amino group; It is characterized by:

[0026] The secondary amino group can be at different positions on the amino-functionalized silicone polymer. [ka] Particularly good effects have been found when using amino-functionalized silicone polymers (a1) which have at least one, preferably several, structural units of the formula:

[0027] In the structural unit of the formula (Si-amino), the abbreviations ALK and ALK2 each independently represent a linear or branched divalent C1-C 20 It is an alkylene group.

[0028] In a further very particularly preferred embodiment, the agent according to the invention has the formula (Si-amino): [ka] [In the formula, ALK1 and ALK2 are each independently linear or branched divalent C1-C 20 represents an alkylene group] The silicone composition is characterized in that it comprises at least one amino-functionalized silicone polymer (a1) which comprises at least one structural unit of

[0029] Sites marked with an asterisk (*) always indicate a bond to other structural units of the silicone polymer, for example, the silicon atom adjacent to the asterisk can be bonded to an additional oxygen atom, and the oxygen atom adjacent to the asterisk can be bonded to an additional silicon atom or to a C1-C6 alkyl group.

[0030] Bivalent C1-C 20 The alkylene group may alternatively be a double bond C-C 20 Also referred to as an alkylene group, this means that each moiety ALK1 or ALK2 can have two bonds.

[0031] In the case of ALK1, the silicon atom is bonded to a portion of ALK1 and the second bond is between ALK1 and the secondary amino group.

[0032] In the case of ALK2, the secondary amino group is bound to a portion of ALK2 and a second bond is formed between ALK2 and the primary amino group.

[0033] Straight chain divalent C1-C 20 Examples of alkylene groups include, for example, methylene (-CH2-), ethylene (-CH2-CH2-), propylene (-CH2-CH2-CH2-) and butylene (-CH2-CH2-CH2-CH2-). Propylene (-CH2-CH2-CH2-) is particularly preferred. Divalent alkylene groups starting from a chain length of 3 C atoms may be branched. Branched divalent C3-C 20 Examples of alkylene groups include (-CH2-CH(CH3)-) and (-CH2-CH(CH3)-CH2-).

[0034] In an additional particularly preferred embodiment, the structural unit of the formula (Si-amino) represents a repeat unit in the amino-functionalized silicone polymer (a1), such that the silicone polymer comprises a plurality of structural units of the formula (Si-amino).

[0035] Below, particularly suitable amino-functionalized silicone polymers (a1) having at least one secondary amino group are mentioned.

[0036] Formula (Si-I) and Formula (Si-II): [ka] Dyeings with the highest colour strength were obtained when an agent comprising at least one amino-functionalised silicone polymer (a1) containing structural units of the formula:

[0037] In an additional explicitly very particularly preferred embodiment, the agent according to the invention comprises a compound represented by the formula (Si-I) and the formula (Si-II): [ka] The composition is characterized in that it comprises at least one amino-functionalized silicone polymer (a1) which comprises structural units of the formula:

[0038] Corresponding amino-functionalized silicone polymers having structural units (Si-I) and (Si-II) are, for example, products DC 2-8566 or Dowsil 2-8566 Amino Fluid available from Dow Chemical Company, which have the name "Siloxane and Silicone, 3-[(2-aminoethyl)amino]-2-methylpropyl Me, di-Me-siloxane" and CAS number 106842-44-8. Another amino-functionalized silicone polymer having structural units (Si-I) and (Si-II) is, for example, DOWSIL AP-8568 Amino Fluid, also available from Dow Chemical Company.

[0039] In another preferred embodiment, the agent according to the invention has the formula (Si-III): [ka] [In the formula, m and n are numbers chosen so that the sum (n+m) is in the range of 1 to 1000; n is a number ranging from 0 to 999, and m is a number ranging from 1 to 1000, R1, R2 and R3 are the same or different and represent a hydroxyl group or a C1-4 alkoxy group; At least one of the R1 to R3 groups represents a hydroxyl group. The composition is characterized in that it comprises at least one amino-functionalized silicone polymer (a1) of the formula:

[0040] A preferred additional agent according to the present invention has the formula (Si-IV): [ka] [In the formula, p and q are numbers chosen so that the sum (p+q) is in the range 1 to 1000, p is a number in the range 0 to 999, and q is a number in the range 1 to 1000, R1 and R2 are different and represent a hydroxy group or a C1-4 alkoxy group, and at least one of the groups R1 to R2 represents a hydroxy group. The composition is characterized by the inclusion of at least one amino-functionalized silicone polymer (a1) of the formula:

[0041] Silicones of formula (Si-III) and (Si-IV) differ by the portion of the Si atom that bears a nitrogen-containing group. In formula (Si-III), R2 represents a hydroxyl group or a C1-4 alkoxy group, while the residue in formula (Si-IV) is a methyl group. The individual Si moieties represented by the subscripts m and n or p and q do not have to be present as blocks; instead, the individual units can be distributed randomly, i.e., in formula (Si-III) and (Si-IV), each R1-Si(CH3)2 group does not necessarily have to be bonded to a -[O-Si(CH3)2] moiety.

[0042] Formula (Si-V): [ka] [In the formula, A represents a -OH, -O-Si(CH3)3, -O-Si(CH3)2OH, or -O-Si(CH3)2OCH3 group; D represents a -H, -Si(CH3)3, -Si(CH3)2OH, or -Si(CH3)2OCH3 group; b, n, and c represent integers between 0 and 1000. (however, n>0 and b+c>0 At least one of the following conditions is satisfied: A=-OH or D=-H (Provided that Agents according to the invention which comprise at least one amino-functionalized silicone polymer (a1) of the formula: have also proven to be particularly effective in terms of the desired effect.

[0043] In the above formula (Si-V), the individual siloxane units having the subscripts b, c and n are randomly distributed, ie, they are not necessarily block copolymers.

[0044] The agent (a) has the formula (Si-VI): M(R a Q b SiO (4-a-b) / 2)x (R c SiO (4-c) / 2)y M (Si-VI) [wherein R is a hydrocarbon or a hydrocarbon group having 1 to about 6 carbon atoms, and Q is a group represented by the general formula -R 1 HZ (in the formula, R 1is a divalent linking group bonded to a hydrogen atom and to a group Z, and is composed of carbon and hydrogen atoms, carbon, hydrogen and oxygen atoms, or carbon, hydrogen and nitrogen atoms, and Z is an organic, amino functional group containing at least one amino functional group; "a" has a value ranging from about 0 to about 2, "b" has a value ranging from about 1 to about 3, "a" + "b" is 3 or less, "c" is a number ranging from about 1 to about 3, x is a number ranging from 1 to about 2,000, preferably from about 3 to about 50, and most preferably from about 3 to about 25, y is a number ranging from about 20 to about 10,000, preferably from about 125 to about 10,000, and most preferably from about 150 to about 1,000, and M is a suitable silicone end group as known in the art, preferably trimethylsiloxy. Non-limiting examples of groups represented by R include alkyl groups such as methyl, ethyl, propyl, isopropyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, isohexyl, and the like; alkenyl groups such as vinyl, halovinyl, alkylvinyl, allyl, haloallyl, and alkylallyl; cycloalkyl groups such as cyclobutyl, cyclopentyl, cyclohexyl, and the like; phenyl groups; benzyl groups; halohydrocarbon groups such as 3-chloropropyl, 4-bromobutyl, 3,3,3-trifluoropropyl, chlorocyclohexyl, bromophenyl, chlorophenyl, and the like; and sulfur-containing groups such as mercaptoethyl, mercaptopropyl, mercaptohexyl, mercaptophenyl, and the like; R is preferably an alkyl group containing from 1 to about 6 carbon atoms, and most preferably R is methyl. 1 Examples of the aryl groups include methylene, ethylene, propylene, hexamethylene, decamethylene, -CH2CH(CH3)CH2-, phenylene, naphthylene, -CH2CH2SCH2CH2-, -CH2CH2OCH2-, -OCH2CH2-, -OCH2CH2CH2-, -CH2CH(CH3)C(O)OCH2-, -(CH2)3C(O)OCH2CH2-, -CH4C6H4-, -C6H4CH2C6H4-; and -(CH2)3C(O)SCH2CH2-. The silicone composition may also include one or more different amino-functionalized silicone polymers represented by the formula:

[0045] Z is an organic amino functional group containing at least one functional amino group. A possible formula for Z is NH(CH2) z NH2, where z is 1 or greater. Another possible formula for Z is -NH(CH2) z (CH2) zz NH, where both z and zz are independently 1 or greater, and the structure includes a diamino ring structure such as piperazinyl. Z is most preferably a -NHCH2CH2NH2 group. Another possible formula for Z is N(CH2) z (CH2) zz NX2 or -NX2, where each X in X2 is independently selected from the group consisting of hydrogen and an alkyl group having 1 to 12 carbon atoms, and zz is 0.

[0046] Q is most preferably a polar, amino functional group of formula -CH2CH2CH2NHCH2CH2NH2, where "a" has a value ranging from about 0 to about 2, "b" has a value ranging from about 2 to about 3, "a" + "b" is 3 or less, and "c" is a number ranging from about 1 to about 3. a Q b SiO (4-a-b) / 2 Units and R c SiO (4-c) / 2 The molar ratio of units ranges from about 1:2 to about 1:65, preferably from about 1:5 to about 1:65, and most preferably from about 1:15 to about 1:20. When one or more silicones of the above formula are used, the various variable substituents in the above formula can be different for the various silicone components present in the silicone mixture.

[0047] Within the scope of another preferred embodiment, the agent according to the invention has the formula (Si-VII): R' a G 3-a -Si(OSiG2) n -(OSiG b R' 2-b ) m -O-SiG 3-a -R' a (Si-VII) [In the formula, ·G is -H, phenyl group, -OH, -O-CH3, -CH3, -O-CH2CH3, -CH2CH3, -O-CH2CH2CH3, -CH2CH2CH3, -O-CH(CH3)2, -CH(CH3)2, -O-CH2CH2CH 2CH3, -CH2CH2CH2CH3, -O-CH2CH(CH3)2, -CH2CH(CH3)2, -O-CH(CH3)CH2CH3, -CH(CH3)CH2CH3, -OC(CH3)3, or -C(CH3)3; a stands for a number between 0 and 3, especially 0; · b stands for a number between 0 and 1, especially 1; m and n are numbers whose sum (m+n) is between 1 and 2000, preferably between 50 and 150, n preferably having a value between 0 and 1999, in particular between 49 and 149, and m preferably having a value between 1 and 2000, in particular between 1 and 10; R' is a monovalent radical selected from the following: -QN(R”)-CH2-CH2-N(R”)2 -QN(R”)2 -QN + (R”)3A - -QN + H(R”)2A - -QN + H2(R”)A - -QN(R”)-CH2-CH2-N + R”H2A - (wherein each Q represents a chemical bond, -CH-, -CH-CH-, -CHCHCHCH-, -C(CH)-, -CHCHCHCHCH-, -CHC(CH)-, or -CH(CH)CHCH-; R″ is selected from the group consisting of -H, -phenyl, -benzyl, and -CH2-CH(CH3)Ph. 20and A represents an anion preferably selected from chloride, bromide, iodide or methosulfate, and the like, preferably -CH, -CHCH, -CHCHCH, -CH(CH), -CHCHCHCHH, -CH(CH), -CHCHCHCHH, -CH(CH)CHCH, -C(CH), and A represents an anion preferably selected from chloride, bromide, iodide or methosulfate. The present invention is characterized in that it comprises at least one amino-functionalized silicone polymer of the formula:

[0048] In another preferred embodiment, the agent according to the invention has the formula (Si-VIIa): [ka] [In the formula, m and n are numbers whose sum (m+n) is 1 to 2,000, preferably 50 to 150, n is preferably a value of 0 to 1,999, particularly 49 to 149, and m is preferably a value of 1 to 2,000, particularly 1 to 10] The composition is characterized in that it comprises at least one amino-functionalized silicone polymer (a1) of the formula:

[0049] These silicones are named according to the INCI name as trimethylsilylamodimethicone.

[0050] In another preferred embodiment, the agent according to the invention has the formula (Si-VIIb): [ka] [wherein R represents an -OH, -O-CH3 or -CH3 group; m, n1 and n2 are numbers such that the sum (m+n1+n2) is between 1 and 2,000, preferably between 50 and 150; the sum (n1+n2) preferably has a value of 0 to 1,999, in particular 49 to 149; and m preferably has a value of 1 to 2,000, in particular 1 to 10] The present invention is characterized in that it comprises at least one amino-functionalized silicone polymer of the formula:

[0051] According to the INCI name, these amino-functionalized silicone polymers are called amodimethicones.

[0052] Regardless of which amino-functionalized silicone is used, the agent according to the present invention preferably comprises an amino-functionalized silicone polymer (a1) with an amine value of more than 0.25 meq / g, preferably more than 0.3 meq / g, in particular more than 0.4 meq / g. The amine value here represents the milliequivalent of amine per gram of amino-functionalized silicone. Said value can be determined by titration and may be expressed in mgKOH / g.

[0053] Additionally, agents containing specific 4-morpholinomethyl substituted silicone polymers (a1) are also suitable. These amino-functionalized silicone polymers are represented by the formulas (Si-VIII) and (Si-IX): [ka] Contains structural units.

[0054] The corresponding 4-morpholinomethyl substituted silicone polymer is shown below.

[0055] A preferred amino-functionalized silicone polymer is known under the name amodimethicone / morpholinomethylsilsesquioxane copolymer and is commercially available in the form of the Wacker raw material Belsil ADM 8301 E.

[0056] For example, 4-morpholinomethyl substituted silicones include those of the formulae (Si-VIII), (Si-IX) and (Si-X): [ka] [In the formula, R1 represents -CH3, -OH, -OCH3, -O-CH2CH3, -O-CH2CH2CH3, or -O-CH(CH3)2; R2 represents -CH3, -OH, or -OCH3. Silicones having the structural units:

[0057] Particularly preferred agents according to the invention are those of the formula (Si-XI): [ka] [In the formula, R1 represents -CH3, -OH, -OCH3, -O-CH2CH3, -O-CH2CH2CH3 or -O-CH(CH3)2; R2 represents -CH3, -OH, or -OCH3; B represents a -OH, -O-Si(CH3)3, -O-Si(CH3)2OH, or -O-Si(CH3)2OCH3 group; D represents a -H, -Si(CH3)3, -Si(CH3)2OH, or -Si(CH3)2OCH3 group; a, b, and c each independently represent an integer between 0 and 1,000 (provided that a+b+c>0); m and n each independently represent an integer between 1 and 1,000 (provided that At least one of the following conditions is satisfied: B=-OH or D=-H. (Provided that the units a, b, c, m and n are distributed randomly or in blocks within the molecule). The silicone comprises at least one 4-morpholinomethyl substituted silicone.

[0058] Structural formula (Si-XI) is intended to show that the siloxane groups n and m do not necessarily have to be directly bonded to the end groups B or D. Instead, in preferred formulas (Si-VI), a>0 or b>0, and in particularly preferred formulas (Si-VI), a>0 and c>0; i.e., the end groups B or D are preferably bonded to dimethylsiloxy groups. Also in formula (Si-VI), the siloxane units a, b, c, m and n are preferably randomly distributed.

[0059] The silicones of formula (Si-VI) used according to the invention are trimethylsilyl-terminated (D or B=-Si(CH3)3), but may also be dimethylsilylhydroxy-terminated at both ends or dimethylsilylhydroxy- and dimethylsilylmethoxy-terminated at one end. In the context of the present invention, silicones that are particularly preferably used are selected from the following silicones: B=-O-Si(CH3)2OH and D=-Si(CH3)3 B=-O-Si(CH3)2OH and D=-Si(CH3)2OH B=-O-Si(CH3)2OH and D=-Si(CH3)2OCH3 B=-O-Si(CH3)3 and D=-Si(CH3)2OH B=-O-Si(CH3)2OCH3 and D=-Si(CH3)2OH These silicones significantly improve the properties of hair treated with the agent according to the invention and provide significantly improved protection during oxidative treatments.

[0060] It has been found to be particularly advantageous if the agent according to the invention comprises a specific range of amounts of amino-functionalized silicone polymer (a1). Particularly good results have been obtained if the agent comprises one or more amino-functionalized silicone polymers (a1) in a total amount of 0.1-8.0% by weight, preferably 0.2-5.0% by weight, more preferably 0.3-3.0% by weight, very particularly preferably 0.4-2.5% by weight, based on the total weight of the agent.

[0061] Within the scope of another particularly preferred embodiment, the agent according to the invention is characterized in that it comprises one or more amino-functionalized silicone polymers (a1) in a total amount of 0.1 to 8.0% by weight, preferably 0.2 to 5.0% by weight, more preferably 0.3 to 3.0% by weight and very particularly preferably 0.4 to 2.5% by weight, based on the total weight of the agent.

[0062] Platelet-type metallic pigments (a2) As a second essential component, the agent according to the invention comprises at least one platelet-type metallic pigment (a2).

[0063] Pigments in the sense of the present invention are understood to mean dye compounds that have a solubility in water at 25°C of less than 0.5 g / L, preferably less than 0.1 g / L, even more preferably less than 0.05 g / L. For example, the solubility in water can be determined using the method described below: 0.5 g of pigment are weighed into a beaker. A stirring bar is added. Then 1 liter of distilled water is added. The mixture is heated to 25°C with stirring with a magnetic stirrer for 1 hour. If after this period undissolved components of the pigment are visible in the mixture, the solubility of the pigment is less than 0.5 g / L. If the pigment-water mixture is finely dispersed and the pigment strength is so high that it cannot be visually assessed, the mixture is filtered. If some of the undissolved pigment remains on the filter paper, the solubility of the pigment is less than 0.5 g / L.

[0064] Metallic pigments are understood to mean pigments that contain at least one metal and / or at least one metal alloy. As metals, any metal suitable for metallic luster pigments is suitable. Such metals are, inter alia, iron and steel, for example platinum, zinc, chromium and molybdenum. Preferred metals are aluminum, copper, silver and gold. Aluminum is very particularly preferred. The metallic pigments according to the invention can also contain mixtures of metals that can be contained in the pigment, for example, in the form of corresponding alloys. Suitable alloys are, for example, aluminum bronze and brass.

[0065] Metals in the sense of the present invention are the corresponding elements referred to in this case having the oxidation state 0, i.e. metal oxides such as aluminum oxide, iron oxide, zinc oxide or copper oxide are expressly not to be understood as metals.

[0066] In a further very particularly preferred embodiment, the agent according to the invention comprises (a2) at least one platelet-type metallic pigment comprising at least one metal from the group consisting of aluminum, copper, silver, gold, platinum, zinc, chromium, molybdenum and iron, particularly preferably aluminum; The present invention is characterized by comprising:

[0067] In a further very particularly preferred embodiment, the agent according to the invention (a2) at least one platelet-type metallic pigment containing aluminum The present invention is characterized by comprising:

[0068] In a further specifically very particularly preferred embodiment, the agent according to the invention comprises (a2) at least one platelet-type metallic pigment, which is at least partially composed of a metal from the group consisting of aluminum, copper, silver, gold, platinum, zinc, chromium, molybdenum and iron, particularly preferably aluminum; The present invention is characterized by comprising:

[0069] In a further specifically very particularly preferred embodiment, the agent according to the invention comprises (a2) at least one platelet-type metallic pigment, which is at least partially composed of an elemental metal from the group consisting of aluminum, copper, silver, gold, platinum, zinc, chromium, molybdenum and iron, very particularly preferably aluminum. The present invention is characterized by comprising:

[0070] The metallic pigment according to the present invention is of platelet type. Platelet is understood to mean a three-dimensional body of regular or irregular shape, whose width and depth are greater dimensions than its thickness. The average dimension is applied as the measuring point for measuring the width, depth and thickness in each case. Alternatively, the platelet type component of the metallic pigment is also called substrate plate.

[0071] Incident light is reflected from a mirror towards the platelet-shaped surface of these metallic pigments, and the optical effect is based on the orientation of the platelets parallel to the surface of the surrounding system, producing a metallic effect to the observer.

[0072] The platelet-type metallic pigments used in the staining agent of the present invention are present in the form of a number of substrate plates, for example, aluminum platelet pigments are pigments consisting of a number of substrate plates that contain aluminum or are at least partially composed of elemental aluminum.

[0073] The platelet-type metallic pigment according to the invention preferably has a metal element content of at least 50% by weight, preferably at least 60% by weight, more preferably at least 70% by weight, even more preferably at least 80% by weight, even more preferably at least 90% by weight, in each case based on the weight of the metallic pigment. If the platelet-type metallic pigment is coated, the above weight data refers to the weight of the uncoated metallic pigment. Within the meaning of the present invention, the aforementioned content of elemental metals is understood to mean the part of the respective metal present in the alloy.

[0074] The substrate plate preferably has a monolithic structure. Monolithic in this context means that it is made of a single self-contained unit without cracks, stratification or inclusions, although structural variations may occur within the substrate plate. The substrate plate is preferably made homogeneously, i.e., there is no concentration gradient within the plate. In particular, it is particularly preferred that the substrate plate is not made of layers and does not have particles dispersed therein.

[0075] The size of the substrate plate can be adapted to the respective application, in particular the desired effect on keratinous materials. The pigments particularly preferably have an average pigment diameter (D50) in the range of from 0.5 μm (0.5 microns) to about 1 mm (1 millimeter), preferably from 3 μm (3 microns) to about 500 μm (500 microns), even more preferably from 5 μm (5 microns) to 100 μm (100 microns) and very particularly preferably from 8 μm (8 microns) to 50 μm (50 microns).

[0076] In another particularly preferred embodiment, the agent according to the invention comprises (a2) at least one platelet-type metallic pigment having an average pigment diameter (D50) of 0.5 μm to 1 mm, preferably 3 μm to 500 μm, more preferably 5 μm to 100 μm, very particularly preferably 8 μm to 50 μm The present invention is characterized by comprising:

[0077] The size distribution of the particles can be determined, for example, by laser granulometry. In this method, the particles can be measured in the form of a powder. The scattering of the irradiated laser light is detected in different spatial directions and evaluated according to the Fraunhofer diffraction theory. In this case, the particles are treated mathematically as spheres. The determined diameters therefore always refer to the equivalent spherical diameters determined over all spatial directions, regardless of the actual shape of the particles. The evaluation of the diffraction data is based on a model that targets the equivalent spherical diameter. Therefore, absolute values ​​are not obtained, but the measured diameters have proven to be reliable relative values ​​in describing the size characteristics of platelet-type metallic pigments. The size distribution is determined calculated in the form of a volume average with respect to the equivalent spherical diameter. This volume-averaged size distribution can be expressed as a cumulative frequency distribution. For simplicity, the cumulative frequency distribution is characterized by various characteristic values, such as, for example, the D50 value. The term "mean pigment diameter" or "D50" in the sense of the present invention means that 50% of the aforementioned particle size distribution, volume averaged by laser granulometry, is below the stated value and 50% of the aforementioned particle size distribution, volume averaged by laser granulometry, is above the stated value. The measurement can be carried out, for example, using a HELOS particle size analyzer from Sympatec GmbH, Clausthal-Zellerfeld, Germany. Unless otherwise stated, the D50 values ​​were measured using a Sympatec Helos type device with Quixel wet dispersion. To prepare the samples, the samples to be investigated were pre-dispersed in isopropanol for 3 minutes.

[0078] The average thickness (h50) of the metallic pigments according to the invention preferably ranges from 1 nm (1 nanometer) to about 500 nm (nanometers), preferably from about 1 nm (1 nanometer) to about 300 mm (1.5 mm), even more preferably from about 1 nm to 100 nm, very particularly preferably from 5 nm to 70 nm. The term "average thickness" or "h50" in the sense of the present invention relates to the arithmetic mean of the thicknesses of at least 100 metallic pigments by scanning electron microscopy (SEM). Here, the best possible orientation of the plates in the application medium must be ensured. For this purpose, the metallic pigments can be pretreated beforehand using suitable additives. The cured lacquer is then polished and, after conventional sample preparation, the cross-sections are observed in the SEM. Only particles with good orientation are selected for counting. Here, the average thickness or h50 value relates to the uncoated metallic pigment.

[0079] The size-thickness ratio, also called aspect ratio and expressed as the ratio of the average size to the average thickness, is preferably at least 80, preferably at least 200, more preferably at least 500, particularly preferably more than 750.

[0080] In the course of research leading to the present invention, it was found that the use of metallic pigments from the group consisting of vacuum deposition pigments (VMP) in the dyeing agent according to the invention leads to particularly good color results on keratin substances or keratin fibers. Thus, it was shown that the combination of VMP pigments (a2) and aminosilicones (a1) not only dyes keratin substances in a particularly long-lasting manner, but that these dyes have a particularly high covering power and give a particularly uniform color result. Surprisingly, the use of platelet-type pigments (a2), in particular VMP pigments and aminosilicones (a1), also results in dyeing materials with a particularly soft feel and pleasant hair feel.

[0081] Vacuum deposition pigments (VMP) are extremely thin metal plates that are produced by a specific method called physical vapor deposition (PVD). These pigments have a uniform and smooth surface, do not peel off and provide an optical micromirror effect.

[0082] Vacuum deposition pigments are characterized by extremely high gloss, exceptional covering power and unique optical properties. Due to their small thickness (approximately 5-70 nm) and very smooth surface, they tend to stick very firmly to the substrate after application. In the case of very smooth substrates, this results in an almost mirror-like appearance. Vacuum deposition pigments (VMP) can be obtained, for example, by peeling off the metal or metal alloy of the corresponding coated film. Substrate plates with pigments metallized in vacuum are also called VMP substrate plates in the context of this application. VMP substrate plates of aluminum can be obtained, for example, by peeling off the aluminum from a metallized film.

[0083] The vacuum deposition substrate plate preferably has an average thickness (h50) of at most 70 nm, preferably less than 50 nm, particularly preferably at most 35 nm, particularly preferably at most 20 nm. The average thickness of the substrate plate is at least 1 nm, preferably at least 2.5 nm, particularly preferably at least 5 nm, for example at least 10 nm. Preferred ranges for the thickness of the substrate plate are 2.5-70 nm, 5-50 nm, 10-35 nm, 2.5-30 nm, and 5-25 nm. Preferably, each substrate plate has a thickness as uniform as possible. Due to the low thickness of the substrate plate, the pigment has a particularly high covering power.

[0084] Pigments based on metal layers produced by the PVD method (physical vapor deposition) are described in more detail, for example, in US Pat. No. 2,839,378 "Method of making metal flakes." There, the production of specular pigments with very thin layer thicknesses, which are deposited on a substrate provided with a "release layer", is described. After application of the metal layer and peeling off the film, the pigments are ground to the desired particle size by mechanical stress. The process of producing metallic pigments with a thickness of 35-45 nm by vapor deposition is described in more detail in US Pat. No. 4,321,087, which includes the application of a release coat, a metallization process, a peeling process in a solvent bath, concentrating the particles and ultrasonic grinding to the desired pigment size.

[0085] In another particularly preferred embodiment, the agent according to the invention comprises (a2) at least one vacuum-deposited pigment as a platelet-type metallic pigment; The present invention is characterized by comprising:

[0086] In another particularly preferred embodiment, the agent according to the invention comprises (a2) at least one vacuum-deposited pigment, as a platelet-type metallic pigment, which is at least partially composed of aluminum The present invention is characterized by comprising:

[0087] When uncoated metallic pigments were used as metallic pigments (a2), dyeings with particularly good covering power and good hair feel were obtained.

[0088] In a further very particularly preferred embodiment, the agent according to the invention comprises (a2) at least one uncoated platelet-type metallic pigment The present invention is characterized by comprising:

[0089] In a further specifically very particularly preferred embodiment, the agent according to the invention comprises (a2) at least one uncoated platelet-type aluminum pigment; The present invention is characterized by comprising:

[0090] Vacuum deposition pigments are commercially available from a variety of suppliers, for example Schlenk vakuum offers metallized pigments under the brand names Decometal® and Alegrace®. TIFF2024527151000013.tif36161

[0091] Further examples are Metalure® (manufactured by Avery Dennison and sold by ECKART), or Metasheen® (Ciba).

[0092] However, in the context of further embodiments, the substrate plate may be passivated from the metal or metal alloy, for example by anodization (oxide layer) or chromate treatment.

[0093] Uncoated VMP substrate plates, especially those made of metals or metal alloys, are highly reflective of the incident light, producing a light-dark flop but no color impression.

[0094] The color impression can be produced, for example, by light interference effects. Such pigments can be based on at least a single coated substrate plate. They exhibit interference effects by superimposing differently refracted and reflected light rays.

[0095] Therefore, pigments based on coated VMP substrate plates may also be suitable. The substrate plate preferably has at least one coating B of a high refractive index metal oxide with a coating thickness of at least 50 nm. Coating A is preferably still present between coating B and the surface of the substrate plate. Optionally, another coating C, different from the underlayer B, is on layer B.

[0096] Suitable materials for coatings A, B and C are all substances that can be applied in the form of a film and permanently to the substrate plate and, in the case of coatings A and B, have the required optical properties. In general, it is sufficient to coat only a part of the surface of the substrate plate to obtain a pigment with a gloss effect. Thus, for example, only the upper and / or lower surface of the substrate plate can be coated, the side surfaces being omitted. Preferably, the entire surface of the substrate plate, optionally passivated, including the side surfaces, is covered by coating B. Thus, the substrate plate is completely enveloped by coating B. This improves the optical properties of the pigment and increases its mechanical and chemical elasticity. The above also applies to layer A and, if layer C is present, preferably also to layer C.

[0097] Although there can always be multiple coatings A, B and / or C, it is preferred that each coated substrate plate has only one coating A, B and, if present, C.

[0098] Coating B is composed of at least one high refractive index metal oxide. The high refractive index material has a refractive index of at least 1.9, preferably at least 2.0, particularly preferably at least 2.4. Coating B preferably comprises at least 95% by weight, particularly preferably at least 99% by weight, of the high refractive index metal oxide.

[0099] Coating B has a thickness of at least 50 nm. The thickness of coating B is preferably not more than 400 nm, particularly preferably at most 300 nm.

[0100] High 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 titanium oxynitride and mixtures with titanium nitride), vanadium(V) oxide (orange), and mixtures thereof. Colorless high refractive index oxides such as titanium dioxide and / or zirconium oxide are also suitable.

[0101] Coating B may contain preferably 0.001 to 5% by weight, particularly preferably 0.01 to 1% by weight, of a selectively absorbing dye, each based on the total amount of coating B. Organic or inorganic dyes which can be stably incorporated into the metal oxide coating are suitable.

[0102] Coating A preferably comprises at least one metal oxide and / or metal oxide hydrate with a low refractive index. Preferably, coating A comprises at least 95% by weight, particularly preferably at least 99% by weight, of a low refractive index metal oxide (hydrate). The low refractive index material has a refractive index of at most 1.8, preferably at most 1.6.

[0103] Suitable low refractive index metal oxides for coating A include, for example, silicon dioxide, silicon oxide hydrate, aluminum oxide, aluminum oxide hydrate, boron oxide, germanium oxide, manganese oxide, magnesium oxide and mixtures thereof, with silicon dioxide being preferred. Coating A preferably has a thickness of 1 to 100 nm, particularly preferably 5 to 50 nm, and particularly preferably 5 to 20 nm.

[0104] The distance between the surface of the substrate plate and the inner surface of coating B is preferably at most 100 nm, particularly preferably at most 50 nm, particularly preferably at most 20 nm. The thickness of coating A and thus the distance between the surface of the substrate plate and coating B is within the above ranges, ensuring that the pigment has high covering power.

[0105] If the pigment has only one layer A based on a VMP substrate plate, it is preferred that the pigment has a VMP substrate plate made of aluminum and a layer A of silicon dioxide. If the pigment has layers A and B based on a VMP substrate plate, it is preferred that the pigment has a VMP substrate plate made of aluminum, a layer A of silicon dioxide and a layer B of iron oxide.

[0106] According to a further embodiment, the pigment has a further coating C consisting of a metal oxide (hydrate) 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, chromium(III) oxide. Silicon dioxide is preferred.

[0107] The thickness of the coating C is preferably 10 to 500 nm, particularly preferably 50 to 300 nm. By providing a coating C based on TiO2, for example, better interference can be achieved while maintaining a high covering power.

[0108] Layers A and C are in particular for corrosion protection and chemical and physical stabilization. It is particularly preferred that layers A and C comprise silicon dioxide or aluminum oxide, which are applied by a sol-gel process. This method comprises dispersing an uncoated VMP substrate plate or a VMP substrate plate already coated with layers A and / or B in a solution of a metal alkoxide, such as tetraethyl orthosilicate or aluminum triisopropanolate (usually an organic solvent or a mixture of an organic solvent and water containing at least 50% by weight of an organic solvent, such as an alcohol having 1 to 4 carbon atoms), adding a weak base or acid to hydrolyze the metal alkoxide and form a film of the metal oxide on the (coated) substrate plate surface.

[0109] Layer B can be formed, for example, by hydrolysis of one or more organometallic compounds and / or by precipitation of one or more dissolved metal salts and optional subsequent post-treatment (e.g., converting the formed hydroxide-containing layer into an oxide layer by tempering).

[0110] Each of coatings A, B and / or C may be composed of a mixture of two or more metal oxides (hydrates), however, each of the coatings is preferably composed of one metal oxide (hydrate).

[0111] The pigments based on coated VMP substrate plates preferably have a thickness of 70-500 nm, particularly preferably 100-400 nm, particularly preferably 150-320 nm, for example 180-290 nm. Due to the low thickness of the substrate plate, the pigments have a particularly high covering power. The low thickness of the coated substrate plate is achieved in particular because of the low thickness of the uncoated substrate plate, but also because the thicknesses of the coatings A and, if present, C, are set to the smallest possible values. The thickness of the coating B determines the color impression of the pigment.

[0112] The adhesion and abrasion resistance of pigments based on coated VMP substrate plates on keratinous materials can be significantly increased by further modifying the outermost layer with organic compounds such as silanes, phosphates, titanates, borates, or carboxylic acids, depending on the structure of layer A, B, or C. The organic compounds are bonded to the surface of the outermost layer, preferably the metal oxide-containing layer A, B, or C. The outermost layer refers to the layer spatially furthest away from the VMP substrate plate. The organic compounds are preferably functional silane compounds that can be bonded to the metal oxide-containing layer A, B, or C. These can be monofunctional or bifunctional compounds. Examples of bifunctional organic compounds include methacryloxypropenyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-acryloxyethyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane, 2-acryloxyethyltriethoxysilane, 3-methacryloxypropyltris(methoxyethoxy)silane, 3-methacryloxypropyltris(butoxyethoxy)silane, 3-methacryloxypropyltris( Examples of suitable silanes include 3-propoxy) silane, 3-methacryloxypropyl tris(butoxy) silane, 3-acryloxypropyl tris(methoxyethoxy) silane, 3-acryloxypropyl tris(butoxyethoxy) silane, 3-acryloxypropyl tris(butoxy) silane, vinyl trimethoxy silane, vinyl triethoxy silane, vinyl ethyl dichloro silane, vinyl methyl diacetoxy silane, vinyl methyl dichloro silane, vinyl methyl diethoxy silane, vinyl triacetoxy silane, vinyl trichloro silane, phenyl vinyl diethoxy silane, or phenyl allyl dichloro silane. In addition, modification with monofunctional silanes, in particular alkyl or aryl silanes, can be carried out. This has only one functional group that can be covalently bonded to the surface of the pigment based on the coated VMP substrate plate (i.e. the outermost metal oxide-containing layer) or to the metal surface if the coverage is not complete. The hydrocarbon functional group of the silane faces away from the pigment.Depending on the type and nature of the hydrocarbon functional group of the silane, different degrees of hydrophobicity of the pigment can be achieved. Examples of such silanes are hexadecyltrimethoxysilane, propyltrimethoxysilane, etc. Particularly preferably, pigments based on silica-coated aluminum substrate plates are surface-modified with monofunctional silanes. Octyltrimethoxysilane, octyltriethoxysilane, hexadecyltrimethoxysilane, and hexadecyltriethoxysilane are particularly preferred. As a result of the change in surface properties / hydrophobicity, improved adhesion, abrasion resistance, and orientation during application can be achieved.

[0113] The amount of platelet-type metallic pigment (a2) used can be selected depending on the desired color effect. Particularly good results have been obtained when the agent contains one or more metallic pigments (a2) in a total amount of 0.01 to 10% by weight, preferably 0.1 to 8% by weight, more preferably 0.2 to 6% by weight, particularly preferably 0.4 to 5.5% by weight, based on the total weight of the agent.

[0114] In another very particularly preferred embodiment, the agent according to the invention is characterized in that it comprises one or more platelet-type metallic pigments (a2) in a total amount of 0.01 to 10% by weight, preferably 0.1 to 8% by weight, more preferably 0.2 to 6% by weight and very particularly preferably 0.4 to 5.5% by weight, based on the total weight of the agent.

[0115] (a3) a further pigment different from (a2); The dye according to the invention may further comprise one or more further pigments (a3) ​​different from the platelet-type metallic pigment (a2). Suitable additional color pigments (a3) ​​may be of inorganic and / or organic origin.

[0116] The preferred color pigments are selected from synthetic or natural inorganic pigments. Naturally occurring inorganic color pigments can be produced, for example, from chalk, ocher, umbra, green earth, burnt sienna, or graphite. In addition, black pigments, for example, iron oxide black, chromatic pigments, for example, ultramarine and iron oxide red, as well as fluorescent and phosphorescent pigments, can also be used as inorganic color pigments.

[0117] Particularly suitable are 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. Particularly preferred color pigments are black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and brown iron oxide (CI 77491), manganese violet (CI 77742), ultramarine (sodium aluminum sulfosilicate, Cl 77007, Pigment Blue 29), chromium oxide hydrate (CI 77289), iron blue (ferric ferrocyanide, Cl 77510) and / or carmine (cochineal).

[0118] Similarly, the color pigments according to the present invention are particularly preferred colored pearlescent pigments. They are usually based on mica and can be coated with one or more metal oxides. Micas are phyllosilicates. The most important representatives of these silicates are muscovite, phlogopite, paragonite, biotite, lepidolite, and margarite. In order to produce pearlescent pigments in combination with metal oxides, mica, mainly muscovite or phlogopite, is coated with metal oxide.

[0119] 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 coated with one or more of the aforementioned metal oxides. The color of the respective pigment can be varied by changing the layer thickness of the metal oxide.

[0120] In another preferred embodiment, the agent according to the invention is characterized in that it further comprises at least one inorganic pigment (a3), which is different from the platelet-type metallic pigment (a2) and is preferably selected from the group consisting of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, complex metal cyanides, metal sulfates and / or colored pigments based on mica coated with at least one metal oxide and / or metal oxychloride.

[0121] Particular preference is therefore given to dyes for keratin materials, in particular human hair, which comprise: (a1) at least one amino-functionalized silicone polymer, and (a2) at least one platelet-type metallic pigment, and (a3) at least one inorganic pigment different from the platelet-type metallic pigment (a2).

[0122] In another preferred embodiment, the agent according to the invention is characterized in that it comprises at least one dye compound (a2) from the group consisting of pigments selected from the group consisting of titanium dioxide (CI 77891), black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and / or brown iron oxide (CI 77491, CI 77499), manganese violet (CI 77742), ultramarine (sodium aluminum sulfosilicate, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI 77289), chromium oxide (CI 77288) and / or pigments based on mica coated with one or more metal oxides from the group consisting of iron blue (ferric ferrocyanide, CI 77510).

[0123] Examples of particularly suitable colour pigments are commercially available, for example, under the trade names Rona®, Colorona®, Xirona®, Dichrona® and Timiron® from Merck, Ariabel® and Unipure® from Sensient, Prestige® from Eckart Cosmetic Colors and Sunshine® from Sunstar.

[0124] Very particularly preferred colour pigments of the trade name Colorona® are, for example: Colorona Copper, Merck, Mica, CI 77491 (Iron Oxides) Colorona Passion Orange, Merck, Mica, CI 77491 (Iron Oxides), Alumina Colorona Patina Silver, Merck, Mica, CI 77499 (Iron Oxides), CI 77891 (Titanium Dioxide) Colorona RY, Merck, CI 77891 (Titanium Dioxide), Mica, CI 75470 (Carmine) Colorona Oriental Beige, Merck, Mica, CI 77891 (Titanium Dioxide), CI 77491 (Iron Oxides) Colorona Dark Blue, Merck, Mica, Titanium Dioxide, Ferric Ferrocyanide Colorona Chameleon, Merck, CI 77491 (iron oxide), mica Colorona Aborigine Amber, Merck, Mica, CI 77499 (Iron Oxides), CI 77891 (Titanium Dioxide) Colorona Blackstar Blue, Merck, CI 77499 (iron oxide), mica Colorona Patagonian Purple, Merck, Mica, CI 77491 (Iron Oxides), CI 77891 (Titanium Dioxide), CI 77510 (Ferric Ferrocyanide) Colorona Red Brown, Merck, Mica, CI 77491 (Iron Oxides), CI 77891 (Titanium Dioxide) Colorona Russet, Merck, CI 77491 (Titanium Dioxide), Mica, CI 77891 (Iron Oxides) Colorona Imperial Red, Merck, Mica, Titanium Dioxide (CI 77891), D&C RED NO. 30 (CI 73360) Colorona Majestic Green, Merck, CI 77891 (titanium dioxide), mica, CI 77288 (chromium oxide green) Colorona Light Blue, Merck, Mica, Titanium Dioxide (CI 77891), Ferric Ferrocyanide (CI 77510) Colorona Red Gold, Merck, Mica, CI 77891 (Titanium Dioxide), CI 77491 (Iron Oxides) Colorona Gold Plus MP 25, Merck, Mica, Titanium Dioxide (CI 77891), Iron Oxide (CI 77491) Colorona Carmine Red, Merck, Mica, Titanium Dioxide, Carmine Colorona Blackstar Green, Merck, Mica, CI 77499 (Iron Oxides) Colorona Bordeaux, Merck, Mica, CI 77491 (Iron Oxides) Colorona Bronze, Merck, Mica, CI 77491 (Iron Oxides) Colorona Bronze Fine, Merck, Mica, CI 77491 (Iron Oxides) Colorona Fine Gold MP 20, Merck, Mica, CI 77891 (Titanium Dioxide), CI 77491 (Iron Oxides) Colorona Sienna Fine, Merck, CI 77491 (iron oxide), mica Colorona Sienna, Merck, Mica, CI 77491 (Iron Oxides) Colorona Precious Gold, Merck, Mica, CI 77891 (Titanium Dioxide), Silica, CI 77491 (Iron Oxides), Tin Oxide Colorona Sun Gold Sparkle MP 29, Merck, Mica, Titanium Dioxide, Iron Oxides, Mica, CI 77891, CI 77491 (EU) Colorona Mica Black, Merck, CI 77499 (iron oxides), mica, CI 77891 (titanium dioxide) Colorona Bright Gold, Merck, Mica, CI 77891 (Titanium Dioxide), CI 77491 (Iron Oxides) Colorona Blackstar Gold, Merck, Mica, CI 77499 (Iron Oxides)

[0125] Further particularly preferred colour pigments having the trade name Xirona® are, for example: Xirona Golden Sky, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide Xirona Caribbean Blue, Merck, Mica, CI 77891 (Titanium Dioxide), Silica, Tin Oxide Xirona Kiwi Rose, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide Xirona Magic Mauve, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide

[0126] Further particularly preferred colour pigments having the trade name Unipure® are, for example: Unipure Red LC 381 EM, Sensient, CI 77491 (iron oxide), silica Unipure Black LC 989 EM, Sensient, CI 77499 (Iron Oxides), Silica Unipure Yellow LC 182 EM, Sensient, CI 77492 (iron oxide), silica

[0127] In another embodiment, the agent according to the invention can also further contain one or more dye compounds (a3) ​​from the group consisting of organic pigments.

[0128] The organic pigments according to the invention are the corresponding insoluble organic dyes or colour lakes, which may be selected, for example, from the group of nitroso, nitro, azo, xanthene, anthraquinone, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, indigo, thioindide, dioxazine and / or triarylmethane compounds.

[0129] Particularly suitable organic pigments include, for example, carmine, quinacridone, phthalocyanine, sorghum, blue pigments having the color index numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100 or CI 74160, yellow pigments having the color index numbers CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000 or CI 47005, green pigments having the color index numbers CI 61565, CI 61570 or CI 74260, orange pigments having the color index numbers CI 11725, CI 15510, CI 45370 or CI 71105, and tallow pigments having the color index numbers CI 12085, CI 12120, CI 12130, CI 12140, CI 121565, CI 121570 or CI 74260. Red pigments having 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.

[0130] In another particularly preferred embodiment, the agent according to the invention is selected from the group consisting of carmine, quinacridone, phthalocyanine, sorghum, blue pigments with the color index numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100 or CI 74160, yellow pigments with the 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 the color index numbers CI 61565, CI 61570 or CI 74260, orange pigments with the color index numbers CI 11725, CI 15510, CI 45370 or CI 71105, and the 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.

[0131] Particular preference is therefore given to dyes for keratin materials, in particular human hair, which comprise: (a1) at least one amino-functionalized silicone polymer, and (a2) at least one platelet-type metallic pigment, and (a3) at least one organic pigment.

[0132] The organic pigment may be a color lake. The term color lake in the sense of the present invention is understood to mean a particle comprising a layer of absorbed dye, the unit consisting of particle and dye being insoluble under the above conditions. The particle may be an inorganic substrate, for example aluminium, silica, calcium borosilicate, calcium aluminium borosilicate or aluminium.

[0133] For example, Alizarin color lake can be used as the color lake.

[0134] Due to their excellent light and heat resistance, the use of the aforementioned pigments in the process according to the invention is very particularly preferred. It is even more preferred if the pigments used have a certain particle size. Thus, according to the invention, at least one pigment has an average particle size D of 1.0 to 50 μm, preferably 5.0 to 45 μm, preferably 10 to 40 μm, in particular 14 to 30 μm. 50 It is advantageous to have an average particle size D 50 can be determined, for example, using dynamic light scattering (DLS).

[0135] The pigment (a3) ​​is preferably used in a certain amount range in the agent.

[0136] Particularly positive results have been obtained when the agent comprises one or more pigments (a3) ​​in a total amount of 0.01 to 10.0% by weight, preferably 0.1 to 5.0% by weight, more preferably 0.2 to 2.5% by weight and particularly preferably 0.25 to 1.5% by weight, based on the total weight of the agent.

[0137] In another very particularly preferred embodiment, the agent according to the invention is characterized in that it comprises one or more pigments (a3) ​​in a total amount of 0.01 to 10.0% by weight, preferably 0.1 to 5.0% by weight, more preferably 0.2 to 2.5% by weight and particularly preferably 0.25 to 1.5% by weight, based on the total weight of the agent.

[0138] In another very particularly preferred embodiment, the agent according to the invention is characterized in that it comprises one or more inorganic pigments (a3) ​​in a total amount of 0.01 to 10.0% by weight, preferably 0.1 to 5.0% by weight, more preferably 0.2 to 2.5% by weight and particularly preferably 0.25 to 1.5% by weight, based on the total weight of the agent.

[0139] In another very particularly preferred embodiment, the agent according to the invention is characterized in that it comprises one or more organic pigments (a3) ​​in a total amount of 0.01 to 10.0% by weight, preferably 0.1 to 5.0% by weight, more preferably 0.2 to 2.5% by weight and particularly preferably 0.25 to 1.5% by weight, based on the total weight of the agent.

[0140] The degree of shade of the obtained color result can be increased by the optional use of additional inorganic or organic pigments (a3) ​​in the dyeing agent according to the invention. Surprisingly, when the platelet-type metallic pigment (a2) and further inorganic and / or organic pigments (a3) ​​are used in a certain weight ratio to one another, in addition to the color change, a sufficiently high smoothness or improvement in the hair feel is also obtained. It has been found to be particularly advantageous when the weight ratio of the total amount of platelet-type metallic pigment (a2) contained in the agent to the total amount of additional pigments (a3) ​​contained in the agent, i.e. the weight ratio (a) / (a3), is between 5.0 and 0.1, preferably between 2.5 and 0.2, more preferably between 1.5 and 0.4, very particularly preferably between 1.0 and 0.5.

[0141] Thus, in a further embodiment, very particular preference is given to (a1) at least one amino-functionalized silicone polymer, and (a2) at least one platelet-type metallic pigment, and (a3) at least one inorganic and / or organic pigment different from the platelet-type metallic pigment (a2); An agent comprising: The weight ratio of the total amount of platelet-type metallic pigments (a2) contained in the agent to the total amount of additional pigments (a3) ​​contained in the agent, i.e. the weight ratio (a) / (a3), is from 5.0 to 0.1, preferably from 2.5 to 0.2, more preferably from 1.5 to 0.4 and very particularly preferably from 1.0 to 0.5.

[0142] In a further very particularly preferred embodiment, the agent according to the invention comprises (a2) at least one platelet-type metallic pigment, and (a3) at least one inorganic and / or organic pigment different from the platelet-type metallic pigment (a2); Including, The weight ratio of the total amount of platelet-type metallic pigments (a2) contained in the agent to the total amount of additional pigments (a3) ​​contained in the agent, i.e. the weight ratio (a) / (a3), is between 5.0 and 0.1, preferably between 2.5 and 0.2, more preferably between 1.5 and 0.4 and very particularly preferably between 1.0 and 0.5.

[0143] Water content in the agent The above-mentioned agents are ready-to-use agents that can be applied to keratinous materials. The ready-to-use agents preferably have a low to medium water content. In particular, it has been found that agents containing 0.1 to 70.0% by weight, preferably 0.5 to 35.0% by weight, more preferably 1.0 to 20.0% by weight, and particularly preferably 1.5 to 7.5% by weight of water, based on the total weight of the agent, are suitable.

[0144] In another obviously very particularly preferred embodiment, the agent according to the invention is characterized in that it contains 0 to 70.0% by weight, preferably 0.1 to 35.0% by weight, more preferably 0.1 to 35.0% by weight, even more preferably 0.2 to 20.0% by weight, particularly preferably 0.3 to 7.5% by weight of water, based on the total weight of the agent.

[0145] Solvent in the agent The use of solvents in the agents according to the invention has given very good results. For this reason, the agents according to the invention can further comprise at least one solvent as an optional component.

[0146] Suitable solvents which can be used are, for example, solvents from the group consisting of poly-C1-C6-alkylene glycols, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, dipropylene glycol, ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol, phenoxyethanol and benzyl alcohol. Very particular preference is given to the use of polyethylene glycols.

[0147] In a further very particularly preferred embodiment, the agent according to the invention is characterized in that it comprises at least one solvent from the group consisting of poly-C1-C6-alkylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, dipropylene glycol, ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol, phenoxyethanol and benzyl alcohol, very particularly preferably polyethylene glycol.

[0148] Alternatively, 1,2-propylene glycol is also known as 1,2-propanediol, with CAS numbers 57-55-6 [(RS)-1,2-dihydroxypropane], 4254-14-2 [(R)-1,2-dihydroxypropane], and 4254-153 [(S)-1,2-dihydroxypropane]. Ethylene glycol is also known as 1,2-ethanediol, with CAS number 107-21-1. Glycerol is also known as 1,2,3-propanetriol, with CAS number 56-81-5. Phenoxyethanol has CAS number 122-99-6.

[0149] All of the above mentioned solvents are commercially available from a variety of chemical suppliers such as Aldrich or Fluka.

[0150] In the context of a further preferred embodiment, the agent according to the invention is characterized in that it comprises one or more solvents from the group consisting of poly-C1-C6-alkylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, dipropylene glycol, ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol, phenoxyethanol and benzyl alcohol in a total amount of 10.0 to 99.0% by weight, preferably 30.0 to 99.0% by weight, more preferably 50.0 to 99.0% by weight and very particularly preferably 70.0 to 99.0% by weight, based on the total weight of the agent.

[0151] Alkylene glycol of formula (AG) Very particularly suitable solvents are those of formula (AG): [ka] [In the formula, x represents an integer from 1 to 10000, preferably an integer from 2 to 800, more preferably an integer from 3 to 600, even more preferably an integer from 3 to 400, and very particularly preferably an integer from 4 to 200. It is an alkylene glycol.

[0152] Thus, in a further very particularly preferred embodiment, the agent according to the invention has the formula (AG): [ka] [In the formula, x represents an integer from 1 to 10000, preferably an integer from 2 to 800, more preferably an integer from 3 to 600, even more preferably an integer from 3 to 400, and very particularly preferably an integer from 4 to 200. The present invention is characterized in that it contains one or more alkylene glycols.

[0153] The alkylene glycols of formula (AG) are protic substances having at least one hydroxy group and, because of their repeating -CH2-CH2-O- units, are also called polyalkylene glycols or polyethylene glycols, as long as x has a value of at least 2. In the alkylene glycols of formula (AG), x is an integer between 1 and 10,000. In the context of the research leading to the present invention, it was found that these polyethylene glycols show a particularly favorable suitability for improving the fastness properties of the dyeing agents, on the one hand, and for optimally adjusting the viscosity of the agents, on the other hand.

[0154] Polyethylene glycols are water-soluble polymers that can be liquid or solid, depending on the length of the chain. Polyethylene glycols with molecular weights between 200 g / mol and 400 g / mol are non-volatile liquids at room temperature. PEG 600 has a melting point of 17-22 °C and a paste-like consistency. PEGs with molecular weights above 3,000 g / mol are solid materials and are commercially available as flakes or powders.

[0155] In particular, the use of low molecular weight alkylene glycols (or, respectively, polyethylene glycols) has proven to be well suited to achieving the objectives according to the invention. In the case of low molecular weight alkylene glycols (or polyethylene glycols) in the context of the present invention, x represents an integer from 1 to 100, preferably an integer from 1 to 80, more preferably an integer from 2 to 60, even more preferably an integer from 3 to 40, even more preferably an integer from 4 to 20 and very particularly preferably an integer from 6 to 15.

[0156] In the context of another very particularly preferred embodiment, the agent according to the invention has the formula (AG-1): [ka] [In the formula, x1 represents an integer from 1 to 100, preferably an integer from 1 to 80, more preferably an integer from 2 to 60, even more preferably an integer from 3 to 40, even more preferably an integer from 4 to 20, and very particularly preferably an integer from 6 to 15. The present invention is characterized in that it contains at least one alkylene glycol.

[0157] A particularly preferred low molecular weight polyethylene glycol is, for example, PEG-8. PEG-8 contains an average of 8 ethylene glycol units (x1=8), has an average molecular weight of 400 g / mol, and has a CAS number of 25322-68-3. PEG-8 is also called PEG400 and is commercially available, for example, from APS.

[0158] Further suitable low molecular weight polyethylene glycols are, for example, PEG-6, PEG-7, PEG-9 and PEG-10.

[0159] Another suitable polyethylene glycol is, for example, PEG-32. PEG-32 contains 32 ethylene glycol units (x1=32), has an average molar mass of 1,500 g / mol, and has the CAS number 25322-68-3. PEG-32 is also called PEG 1500 and is commercially available, for example, from Clariant.

[0160] Furthermore, the use of polyethylene glycols with high molecular weight has also proven suitable for achieving the objectives according to the invention.

[0161] High molecular weight polyethylene glycols in the sense of the present invention are represented by the formula (AG-2): [ka] where the exponent x2 represents an integer from 101 to 10,000.

[0162] In the case of very suitable high molecular weight polyethylene glycols, x2 represents an integer from 101 to 1,000, preferably an integer from 105 to 800, more preferably an integer from 107 to 600, even more preferably an integer from 109 to 400, and very particularly preferably an integer from 110 to 200.

[0163] In another very particularly preferred embodiment, the agent according to the invention has the formula (AG-2): [ka] [In the formula, x2 represents an integer of 101 to 1,000, preferably an integer of 105 to 800, more preferably an integer of 107 to 600, even more preferably an integer of 109 to 400, and very particularly preferably an integer of 110 to 200. The present invention is characterized in that it contains at least one alkylene glycol.

[0164] A particularly suitable high molecular weight polyethylene glycol is commercially available from National Starch Co., Ltd. (China), for example PEG 6000. PEG 6000 has a molecular weight of 6000-7500 g / mol, which corresponds to an x2 value of 136-171.

[0165] Another suitable polyethylene glycol is PEG 12000, available, for example, from CG Chemicals under the trade name Polyethylene Glycol 12000 S (or PEG 12000 S). PEG 12000 has a molecular weight of 10,500-15,000 g / mol, corresponding to an x2 value of 238-341.

[0166] Another suitable polyethylene glycol is PEG 20000, which is commercially available from Clariant under the trade name Polyglycol 20000 P or alternatively PEG-350. PEG 20000 has an average molecular weight of 20,000 g / mol, which corresponds to an x2 value of 454.

[0167] Surprisingly, it has been found that staining agents comprising both low and high molecular weight polyethylene glycols have particularly favorable application properties, since both of these agents have very good fastness properties and are optimized with regard to their rheological profile.

[0168] Within the scope of another obviously very particularly preferred embodiment, the agent according to the invention comprises ·Formula (AG-1): [ka] [In the formula, x1 represents an integer from 1 to 100, preferably an integer from 1 to 80, more preferably an integer from 2 to 60, even more preferably an integer from 3 to 40, even more preferably an integer from 4 to 20, and very particularly preferably an integer from 6 to 15. and at least one first alkylene glycol of ·Formula (AG-2): [ka] [In the formula, x2 represents an integer of 101 to 1,000, preferably an integer of 105 to 800, more preferably an integer of 107 to 600, even more preferably an integer of 109 to 400, and very particularly preferably an integer of 110 to 200. At least one second alkylene glycol The present invention is characterized by comprising:

[0169] In order to further optimize the application properties, the agent according to the invention preferably comprises alkylene glycol (AG) in a certain amount range, for example in the range of 10.0 to 99.0% by weight, preferably 30.0 to 99.0% by weight, more preferably 50.0 to 99.0% by weight and very particularly preferably 70.0 to 99.0% by weight, based on the total weight of the agent.

[0170] Within the scope of another obviously very particularly preferred embodiment, the agent according to the invention is therefore characterized in that it comprises one or more alkylene glycols corresponding to formula (AG) in a total amount of 10.0 to 99.0% by weight, preferably 30.0 to 99.0% by weight, more preferably 50.0 to 99.0% by weight and very particularly preferably 70.0 to 99.0% by weight, based on the total weight of the agent.

[0171] The agent according to the invention preferably comprises one or more alkylene glycols of the formula (AG-1) in a total amount of 20.0 to 99.0% by weight, preferably 40.0 to 95.0% by weight, particularly preferably 60.0 to 90.0% by weight, based on the total weight of the agent.

[0172] The agent according to the invention preferably comprises one or more alkylene glycols of the formula (AG-2) in a total amount of 1.0 to 35.0% by weight, preferably 3.0 to 30.0% by weight, particularly preferably 4.0 to 25.0% by weight, based on the total weight of the agent.

[0173] Within the scope of another very particularly preferred embodiment, the agent according to the invention is characterized in that it contains a total amount of 20.0 to 99.0% by weight, preferably 40.0 to 95.0% by weight, more preferably 60.0 to 90.0% by weight of one or more alkylene glycols of the formula (AG-1) and / or a total amount of 1.0 to 35.0% by weight, preferably 3.0 to 30.0% by weight, particularly preferably 4.0 to 25.0% by weight of one or more alkylene glycols of the formula (AG-2), based on the total weight of the agent.

[0174] Within the scope of another very particularly preferred embodiment, the agent according to the invention comprises, based on the total weight of the agent: a total amount of 20.0 to 99.0% by weight of one or more alkylene glycols of formula (AG-1), and A total amount of 1.0 to 35.0% by weight of one or more alkylene glycols of formula (AG-2) The present invention is characterized by including:

[0175] Thereby, the total of all alkylene glycol (AG), pigment (a2) (or optionally further pigment (a3)) and amino-functionalized silicone polymer (a1) contained in the agent does not exceed 100% by weight. Furthermore, if any optional components are also used in the agent, the total of said components is reduced to a corresponding extent to a value less than 100% by weight.

[0176] Additional ingredients in the formulation The agents according to the invention may comprise fatty components, structuring agents such as glucose, maleic acid and lactic acid; hair conditioning compounds such as phospholipids, for example lecithin and cephalin; perfume oils, dimethyl isosorbide and cyclodextrin; polymers, for example anionic, nonionic and cationic polymers; surfactants, for example anionic, nonionic, cationic, zwitterionic and amphoteric surfactants; fatty components; fibre structure improving active ingredients, in particular mono-, di- and oligosaccharides, for example glucose, galactose, fructose, fructose and lactose; dyes for colouring the agents; antidandruff active ingredients, for example piroctone olamine, zinc omadine and climbazole; amino acids and oligopeptides; protein hydrolysates based on animal and / or plant, as well as their fatty acid condensation products or optionally in the form of anionic or cationic modified derivatives; vegetable oils; light stabilizers and UV-screening agents; active ingredients, for example panthenol, pantothenic acid, pantolactone, allantoin, pyrrolid ... Further active ingredients, auxiliaries and additives may also be included, such as non-carboxylic acids and their salts, and bisabolol; polyphenols, in particular hydroxycinnamic acids, 6,7-dihydroxycoumarin, hydroxybenzoic acids, catechins, tannins, leucoanthocyanidins, anthocyanidins, flavanones, flavones and flavonols; ceramides or pseudoceramides; vitamins, provitamins and vitamin precursors; plant extracts; fats and waxes, such as fatty alcohols, beeswax, montan wax and paraffin; swelling and penetrating agents, such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidine, urea and primary, secondary and tertiary phosphates; opacifying agents, such as latex, styrene / PVP and styrene / acrylamide copolymers; pearlescent agents, such as ethylene glycol mono- and distearate, and PEG-3 distearate; foaming agents, such as propane-butane mixtures, N2O, dimethyl ether, CO2 and air.

[0177] The selection of these additional substances is made by the skilled person according to the desired properties of the agent. Regarding other optional ingredients and the amounts of said ingredients to be employed, explicit reference should be made to the relevant manuals known to those skilled in the art. The additional active ingredients and auxiliary agents are preferably always used in the preparations according to the invention in an amount of 0.0001-25% by weight, in particular 0.0005-15% by weight, based on the total weight of the particular agent.

[0178] Method for dyeing keratinous materials The above-mentioned agents can be used outstandingly in a process for dyeing keratinous materials, in particular human hair.

[0179] A second object of the present invention is therefore a method for dyeing keratinous materials, in particular human hair, in which an agent as disclosed in detail in the description of the first object of the present invention is applied to the keratinous fibres and, if necessary, rinsed again after an exposure time of between 30 seconds and 45 minutes.

[0180] Thus, a second object of the present invention is to provide a process for dyeing keratinous materials, in particular human hair, comprising the steps of: (1) A step of applying a dye onto a keratinous material, said dye being an agent as disclosed in detail in the description of the first object of the present invention. (2) exposing the dye to the keratinous material; and (3) The dye is washed away with water. The method includes:

[0181] In step (1) of the method according to the invention, the agent of the first object of the invention is applied to keratinous material, which is very particularly preferably human hair.

[0182] In step (2) of the method according to the invention, after application of the agent, the agent is allowed to act on the keratinous materials. In this context, various exposure times are conceivable, for example between 30 seconds and 60 minutes.

[0183] However, a major advantage of the dyeing system according to the invention is that after short exposure times, an intense coloring result is obtained even in a very short time, for which reason the application mixture is advantageously left on the keratinous materials after application for only a relatively short time of 30 seconds to 15 minutes, preferably 30 seconds to 10 minutes, particularly preferably 1 to 5 minutes.

[0184] In another preferred embodiment, the method according to the invention comprises (2) Exposing the keratinous material to the dye for 30 seconds to 15 minutes, preferably 30 seconds to 10 minutes, more preferably 1 to 5 minutes. It is characterized by:

[0185] After the action of the application mixture on the keratinous materials, in step (3) of the process, said keratinous materials are rinsed with water.

[0186] In one embodiment, the applied mixture can be washed off with water alone, i.e. without the aid of a post-treatment agent or shampoo. It is also possible in principle to use a post-treatment agent or conditioner in step (6).

[0187] However, in order to achieve the objectives according to the invention and to enhance application comfort, it has been found to be very particularly preferable to rinse off the agent exclusively with water in step (3) without the aid of additional after-treatment agents, shampoos or conditioners.

[0188] In another preferred embodiment, the method according to the invention comprises (3) Rinse off the dye with water only It is characterized by:

[0189] Method for dyeing keratinous materials, producing a ready-to-use agent for the first time As mentioned above, the agent of the first object of the present invention is a ready-to-use agent that is either provided directly to the user in a ready-to-use form or is prepared by mixing various agents immediately prior to use.

[0190] In order to ensure a particularly fine distribution of the pigments according to the invention, it has been found to be very particularly preferable to prepare a ready-to-use agent by mixing at least two different agents immediately prior to application.

[0191] Within the scope of particularly preferred embodiments, the ready-to-use agent is suitably prepared by mixing at least two different agents, the first of which comprises at least one amino-functionalized silicone polymer (a1) and the second of which comprises at least one platelet-type metallic pigment (a2).

[0192] Therefore, another object of the present application is to provide a method for producing a pharmaceutical composition comprising the steps of: (1) providing an agent (I), said agent (I) comprising: (a1) at least one amino-functionalized silicone polymer (2) providing an agent (II), said agent (II) comprising: (a2) at least one platelet-type metallic pigment (3) mixing the agent (I) and the agent (II) to produce an application mixture; (4) applying the application mixture prepared in step (3) to a keratinous material. (5) exposing the keratinous material to the application mixture applied in step (4); and (6) Rinse the applied mixture with water. (wherein components (a1) and (a2) have already been disclosed in detail in the description of the first object of the present invention) The present invention relates to a method for dyeing keratinous materials, particularly human hair, comprising:

[0193] Agent (I) and / or agent (II) may each optionally contain one or more of the additionally usable ingredients listed above.

[0194] Multi-component packaging unit To enhance the comfort of the user, the above-mentioned agents can be provided to the user in the form of a multi-component packaging unit.

[0195] Another object is therefore to provide a multi-component packaging unit (kit-of-parts) for dyeing keratinous materials, in particular human hair, comprising the following separately prepared components: a first container containing an agent (I), said agent (I) comprising: (a1) at least one amino-functionalized silicone polymer a second container containing an agent (II), said agent (II) comprising: (a2) at least one platelet-type metallic pigment (wherein components (a1) and (a2) have already been disclosed in detail in the description of the first object of the present invention) Includes.

[0196] Another object of the present invention is therefore a multi-component packaging unit (kit-of-parts) for dyeing keratinous materials, in particular human hair, comprising the following separately prepared components: a first container containing an agent (I), said agent (I) comprising: (a1) at least one amino-functionalized silicone polymer a second container containing an agent (II), said agent (II) comprising: (a2) at least one platelet-type metallic pigment a third container containing an agent (III), said agent (III) comprising: Formula (AG): [ka] [In the formula, x represents an integer from 1 to 10000, preferably an integer from 2 to 800, more preferably an integer from 3 to 600, even more preferably an integer from 3 to 400, and very particularly preferably an integer from 4 to 200. At least one alkylene glycol (wherein components (a1), (a2) and (AG) have already been disclosed in detail in the description of the first object of the present invention). Includes.

[0197] With regard to the further preferred embodiments of the method according to the invention and the multicomponent packaging unit according to the invention, what was said for the agent according to the invention applies mutatis mutandis. EXAMPLES

[0198] 1. Preparation The following ready-to-use stains were prepared (all data in weight percent unless otherwise noted):

[0199] [Table 1]

[0200] 2. Application The previously prepared ready-to-use agent was applied (liquid ratio: 1 g agent per 1 g hair strand) to hair strands (Kerling, type "Euronatur hair white" (ENH)) and left to act for 3 minutes. The hair strands were then thoroughly washed with water (1 minute) and dried.

[0201] 3. Evaluation of washing fastness and hair feel The dyed strands were evaluated by five trained people with regard to color intensity and hair feel. Each strand was then washed by hand. For this purpose, each strand was moistened with water, then a commercial shampoo (Schauma 7-Krauter) was applied to the strand (0.25 g shampoo per gram of hair) and massaged with the fingers for 30 seconds. The strands were then rinsed with lukewarm running water for 1 minute and the hair strands were dried. The above process corresponds to washing the hair. This process was repeated for each subsequent washing. After three washings, the strands were compared again by five trained people with regard to color intensity and hair feel. In each case, an average value was created from the individual values. +++=very strong color intensity ++=medium color intensity +=weak color intensity

[0202] [Table 2]

[0203] 3. Further Preparation Examples The following ready-to-use stains were prepared (all data in weight percent unless otherwise stated):

[0204] [Table 3]

[0205] Hair strands dyed with formulations E2, E3 and E4 had intense color and a pleasant, soft feel.

Claims

1. An agent for dyeing keratinous substances, in particular human hair, comprising: (a1) at least one amino-functionalized silicone polymer, and (a2) at least one platelet-type metallic pigment.

2. The agent according to claim 1, characterized in that it comprises (a1) at least one amino-functionalized silicone polymer having at least one secondary amino group.

3. Formula (Si - amino): 【Chemical Formula 1】 [wherein, ALK1 and ALK2, independently of one another, are linear or branched divalent C １ -C ２０ representing an alkylene group] The agent according to claim 1, characterized in that it comprises at least one amino-functionalized silicone polymer (a1) containing at least one structural unit of.

4. Formulas (Si - I) and (Si - II): [Chemical 2] The agent according to claim 1, characterized in that it comprises at least one amino-functionalized silicone polymer (a1) containing the structural unit of.

5. Based on the total weight of the agent, one or more amino-functionalized silicone polymers (a1) in a total amount of 0.1 to 8.0% by weight, preferably 0.2 to 5.0% by weight, more preferably 0.3 to 3.0% by weight, very particularly preferably 0.4 to 2.5% by weight. The agent according to claim 1, characterized by containing.

6. (a2) at least one platelet-type metallic pigment containing at least one metal from the group consisting of aluminum, copper, silver, gold, platinum, zinc, chromium, molybdenum and iron, particularly preferably aluminum. The agent according to claim 1, characterized by containing.

7. (a2) at least one platelet-type metallic pigment having an average pigment diameter (D50) of 0.5 μm to 1 mm, preferably 3 μm to 500 μm, more preferably 5 μm to 100 μm, very particularly preferably 8 μm to 50 μm. The agent according to claim 1, characterized by containing.

8. (a2) As the platelet-type metallic pigment, preferably at least one vacuum deposition pigment at least partially composed of aluminum. The agent according to claim 1, characterized by containing.

9. (a2) at least one uncoated platelet-type metallic pigment, preferably at least one uncoated platelet-type aluminum pigment. The agent according to claim 1, characterized by containing.

10. Based on the total weight of the agent, it contains one or more platelet-type metallic pigments (a2) in a total amount of 0.01 to 10% by weight, preferably 0.1 to 8% by weight, more preferably 0.2 to 6% by weight, and very particularly preferably 0.25 to 5.5% by weight. The agent according to claim 1 is characterized by this.

11. Different from the platelet-type metallic pigment (a2), it further contains at least one inorganic pigment (a3) preferably selected from the group consisting of non-ferrous metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, complex metal cyanides, metal sulfates, and / or mica-based colored pigments coated with at least one metal oxide and / or metal oxychloride. The agent according to claim 1 is characterized by this.

12. Carmine, quinacridone, phthalocyanine, sorghum, blue pigments with Color Index numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with Color Index numbers CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, 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 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. The agent according to claim 1 is preferably characterized by containing at least one organic pigment (a3) selected from the group consisting of these.

13. (a2) at least one platelet-type metallic pigment, and (a3) at least one inorganic and / or organic pigment different from the platelet-type metallic pigment (a2) comprising The agent according to claim 11, characterized in that the weight ratio of the total amount of the platelet-type metallic pigment (a2) contained in the agent to the total amount of the additional pigment (a3) contained in the agent, i.e., the weight ratio (a2) / (a3), is 5.0 to 0.1, preferably 2.5 to 0.2, more preferably 1.5 to 0.4, and very particularly preferably 1.0 to 0.

5.

14. The agent according to claim 1, characterized in that it contains 0 to 70.0% by weight, preferably 0.1 to 35.0% by weight, more preferably 0.2 to 20.0% by weight, and particularly preferably 0.3 to 7.5% by weight of water based on the total weight of the agent.

15. Poly-C １ -C ６ The agent according to claim 1, characterized in that it contains at least one solvent selected from the group consisting of alkylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, dipropylene glycol, ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol, phenoxyethanol and benzyl alcohol, very particularly preferably polyethylene glycol.

16. Formula (AG): 【Chemical Formula 3】 [wherein, x represents an integer from 1 to 10000, preferably an integer from 2 to 800, more preferably an integer from 3 to 600, even more preferably an integer from 3 to 400, and very particularly preferably an integer from 4 to 200] comprising one or more polyalkylene glycols of The agent according to claim 1, characterized in that the polyalkylene glycol of formula (AG) is preferably contained in a total amount of 10.0 to 99.0% by weight, preferably 30.0 to 99.0% by weight, more preferably 50.0 to 99.0% by weight, and very particularly preferably 70.0 to 99.0% by weight based on the total weight of the agent.

17. A method for dyeing keratinous substances, especially human hair, comprising applying the agent according to claim 1 to keratin fibers and, after an exposure time of 30 seconds to 45 minutes, rinsing if applicable.

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