Agents for coloring keratinous substances, comprising aminosilicones, coloring compounds, and addition products of C1-C6 alkylene oxides to esters of fatty acids and aromatic alcohols.

Abstract

The present invention provides a composition comprising (a1) at least one amino-functionalized silicone polymer, and (a2) at least one color-imparting compound, and (a3) ​​at least one C 12- C 30 Fatty acids and C 1- C 12 C to esters with aromatic alcohols 1- The present invention relates to a method for coloring keratinous materials, in particular human hair, comprising an addition product of a C6 alkylene oxide.The present invention also relates to a method for dyeing keratinous materials, in which the agent is used in the keratinous materials.

Description

[Technical Field]

[0001] The subject matter of this application is at least one amino-functionalized silicone polymer (a1), at least one colored compound (a2), and C to an ester of at least one fatty acid and an aromatic alcohol. 1- This is a keratinous substance containing the addition product of C6 alkylene oxide, and is particularly used as a coloring agent for human hair.

[0002] The second subject matter of this application is a method for dyeing a keratinous substance, particularly human hair, wherein the agent of the first subject matter of the present invention is applied to the keratinous substance, allowed to act, and then rinsed again with water. [Background technology]

[0003] The alteration of keratinous substances, particularly human hair, in terms of shape and color, is a significant area of ​​modern cosmetics. To change hair color, professionals are familiar with various coloring systems to meet different coloring requirements. For long-lasting, strong coloration with good colorfastness and gray coverage, oxidative dyes are typically used. Such colorants usually contain oxidative dye precursors (so-called color-developing components) and color-developing components, which, under the influence of oxidizing agents such as hydrogen peroxide, combine to produce the actual dye. Oxidative dyes are characterized by their extremely long-lasting coloring results.

[0004] When using direct dyes, the pre-prepared dye diffuses from the colorant into the hair fibers. Compared to oxidative dyeing, dyeing with direct dyes has a shorter color retention time and is easier to wash out. Dye from direct dyes typically remains in the hair for 5 to 20 washes.

[0005] The use of coloring pigments is known to temporarily alter the color of hair and / or skin. Coloring pigments are generally understood to be insoluble coloring substances. They exist as small particles in the dye composition, undissolved, and only adhere to the surface of hair fibers and / or skin from the outside. Therefore, coloring pigments can usually be removed again without residue by washing several times with a detergent containing a surfactant. Various products of this type are commercially available under the name "hair mascara."

[0006] Until now, oxidative dyes were the only option, especially when users desired long-lasting hair coloring. However, despite numerous optimization attempts, it is impossible to completely avoid the unpleasant odor of ammonia or amines with oxidative dyes. Furthermore, the hair damage associated with the use of oxidative dyes negatively impacts the user's hair. Therefore, the ongoing challenge is the research into alternative, high-performance dyeing processes. For this purpose, pigment-based colorants have become very popular. However, the color intensity and fastness of pigment-based colorants, in particular, still need significant improvement. [Overview of the project] [Problems that the invention aims to solve]

[0007] The object of the present invention is to provide a colorant capable of fixing pigments to hair in an extremely durable manner. When the agent is used in the dyeing process, a particularly strong dyeing result should be obtained. Furthermore, dyeing with good wash fastness, good leveling ability, and especially uniform coloring results should be achieved. Moreover, the abrasion of these pigment colorants should be particularly low; that is, the colorant should also have particularly good friction fastness when in mechanical contact with clothing or other knitted fabrics. Furthermore, keratinous substances, especially hair, should not feel heavy, dull, or sticky after the application of the pigment colorant, and should have as comfortable a feel as possible. [Means for solving the problem]

[0008] Surprisingly, keratinous substances, especially hair, when colored with an agent containing at least one amino-functionalized silicone polymer (a1), at least one coloring compound (a2), and at least one C 12- C 30 fatty acid and aromatic C 1- C 12 addition product of C 1- C6 alkylene oxide (a3), it has been found that the above problems are very well solved.

DETAILED DESCRIPTION OF THE INVENTION

[0009] The first subject of the present invention is (a1) at least one amino-functionalized silicone polymer, and (a2) at least one coloring compound, and (a3) at least one C 12- C 30 fatty acid and C 1- C 12 addition product of C 1- C6 alkylene oxide to an ester with an aromatic alcohol An agent for coloring keratinous substances, especially human hair, containing

[0010] In the process of the research leading to the present invention, surprisingly, the use of alkoxylated fatty acid esters (a3) in agents containing aminosilicones (a1) and coloring compounds (a2) has been shown to result in an improvement in color intensity and washing fastness when the agent is applied in the dyeing process of keratinous substances, especially human hair.

[0011] 〔Keratinous Substances〕 Keratinous substances include hair, skin, nails (e.g., fingernails and / or toenails). Wool, fur, and feathers also fall within the definition of keratinous substances. Preferably, keratinous substances are understood to mean human hair, human skin, and human nails, especially fingernails and toenails. Keratinous substances are especially understood to be human hair.

[0012] [Coloring agents] In the context of this invention, the term "coloring agent" refers to a coloring compound, particularly a pigment, used for coloring keratinous substances, especially hair. In this coloring process, the pigment is deposited on the surface of the keratinous substance as a coloring compound, particularly in a homogeneous, uniform, and smooth film.

[0013] The agent of the present invention preferably contains essential components (a1), (a2), and (a3) ​​in a cosmetic medium.

[0014] [Amino-functionalized silicone polymer (a1)] As a first component (a1) essential to the present invention, the agent contains at least one amino-functionalized silicone polymer. The amino-functionalized silicone polymer may also be referred to as aminosilicone or amodimethicone.

[0015] Silicone polymers are generally macromolecules having a molecular weight of at least 500 g / mol, preferably at least 1000 g / mol, more preferably at least 2500 g / mol, and particularly preferably at least 5000 g / mol, and contain repeating organic units.

[0016] The maximum molecular weight of a silicone polymer depends on the degree of polymerization (number of monomers polymerized) and batch size, and is in part determined by the polymerization method. For the purposes of this invention, the maximum molecular weight of the silicone polymer is 10 7 g / mol or less, preferably 10 6 g / mol or less, particularly preferably 10 5 It is preferable that the concentration is less than or equal to g / mol.

[0017] Silicone polymers contain many Si-O repeating units, and the Si atoms may have organic residues, such as alkyl groups or substituted alkyl groups. Therefore, silicone polymers are also sometimes referred to as polydimethylsiloxanes.

[0018] Silicone polymers, corresponding to high molecular weights, are based on more than 10 Si-O repeating units, preferably more than 50 Si-O repeating units, more preferably more than 100 Si-O repeating units, and most preferably more than 500 Si-O repeating units.

[0019] The term "amino-functionalized silicone polymer" is understood to mean a functionalized silicone having at least one structural unit having an amino group. Preferably, the amino-functionalized silicone polymer has multiple structural units, each having at least one amino group. The amino group is understood to mean a primary amino group, a secondary amino group, and a tertiary amino group. All of these amino groups can be protonated in an acidic environment and exist in their cationic form.

[0020] In principle, good results could be obtained when the amino-functionalized silicone polymer (a1) had at least one primary, at least one secondary, and / or at least one tertiary amino group. However, the stain with the highest wash fastness was observed when the amino-functionalized silicone polymer (a1) containing at least one secondary amino group was used in the agent.

[0021] In one particularly preferred embodiment, the agent of the present invention is characterized by comprising at least one amino-functionalized silicone polymer (a1) having at least one secondary amino group.

[0022] Secondary amino groups may be located in various parts of the amino-functionalized silicone polymer. At least one, preferably more than one, of the formula (Si-amino): [ka] Particularly good results were obtained when using an amino-functionalized silicone polymer (a1) having the structural unit.

[0023] In the structural unit of formula (Si-amino), the abbreviations ALK1 and ALK2 independently represent linear or branched divalent carbon atoms. 1- C 20 Represents an alkylene group.

[0024] In another very particular embodiment, the agent of the present invention is of formula (Si-amino): [ka] [In the formula, ALK1 and ALK2 independently form linear or branched C 1- C 20 [Represents a divalent alkylene group] The present invention is characterized by comprising at least one amino-functionalized silicone polymer (a1) which includes at least one structural unit of the present invention.

[0025] Positions marked with an asterisk (*) indicate bonding to further structural units of the silicone polymer. For example, a silicon atom adjacent to an asterisk may be bonded to another oxygen atom, and an oxygen atom adjacent to an asterisk may be bonded to another silicon atom or even C 1- It may be bonded to a C6 alkyl group.

[0026] Divalent C 1- C 20 Alkylene groups can be substituted with divalent or divalent C. 1- C 20 These can be called alkylene groups, which means that each ALK1 or AK2 group can form two bonds.

[0027] In the case of ALK1, one bond is formed from the silicon atom to the ALK1 group, and a second bond is formed between ALK1 and the secondary amino group.

[0028] In the case of ALK2, one bond extends from the secondary amino group to the ALK2 group, and the second bond is located between ALK2 and the primary amino group.

[0029] Linear divalent carbon 1- C20 An example of an alkylene group is the methylene group (-CH 2- ), ethylene group (-CH 2- CH 2- ), propylene group (-CH 2- CH 2- CH 2- ), and butylene group (-CH 2- CH 2- CH 2- CH 2- ) are examples. Propylene group (-CH 2- CH 2- CH 2- ) is particularly preferred. The divalent alkylene group can also be branched from the chain length of the three C atoms. Branched divalent, divalent C 3- C 20 An example of an alkylene group is (-CH 2- CH(CH3)-) and (-CH 2- CH(CH3)-CH 2- )

[0030] In another particularly preferred embodiment, the structural unit of formula (Siamino) represents a repeating unit in the amino-functionalized silicone polymer (a1), since the silicone polymer contains multiple structural units of formula (Siamino).

[0031] The following are particularly suitable amino-functionalized silicone polymers (a1) having at least one secondary amino group.

[0032] In the method of the present invention, formulas (Si-I) and (Si-II): [ka] When at least one agent containing at least one amino-functionalized silicone polymer (a1) including the structural unit of was applied to a keratinous substance, a stain with very good wash fastness could be obtained.

[0033] In a further clearly very particularly preferred embodiment, the agent according to the present invention is of formula (Si-I) and formula (Si-II): [ka] It is characterized by containing at least one amino-functionalized silicone polymer (a1) that includes the structural unit of .

[0034] Corresponding amino-functionalized silicone polymers having structural units (Si-I) and (Si-II) are, for example, the commercially available DC 2-8566 or Dowsil 2-8566 Amino Fluid, which is marketed by Dow Chemical Company and is given 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, the commercially available Dowsil® AP-8658 Amino Fluid, which is also marketed by Dow Chemical Company.

[0035] In another preferred embodiment, the agent of the present invention is of formula (Si-III): [ka] [In the formula, m and n are numbers selected such that the sum (n+m) is in the range of 1 to 1000. n is a number in the range of 0 to 999, and m is a number in the range of 1 to 1000. R1, R2, and R3 are the same or different, and each has a hydroxyl group or C 1-4 Represents an alkoxy group, Here, at least one of R1 to R3 represents a hydroxyl group. The present invention is characterized by containing at least one amino-functional silicone polymer (a1) of the formula.

[0036] A further preferred agent according to the present invention is of formula (Si-IV): [ka] [Here, p and q are numbers selected such that their sum (p+q) is in the range of 1 to 1000. • p is a number in the range of 0 to 999, and q is a number in the range of 1 to 1000. R1 and R2 are different, and are either hydroxyl groups or C 1-4 [Represents an alkoxy group, and at least one of R1 to R2 represents a hydroxyl group.] The present invention is characterized by containing at least one amino-functional silicone polymer (a1) of the formula.

[0037] Silicones of formula (Si-III) and silicones of formula (Si-IV) differ in the group on the Si atom that contains the nitrogen group: in formula (Si-III), R2 is either a hydroxyl group or C 1-4 The alkoxy group is represented, while the group in formula (Si-IV) is a methyl group. The individual Si groups indicated by the subscripts m and n or p and q do not necessarily exist as blocks; rather, the individual units may exist in a statistically distributed manner, that is, in formulas (Si-III) and (Si-IV), not every R1-Si(CH3)2 group is necessarily bonded to a -[O-Si(CH3)2] group.

[0038] Equation (Si-V): [ka] [Here, A represents the group -OH, -O-Si(CH3)3, -O-Si(CH3)2OH, -O-Si(CH3)2OCH3, D represents the groups -H, -Si(CH3)3, -Si(CH3)2OH, and -Si(CH3)2OCH3. b, n, and c represent integers between 0 and 1000. For more details n>0 and b+c>0 • At least one of the following conditions is met: A = -OH or D = -H. It has also been found that the agent of the present invention, which contains at least one amino-functional silicone polymer (a1) of the formula, is particularly effective with respect to the desired effect.

[0039] In the above formula (Si-V), the individual siloxane units having subscripts b, c, and n are statistically distributed; that is, they are not necessarily block copolymers.

[0040] The agent is given by formula (Si-VI): [ka] The formula may further contain one or more different amino-functionalized silicone polymers represented by the formula -R, where R is a hydrocarbon or hydrocarbon residue having 1 to about 6 carbon atoms, and Q is the general formula -R 1 HZ is a polar group, where R 1is a divalent linking group bonded to a hydrogen atom and a Z residue, consisting of a carbon atom and a hydrogen atom, a carbon atom, a hydrogen atom and an oxygen atom, or a carbon atom, a hydrogen atom and a nitrogen atom, where Z is an organic amino functional residue containing at least one amino functional group; "a" takes a value in the range of about 0 to about 2, "b" takes a value in the range of about 1 to about 3, "a" + "b" is 3 or less, "c" is a numerical value in the range of about 1 to about 3, x is a numerical value in the range of 1 to about 2,000, preferably about 3 to about 50, most preferably about 3 to about 25, y is a numerical value in the range of about 20 to about 10,000, preferably about 125 to about 10,000, most preferably about 150 to about 1,000, and M is a suitable silicone end group known in the prior art, preferably trimethylsiloxy. Non-limiting examples of the group represented by R include alkyl groups, e.g., methyl, ethyl, propyl, isopropyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, isohexyl; alkenyl groups, e.g., vinyl, halovinyl, alkylvinyl, allyl, haloallyl, alkylallyl; cycloalkyl groups, e.g., cyclobutyl, cyclopentyl, cyclohexyl; phenyl groups, benzyl groups, halohydrocarbon residues, e.g., 3-chloropropyl, 4-bromobutyl, 3,3,3-trifluoropropyl, chlorocyclohexyl, bromophenyl, chlorophenyl; and sulfur-containing groups, e.g., mercaptoethyl, mercaptopropyl, mercaptohexyl, mercaptophenyl; preferably, R is an alkyl group containing 1 to about 6 carbon atoms, and most preferably R is methyl. 1 Examples include methylene, ethylene, propylene, hexamethylene, decamethylene, and -CH2CH(CH3)CH 2- Phenylene, naphthylene, -CH2CH2SCH2CH 2- ,-CH2CH2OCH 2- ,-OCH2CH 2- ,-OCH2CH2CH 2- -CH2CH(CH3)C(O)OCH 2- ,-(CH2)3CC(O)OCH2CH 2- -C6H4C6H4-, -C6H4CH2C6H4-; and -(CH2)3C(O)SCH2CH 2-These are some examples.

[0041] Z is an organic amino functional group containing at least one amino functional group. One possible formula for Z is NH(CH2). z The expression is NH2, where z is greater than or equal to 1. Another possible expression for Z is -NH(CH2). z (CH2) zz The formula is NH, where z and zz are both independently 1 or greater, and this structure includes a diamino ring structure, such as piperazinyl. Z is most preferably the -NHCH2CH2NH2 group. Another possible formula for Z is -N(CH2) z (CH2) zz The formula is NX2 or -NX2, where each X in X2 is independently selected from the group consisting of hydrogen and alkyl groups having 1 to 12 carbon atoms, and zz is 0.

[0042] Q is most preferably a polar amine functional residue of the formula -CH2CH2CH2NHCH2CH2NH2. In the formula, "a" takes a value in the range of approximately 0 to approximately 2, "b" takes a value in the range of approximately 2 to approximately 3, "a" + "b" is 3 or less, and "c" is a numerical value in the range of approximately 1 to approximately 3. a Q b SiO (4-a-b) / 2 Unit: R c SiO (4-c) / 2 The molar ratio of the units is approximately 1:2 to 1:65, preferably approximately 1:5 to 1:65, and most preferably approximately 1:15 to 1:20. If one or more silicones of the above formula are used, the various variable substituents in the above formula may differ depending on the various silicone components present in the silicone mixture.

[0043] In one particularly preferred embodiment, the agent of the present invention is characterized by comprising at least one amino-functional silicone polymer of formula (Si-VII): [ka] Here, below: ·G is -H, phenyl group, -OH, -O-CH3, -CH3, -O-CH2CH3, -CH2CH3, -O-CH2CH2CH3, -CH2CH2CH3, -O-CH(CH3)2, -CH(CH3)2, -O-CH2CH2C H2CH3, -CH2CH2CH2CH3, -O-CH2CH(CH3)2, -CH2CH(CH3)2, -O-CH(CH3)CH2CH3, -CH(CH3)CH2CH3, -OC(CH3)3, -C(CH3)3; • 'a' represents a number between 0 and 3, especially 0; • b represents a number between 0 and 1, especially 1. m and n are numerical values ​​such that their sum (m+n) is between 1 and 2000, preferably between 50 and 150, where n is preferably between 0 and 1999, particularly between 49 and 149, and m is preferably between 1 and 2000, particularly between 1 and 10. ·R' is, -QN(R'')-CH 2- CH 2- N(R'')2 -QN(R'')2 -QN + (R'')3A - -QN + H(R'')2A - -QN + H2(R'')A - -QN(R'')-CH 2- CH 2- N + R''H2A - , A monovalent base selected from, Here, each Q is a chemical bond, -CH 2- ,-CH 2- CH 2- -CH2CH2CH 2- -C(CH3) 2- ,-CH2CH2CH2CH 2- -CH2C(CH3) 2- -CH(CH3)CH2CH 2- And, R'' represents -H, -phenyl, -benzyl, -CH 2-CH(CH3)Ph, C 1-20 A represents an alkyl group, preferably the same or different groups selected from the group consisting of -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2CH2CH2H3, -CH2CH(CH3)2, -CH(CH3)CH2CH3, and -C(CH3)3, and A represents an anion preferably selected from chloride, bromide, iodide, or methosulfate. It means...

[0044] In another preferred embodiment, the agent of the present invention is of formula (SiVIIa): [ka] [In the formula, m and n are numerical values ​​such that their sum (m+n) is between 1 and 2000, preferably between 50 and 150, where n is preferably between 0 and 1999, particularly between 49 and 149, and m is preferably between 1 and 2000, particularly between 1 and 10.] The present invention is characterized by comprising at least one amino-functionalized silicone polymer (a1).

[0045] According to the INCI declaration, such silicones are called trimethylsilylamodimethicone.

[0046] Regarding further preferred embodiments, the agent of the present invention is of formula (Si-VIIb): [ka] [In the formula, R represents an -OH, -O-CH3, or -CH3 group; m, n1, and n2 are numerical values ​​such that their sum (m+n1+n2) is between 1 and 2000, preferably between 50 and 150; the sum (n1+n2) is preferably between 0 and 1999, particularly between 49 and 149; and m is preferably between 1 and 2000, particularly between 1 and 10.] The present invention is characterized by comprising at least one amino-functionalized silicone polymer (a1).

[0047] According to the INCI declaration, such amino-functionalized silicone polymers are called amodimethicones.

[0048] Regardless of which amino-functional silicone is used, the agent of the present invention is preferred to contain an amino-functional silicone polymer having an amine value greater than 0.25 meq / g, preferably greater than 0.3 meq / g, and particularly greater than 0.4 meq / g. The amine value represents the milligram equivalent of amine per gram of amino-functional silicone. This can be determined by titration and is also expressed in units of mg KOH / g.

[0049] Furthermore, agents containing a special 4-morpholinomethyl-substituted silicone polymer (a1) are also suitable. This amino-functionalized silicone polymer contains structural units of formula (SI-VIII) and formula (Si-IX). [ka]

[0050] The corresponding 4-morpholinomethyl-substituted silicone polymers are listed below.

[0051] A particularly preferred amino-functionalized silicone polymer is known as amodimethicone / morpholinomethylsilsesquioxane copolymer and is commercially available from Wacker in the form of the raw material Belsil ADM 8301 E.

[0052] As 4-morpholinomethyl-substituted silicones, for example, silicones having structural units of formulas (SI-VIII), (Si-IX), and (Si-X) can be used. [ka] During the ceremony, R1 is -CH3, -OH, -OCH3, -O-CH2CH3, -O-CH2CH2CH3, or -O-CH(CH3)2; R2 is -CH3, -OH, or -OCH3.

[0053] A particularly preferred composition of the present invention comprises at least one 4-morpholinomethyl-substituted silicone of formula (Si-XI), [ka] Here, R1 is -CH3, -OH, -OCH3, -O-CH2CH3, -O-CH2CH2CH3, or -O-CH(CH3)2; R2 is -CH3, -OH, or -OCH3. B represents the group -OH, -O-Si(CH3)3, -O-Si(CH3)2OH, -O-Si(CH3)2OCH3, D represents the groups -H, -Si(CH3)3, -Si(CH3)2OH, and -Si(CH3)2OCH3. a, b, and c independently represent integers between 0 and 1000, given the condition a+b+c>0. m and n are independent integers representing numbers from 1 to 1000. however, • At least one of the conditions B = -OH or D = -H is satisfied. The units a, b, c, m, and n are either statistically distributed or block-like in the numerator.

[0054] The structural formula (Si-XI) is intended to show that the siloxane groups n and m do not necessarily have to be directly bonded to terminal groups B or D, respectively. Rather, in the preferred formula (Si-VI), a>0 or b>0, and in the particularly preferred formula (Si-VI), a>0 and c>0, i.e., terminal groups B or D are preferably bonded to a dimethylsiloxy group. Furthermore, in formula (Si-VI), the siloxane units a, b, c, m and n are preferably statistically distributed.

[0055] The silicone represented by formula (Si-VI) used in accordance with the present invention may be trimethylsilyl-terminated (D or B=-Si(CH3)3), but may also be dimethylsilylhydroxy-terminated at both ends or dimethylsilylhydroxy-terminated and dimethylsilylmethoxy-terminated at one end. Particularly preferred silicones in relation to the present invention are: 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 are selected from among the following. These silicones result in a considerable improvement in the hair properties of hair treated with the agent of the present invention, and a seriously improved protection in oxidation treatment.

[0056] It has been found that the agent of the present invention is particularly advantageous when it contains an amino-functionalized silicone polymer (a1) in a specific range of amounts. Particularly good results were obtained when the agent contains (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 most preferably 0.4 to 2.5% by weight, based on the total weight of the agent.

[0057] In another particularly preferred embodiment, the agent of the present invention is characterized by containing 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.

[0058] [Coloring compound (a2)] As a second essential component, the composition of the present invention contains at least one color-imparting compound (a2).

[0059] In the object of the present invention, the coloring compound is a substance that can impart color to a keratin substance. Particularly suitable coloring compounds can be selected from the group consisting of pigments, direct dyes, photochromic dyes, and thermochromic dyes.

[0060] In a more preferred embodiment, the composition of the present invention is characterized by comprising at least one coloring compound (a2) selected from the group consisting of pigments, direct dyes, photochromic dyes, or thermochromic dyes.

[0061] Pigments within the scope of the present invention are coloring compounds having a solubility in water of less than 0.5 g / L, preferably less than 0.1 g / L, and more preferably less than 0.05 g / L at 25°C. Water solubility can be determined, for example, by the following method: Weigh 0.5 g of pigment into a beaker. Add a stirring bar. Then add 1 liter of distilled water. Heat the mixture to 25°C for 1 hour while stirring with a magnetic stirrer. If undissolved components of the pigment are still visible in the mixture after this period, the solubility of the pigment is less than 0.5 g / L. If the pigment-water mixture cannot be visually evaluated due to the high intensity of the pigment which is thought to be finely dispersed, filter the mixture. If portions of undissolved pigment remain on the filter paper, the solubility of the pigment is less than 0.5 g / L.

[0062] Suitable coloring pigments may be of inorganic and / or organic origin.

[0063] In a preferred embodiment, the agent according to the present invention is characterized by comprising at least one coloring compound (a2) selected from the group consisting of inorganic and / or organic pigments.

[0064] Preferred coloring pigments are selected from synthetic or natural inorganic pigments. Naturally derived inorganic coloring pigments can be produced from, for example, chalk, ochre, amber, green earth, burnt terra ciena, or graphite. In addition, as inorganic coloring pigments, black pigments such as black iron oxide, coloring pigments such as ultramarine or red iron oxide, and fluorescent or phosphorescent pigments can be used.

[0065] 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 colored 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, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI 77289), iron blue (ferric ferrocyanide, CI 77510), and / or carmine (cochineal).

[0066] According to the present invention, colored pearlescent pigments are also particularly preferred colored pigments. These are typically mica and / or mica-based and can be coated with one or more metal oxides. Mica belongs to the layered silicate group. The most important representatives of these silicates are muscovite, phlogopite, soda mica, biotite, thiamite, and margareite. To produce pearlescent pigments in combination with metal oxides, mica, mainly muscovite or phlogopite, is coated with a metal oxide.

[0067] As an alternative to natural mica, synthetic mica coated with one or more metal oxides can also be used as a pearlescent pigment. Particularly preferred pearlescent pigments are those based on natural or synthetic mica (mica) coated with one or more of the above-mentioned metal oxides. The color of each pigment can be changed by varying the thickness of the layer of one or more metal oxides.

[0068] In a more preferred embodiment, the agent of the present invention is characterized by containing at least one coloring compound (a2) selected from the group of inorganic pigments, the inorganic pigment being selected from the group of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, complex metal cyanides, metal sulfates, and bronze pigments, and / or mica or mica-based pigments coated with at least one metal oxide and / or metal oxychloride.

[0069] In a more preferred embodiment, the composition of the present invention is characterized by comprising (a) at least one coloring compound (a2) selected from the group of pigments selected from: titanium dioxide (CI77891), black iron oxide (CI77499), yellow iron oxide (CI77492), red and / or brown iron oxide (CI77491, CI77499), manganese violet (CI77742), ultramarine (sodium aluminum sulfosilicate, CI77007, Pigment Blue 29), chromium oxide hydrate (CI77289), chromium oxide (CI77288), and / or iron blue (ferric ferrocyanide, CI77510), reacted with mica or mica-based pigment.

[0070] Examples of particularly suitable coloring pigments are commercially available 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.

[0071] Particularly preferred coloring pigments bearing the trade name Colorona® include, for example, the following: Colorona Copper, Merck, Mica, CI77491 (Iron Oxide) Colorona Passion Orange, Merck, Mica, CI77491 (Iron Oxide), Alumina Colorona Patina Silver, Merck, Mica, CI77499 (Iron Oxide), CI77891 (Titanium Dioxide) Colorona RY, Merck, CI77891 (Titanium Dioxide), Mica, CI75470 (Carmine) Colorona Oriental Beige, Merck, Mica, CI77891 (Titanium Dioxide), CI77491 (Iron Oxide) Colorona Dark Blue, Merck, Mica, Titanium Dioxide, Ferric Ferrocyanide Colorona Chameleon, Merck, CI77491 (iron oxide), mica Colorona Aborigine Amber, Merck, Mica, CI77499 (Iron Oxide), CI77891 (Titanium Dioxide) Colorona Blackstar Blue, Merck, CI77499 (iron oxide), mica Colorona Patagonian Purple, Merck, Mica, CI77491 (Iron Oxide), CI77891 (Titanium Dioxide), CI77510 (Ferric Ferrocyanide) Colorona Red Brown, Merck, Mica, CI77491 (Iron Oxide), CI77891 (Titanium Dioxide) Colorona Russet, Merck, CI77491 (titanium dioxide), mica, CI77891 (iron oxide) Colorona Imperial Red, Merck, Mica, Titanium Dioxide (CI77891), D&C RED NO.30 (CI73360) Colorona Majestic Green, Merck, CI77891 (Titanium Dioxide), Mica, CI77288 (Chromium oxide green) Colorona Light Blue, Merck, Mica, Titanium Dioxide (CI 77891), Ferric Ferrocyanide (CI 77510) Colorona Red Gold, Merck, Mica, CI77891 (Titanium Dioxide), CI77491 (Iron Oxide) 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, CI77499 (Iron Oxide) Colorona Bordeaux, Merck, mica, CI77491 (iron oxide) Colorona Bronze, Merck, Mica, CI77491 (Iron Oxide) Colorona Bronze Fine, Merck, Mica, CI 77491 (Iron Oxide) Colorona Fine Gold MP 20, Merck, Mica, CI77891 (Titanium Dioxide), CI77491 (Iron Oxide) Colorona Sienna Fine, Merck, CI77491 (Iron Oxide), Mica Colorona Sienna, Merck, Mica, CI77491 (Iron Oxide) Colorona Precious Gold, Merck, Mica, CI77891 (Titanium Dioxide), Silica, CI77491 (Iron Oxide), Tin Oxide Colorona Sun Gold Sparkle MP 29, Merck, Mica, Titanium Dioxide, Iron Oxides, Mica, CI 77891, CI 77491 (EU) Colorona Mica Black, Merck, CI77499 (iron oxide), mica, CI77891 (titanium dioxide) Colorona Bright Gold, Merck, Mica, CI77891 (Titanium Dioxide), CI77491 (Iron Oxide) Colorona Blackstar Gold, Merck, mica, CI77499 (iron oxide).

[0072] Other particularly preferred coloring pigments bearing the trade name Xirona® include, for example, the following: Xirona Golden Sky, Merck, Silica, CI77891 (Titanium Dioxide), Tin Oxide Xirona Caribbean Blue, Merck, Mica, CI77891 (Titanium Dioxide), Silica, Tin Oxide Xirona Kiwi Rose, Merck, Silica, CI77891 (Titanium Dioxide), Tin Oxide Xirona Magic Mauve, Merck, silica, CI77891 (titanium dioxide), tin oxide.

[0073] In addition, particularly preferred coloring pigments bearing the trade name Unipure® include, for example, the following: Unipure Red LC 381 EM, Sensient CI77491 (Iron Oxide), Silica Unipure Black LC 989 EM, Sensient, CI77499 (Iron Oxide), Silica Unipure Yellow LC 182 EM, Sensient, CI77492 (Iron Oxide), Silica.

[0074] In further embodiments, the agent of the present invention may contain one or more coloring compounds (a2) selected from the group consisting of organic pigments.

[0075] The organic pigment according to the present invention is a correspondingly insoluble organic dye or color lacquer, which can be selected from the group consisting of, for example, nitroso, nitro-azo, xanthene, anthraquinone, isoindolinone, isoindolinone, quinacridone, perinone, perylene, diketopyrrolopyrrole, indigo, thioindide, dioxazine, and / or triarylmethane compounds.

[0076] Particularly suitable examples of organic pigments include carmine, quinacridone, phthalocyanine, sorghum, blue pigments with color index numbers CI42090, CI69800, CI69825, CI73000, CI74100, CI74160, yellow pigments with color index numbers CI11680, CI11710, CI15985, CI19140, CI20040, CI21100, CI21108, CI47000, CI47005, green pigments with color index numbers CI61565, CI61570, CI74260, and color index Orange pigments with color index numbers CI11725, CI15510, CI45370, CI71105; red pigments with color index numbers CI12085, CI12120, CI12370, CI12420, CI12490, CI14700, CI15525, CI15580, CI15620, CI15630, CI15800, CI15850, CI15865, CI15880, CI17200, CI26100, CI45380, CI45410, CI58000, CI73360, CI73915, and / or CI75470.

[0077] In another particularly preferred embodiment, the agent of the present invention is characterized by comprising at least one coloring compound (a2) selected from the group of organic pigments, the organic pigment being carmine, quinacridone, phthalocyanine, sorghum, blue pigments having color index numbers CI42090, CI69800, CI69825, CI73000, CI74100, CI74160, yellow pigments having color index numbers CI11680, CI11710, CI15985, CI19140, CI20040, CI21100, CI21108, CI47000, CI47005, color index numbers CI61565, CI61570, C Preferably selected from the group consisting of a green pigment having I74260, an orange pigment having color index numbers CI11725, CI15510, CI45370, CI71105, and a red pigment having color index numbers CI12085, CI12120, CI12370, CI12420, CI12490, CI14700, CI15525, CI15580, CI15620, CI15630, CI15800, CI15850, CI15865, CI15880, CI17200, CI26100, CI45380, CI45410, CI58000, CI73360, CI73915, and / or CI75470.

[0078] The organic pigment may also be a color paint. In the sense of the present invention, the term color lacquer means particles containing a layer of absorbed dye, and the particles and dye units are insoluble under the conditions described above. The particles may be, for example, an inorganic substrate. This may be aluminum, silica, calcium borosilicate, calcium aluminum borosilicate, or even aluminum.

[0079] For example, Alizarin color varnish can be used.

[0080] Due to their excellent light and heat resistance, the use of the above pigments in the agent of the present invention is particularly preferred. It is also preferred that the pigments used have a specific particle size. Therefore, according to the present 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, particularly 14 to 30 μm. 50 It is advantageous to have. The average particle size D 50 can be determined, for example, using dynamic light scattering (DLS).

[0081] The coloring compound (a2), particularly the coloring compound selected from the group of pigments, is the second essential component of the agent of the present invention and is preferably used in a specific range of amounts in the agent. When the agent contains one or more pigments (a2) 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, very preferably 0.25 to 1.5% by weight based on the total weight of the agent, particularly good results were obtained.

[0082] In another very particularly preferred embodiment, the agent of the present invention is characterized in that the agent contains one or more pigments (a2) in a total amount of 0.01 to 10.0% by weight, preferably 0.1 to 5. %> by weight, more preferably 0.2 to 2.5% by weight, very particularly preferably 0.25 to 1.5% by weight based on the total weight of the agent.

[0083] As the coloring compound (a2), the agent of the present invention may contain one or more direct dyes. Direct dyes are dyes that are directly absorbed into the hair and do not require an oxidation process to form color. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones, triarylmethane dyes, or indophenols.

[0084] Direct dyes within the scope of the present invention have a solubility in water (760 mmHg) exceeding 0.5 g / L at 25 °C and should not be regarded as pigments.

[0085] Preferably, direct dyes within the scope of the present invention have a solubility in water greater than 1.0 g / L (760 mmHg) at 25°C.

[0086] Direct dyes can be classified into anionic, cationic, and nonionic direct dyes.

[0087] In further embodiments, the method of the present invention is characterized in that the agent comprises at least one coloring compound (a2) selected from the group consisting of anionic, nonionic, and cationic direct dyes.

[0088] Suitable cationic direct dyes include Basic Blue 7, Basic Blue 26, HC Blue 16, Basic Violet 2 and Basic Violet 14, Basic Yellow 57, Basic Red 76, Basic Blue 16, Basic Blue 347 (Cationic Blue 347 / Dystar), HC Blue No. 16, Basic Blue 99, Basic Brown 16, Basic Brown 17, Basic Yellow 57, Basic Yellow 87, Basic Orange 31, Basic Red 51, and Basic Red 76.

[0089] As nonionic direct dyes, nonionic nitro and quinone dyes and neutral azo dyes can be used. Suitable nonionic direct dyes are those listed by the following international names or trade names: HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, HC Red BN, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, known compounds, as well as 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis-(2-hydroxyethyl)-amino-2-nitrobenzene, 3-nitro-4-(2-hydroxyethyl)-aminophenol 2-(2-hydroxyethyl)amino-4,6-dinitrophenol, 4-[(2-hydroxyethyl)amino]-3-nitro-1-methylbenzene, 1-amino-4-(2-hydroxyethyl)-amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1-(2'-ureidoethyl)amino-4-nitrobenzene, 2-[(4-amino-2-nitrophenyl)amino]benzoic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid, and 2-chloro-6-ethylamino-4-nitrophenol.

[0090] Anionic direct dyes are also called acid dyes. Acid dyes are direct dyes that have at least one carboxylic acid group (-COOH) and / or one sulfonic acid group (-SO3H). Depending on the pH value, the protonated form (-COOH, -SO3H) of the carboxylic acid group or sulfonic acid group is their deprotonated form (-COOH). - , -SO3 -They are in equilibrium with (they are present). The proportion of the protonated form increases with decreasing pH. When the direct dyes are used in the form of their salts, the carboxylic acid group or sulfonic acid group exists in the deprotonated form and is neutralized with the corresponding stoichiometric equivalent of cation to maintain electrical neutrality. The acid dyes of the present invention can also be used in the form of their sodium salts and / or their potassium salts.

[0091] Acid dyes within the scope of the present invention have a solubility in water greater than 0.5 g / L (760 mmHg) at 25°C and therefore should not be considered pigments. Preferably, acid dyes within the scope of the present invention have a solubility in water greater than 1.0 g / L (760 mmHg) at 25°C.

[0092] Alkaline earth salts (such as calcium and magnesium salts) or aluminum salts of acid dyes often have lower solubility than their corresponding alkali salts. If the solubility of these salts is less than 0.5 g / L (25°C, 760 mmHg), they do not fall under the definition of direct dyes.

[0093] An essential characteristic of acid dyes is their ability to form anionic charges, thereby the carboxylic acid or sulfonic acid groups involved are usually bonded to different chromophore systems. Suitable chromophore systems can be found, for example, in the structures of nitrophenylenediamine, nitroaminophenol, azo dyes, anthraquinone dyes, triarylmethane dyes, xanthene dyes, rhodamine dyes, oxazine dyes, and / or indophenol dyes.

[0094] In a further embodiment, a method for staining a keratinous substance comprises at least one anionic direct dye selected from the group consisting of nitrophenylenediamine, nitroaminophenol, azo dyes, anthraquinone dyes, triarylmethane dyes, xanthene dyes, rhodamine dyes, oxazine dyes and / or indophenol dyes, wherein each dye from the above group has at least one carboxylic acid group (-COOH), a sodium carboxylate group (-COONa), a potassium carboxylate group (-COOK), a sulfonic acid group (-SO3H), a sodium sulfonate group (-SO3Na), and / or a potassium sulfonate group (-SO3K).

[0095] A suitable acid dye may include, for example, one or more compounds selected from the following group: Acid Yellow 1 (D&C Yellow 7, Citronin A, Ext. D&C Yellow No. 7, Japan Yellow 403, CI 10316, COLIPA n°B001), Acid Yellow 3 (COLIPA n°C54, D&C Yellow N°10, Quinoline Yellow, E104, Food Yellow 13), Acid Yellow 9 (CI 13015), Acid Yellow 17 (CI 18965), Acid Yellow 23 (COLIPA n°29, Covacap Jaune W1100 (LCW), Sicovit Tartrazine 85E102 (BASF), Tartrazine, Food Yellow 4, Japan Yellow 4, FD&C Yellow No. 5), Acid Yellow 36 (CI 13065), Acid Yellow 121 (CI 18690), Acid Orange 6 (CI 14270), Acid Orange 7 (2-Naphthol Orange, Orange II, CI 15510, D&C Orange 4, COLIPA n℃015), Acid Orange 10 (CI 16230; Orange G sodium salt), Acid Orange 11 (CI 45370), Acid Orange 15 (CI 50120), Acid Orange 20 (CI 14600), Acid Orange 24 (BROWN 1; CI 20170; KATSU201; nosodiumsalt; Brown No.201; RESORCIN BROWN; ACID ORANGE24; Japan Brown201; D&C Brown No.1), Acid Red 14 (CI 14720), Acid Red 18 (E124, Red 18; CI 16255), Acid Red27 (E123, CI16185, C-Rot46, Real red D, FD&C Red Nr.2, Food Red9, Naphthol red S), Acid Red33 (Red33, Fuchsia red, D&C Red33, CI17200), Acid Red35 (CIC.I.18065)、Acid Red51(CI45430、Pyrosin B、テトライオドフルオレセイン、Eosin J、イオデオシン)、Acid Red52(CI45100、Food Red106、Solar Rhodamine B、Acid Rhodamine B、Red n°106 Pontacyl Brilliant Pink)、Acid Red73(CI27290)、Acid Red87(Eosin、CI45380)、Acid Red92(COLIPA n℃53、CI45410)、Acid Red95(CI45425、Erythtosine、Simacid Erythrosine Y)、Acid Red184(CI15685)、Acid Red195、Acid Violet43(Jarocol Violet43、Ext.D&C Violet n°2、C.I.60730、COLIPA n℃063)、Acid Violet49(CI42640)、Acid Violet50(CI50325)、Acid Blue1(Patent Blue、CI42045)、Acid Blue3(Patent Blue V、CI42051)、Acid Blue7(CI42080)、Acid Blue104(CI42735)、Acid Blue9(E133、Patent Blue AE、Amido blue AE、Erioglaucin A、CI42090、C.I.Food Blue2)、Acid Blue62(CI62045)、Acid Blue74(E132、CI73015)、Acid Blue80(CI61585)、Acid Green3(CI42085、Foodgreen1)、Acid Green5(CI42095)、Acid Green9(C.I.42100)、Acid Green22(C.I.42170)、Acid Green25(CI61570、Japan Green201、D&C Green No.5)、Acid Green50(Brilliant Acid Green BS、C.I.44090, Acid Brilliant Green BS, E142), Acid Black1(Black n°401, Naphthalene Black10B, Amido Black10B, CI20 470, COLIPA n°B15), Acid Black52(CI15711), Food Yellow8(CI14270), Food Blue5, D&C Yellow8, D&C Green5, D&C Orange10, D&C Orange11, D&C Red21, D&C Red27, D&C Red33, D&C Violet2, and / or D&C Brown1. .

[0096] For example, the water solubility of anionic direct dyes can be determined as follows: Place 0.1 g of anionic direct dye in a beaker. Add a stirring bar. Then add 100 mL of water. Heat this mixture to 25°C while stirring with a magnetic stirrer. Stir for 60 minutes. Then visually evaluate the aqueous mixture. If there is still undissolved residue, increase the amount of water in increments of 10 mL, for example. Add water until the amount of dye used is completely dissolved. If the dye-water mixture cannot be visually evaluated due to the high concentration of the dye, filter the mixture. If undissolved dye remains on the filter paper, repeat the solubility test with a larger amount of water. If 0.1 g of anionic direct dye dissolves in 100 mL of water at 25°C, the solubility of the dye is 1.0 g / L.

[0097] Acid Yellow 1 is called 8-hydroxy-5,7-dinitro-2-naphthalenesulfonic acid disodium salt and has a solubility of at least 40 g / L (25°C) in water.

[0098] Acid Yellow 3 is a mixture of mono- and cisulfonic acid sodium salts of 2-(2-quinolyl)-1H-indene-1,3(2H)-dione, and has water solubility at 20 g / L (25°C).

[0099] Acid Yellow 9 is called the disodium salt of 8-hydroxy-5,7-dinitro-2-naphthalenesulfonic acid and has a solubility in water of more than 40 g / L (at 25°C).

[0100] Acid Yellow 23 is the trisodium salt of 4,5-dihydro-5-oxo-1-(4-sulfophenyl)-4-((4-sulfophenyl)azo)-1H-pyrazole-3-carboxylic acid, and is readily soluble in water at 25°C.

[0101] Acid Orange 7 is the sodium salt of 4-[(2-hydroxy-1-naphthyl)azo]benzenesulfonate. Its water solubility is greater than 7 g / L (at 25°C).

[0102] Acid Red18 is the trinarium salt of 7-hydroxy-8-[(E)-(4-sulfonato-1-naphthyl)-diazenyl)]-1,3-naphthalenedisulfonate and has very high water solubility of over 20% by weight.

[0103] Acid Red 33 is the dianthorium salt of 5-amino-4-hydroxy-3-(phenylazo)-naphthalene-2,7-disulfonate, and its solubility in water is 2.5 g / L (25°C).

[0104] Acid Red92 is the disodium salt of 3,4,5,6-tetrachloro-2-(1,4,5,8-tetrabromo-6-hydroxy-3-oxoxanthene-9-yl)benzoic acid, and its solubility in water is shown to be greater than 10 g / L (25°C).

[0105] Acid Blue 9 is the disodium salt of 2-({4-[N-ethyl(3-sulfonatobenzyl)amino]phenyl}{4-[(N-ethyl(3-sulfonatobenzyl)imino]-2,5-cyclohexadiene-1-ylidene}methyl)-benzenesulfonate and has a solubility in water of more than 20% by weight (at 25°C).

[0106] Therefore, in further embodiments, the agent according to the present invention is Acid Yellow 1, Acid Yellow 3, Acid Yellow 9, Acid Yellow 17, Acid Yellow 23, Acid Yellow 36, Acid Yellow 121, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 11, Acid Orange 15, Acid Orange 20, Acid Orange 24, Acid Red 14, Acid Red 27, Acid Red 33, Acid Red 35, Acid Red 51, Acid Red 52, Acid Red 73, Acid Red 87, Acid Red 92, Acid Red 95, Acid Red 184, Acid Red 195, Acid Violet 43, Acid Violet 49, Acid Violet 50, Acid Blue 1, Acid Blue 3, Acid Blue 7, Acid Blue 104, Acid Blue 9, Acid Blue 62, Acid Blue 74, Acid Blue 80, Acid Green 3, Acid Green 5, Acid The present invention is characterized by comprising at least one direct dye (a2) selected from the group consisting of Green9, Acid Green22, Acid Green25, Acid Green50, Acid Black1, Acid Black52, Food Yellow8, Food Blue5, D&C Yellow8, D&C Green5, D&C Orange10, D&C Orange11, D&C Red21, D&C Red27, D&C Red33, D&C Violet2, and / or D&C Brown1.

[0107] One or more direct action dyes can be used in various amounts in the agent of the present invention, depending on the desired color intensity. Good results were obtained when the agent contained one or more direct dyes (a2) in a total amount of 0.01 to 10.0% by weight, preferably 0.1 to 8.0% by weight, more preferably 0.2 to 6.0% by weight, and most preferably 0.5 to 4.5% by weight, based on the total weight of the agent.

[0108] Furthermore, the agent may contain at least one photochromic dye or thermochromic dye as the coloring compound (a2).

[0109] A photochromic dye is a dye that exhibits a reversible change in hue upon irradiation with UV light (sunlight or black light). In this process, the UV light changes the chemical structure of the dye and thus its absorption behavior (photochromism).

[0110] A thermochromic dye is a dye that exhibits a reversible change in hue in response to a temperature change. In this process, the temperature change alters the chemical structure of the dye and thus its absorption behavior (thermochromism).

[0111] The agent may contain one or more photochromic dyes (a2) in a total amount of 0.01 to 10.0% by weight, preferably 0.1 to 8.0% by weight, more preferably 0.2 to 6.0% by weight, and most preferably 0.5 to 4.5% by weight, based on the total weight of the agent.

[0112] [C 12- C 30 An addition product (a3) of C 1- C 12 C6 alkylene oxide to an ester of a fatty acid and C 1- C aromatic alcohol] As a third essential component (a3), the agent of the present invention contains at least one C 12- C 30 An addition product of C 1- C 12 C6 alkylene oxide to an ester of a fatty acid and C 1- C aromatic alcohol and contains.

[0113] C 12- C 30 An addition product of C 1- C 12 C6 alkylene oxide to an ester of a fatty acid and C 1-The addition product (a3) of C6 alkylene oxide is hereinafter also abbreviated as alkoxylated fatty acid ester (a3).

[0114] C 1- C6-alkylene oxide is the epoxide of C 1- C6-alkane. Particularly suitable C 1- Examples of C6 alkylene oxide include ethylene oxide (1,2-epoxyethane), propylene oxide (1,2-epoxypropane), and butylene oxide (1,2-epoxybutane and 2,3-epoxybutane).

[0115] Ethoxylated fatty acid ester (a3) is based on C 12- C 30 fatty acids. These C 12- C 30 fatty acids are linear or branched, saturated or mono-unsaturated or poly-unsaturated fatty acids, which may have one or more hydroxy groups. The C 12- C 24 fatty acids according to the invention are characterized by containing 12 to 30 carbon atoms, preferably 12 to 24 carbon atoms. Furthermore, C 12- C 24 -fatty acids have at least one carboxylic acid group.

[0116] To form the ethoxylated fatty acid ester (a3) ​​according to the present invention, one or more fatty acids are selected from the group consisting of, for example, dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), tetracosanoic acid (lignoceric acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), petroseric acid [(Z)-6-octadecenoic acid], palmitoleic acid [(9Z)-hexadeca-9-enoic acid], oleic acid [(9Z)-octadeca-9-enoic acid], elaidic acid [(9E)-octa Deca-9-enoic acid, erucic acid [(13Z)-docos-13-enoic acid], linoleic acid [(9Z,12Z)-octadeca-9,12-dienoic acid, linolenic acid [(9Z,12Z,15Z)]-octadeca-9,12,15-trienoic acid, eleostearic acid [(9Z,11E,13E)-octadeca-9,11,3-trienoic acid], arachidonic acid [(5Z,8Z,11Z,14Z)-icosa-5,8,11,14-tetraenoic acid], nervonic acid [(15Z)-tetracos-15-enoic acid] and / or castor oleic acid ((9Z,12R)-12-hydroxy-9-octadecenoic acid).

[0117] Ethoxylated fatty acid ester (a3) ​​is the same as C mentioned earlier. 12- C 24 Fatty acids and C 1- C 12 C to esterification with aromatic alcohols 1- This represents the addition product of a C6 alkylene oxide. Characteristically, it is aromatic C6. 1- C 12 Alcohols contain 1 to 12 carbon atoms and at least one aromatic ring system. Aromatic C 1- C 12 Each alcohol has at least one hydroxyl group, which may be directly located on the aromatic compound (e.g., as in phenol) or linked to the aromatic compound via an aliphatic unit (e.g., as in benzyl alcohol or 2-phenoxyethanol). Aromatic C 1- C 12The structure of an alcohol may further contain heteroatoms such as oxygen or nitrogen.

[0118] Corresponding aromatic C 1- C 12 The alcohol may be monohydric or polyhydric, that is, it may have one or more hydroxyl groups.

[0119] Monovalent aromatic compound C 1- C 12 Alcohols are particularly preferred. This type of compound contains exactly one hydroxyl group. Suitable examples include phenol, benzyl alcohol, 2-phenylethyl alcohol, and 2-phenoxyethanol.

[0120] Therefore, keratinous substances containing the following, especially agents for dyeing human hair, are particularly preferred: (a1) at least one amino-functionalized silicone polymer, and (a2) at least one color-imparting compound, and (a3) at least one C 12- C 30 Fatty acids and C 1- C 12 C to esterification with monohydric aromatic alcohols 1- Addition product of C6 alkylene oxide.

[0121] C 12- C 30 A fatty acid and an aromatic C selected from the group consisting of benzyl alcohol, phenol, 2-phenylethyl alcohol, and 2-phenoxyethanol. 1- C 12 C to the ester obtained by esterification with alcohol 1- When at least one adduct (a3) ​​of C6 alkylene oxide is used in the agent of the present invention, particularly good cleaning and frictional resistance can be obtained.

[0122] In a further preferred embodiment, the agent of the present invention is characterized by comprising the following: (a3)C 12- C 24 A fatty acid and C selected from the group consisting of benzyl alcohol, phenol, 2-phenylethyl alcohol, and 2-phenoxyethanol, most preferably selected from the group consisting of benzyl alcohol. 1- C 12 At least one C is added to the ester obtained by esterification with an aromatic alcohol. 1- Addition product of C6 alkylene oxide.

[0123] Within the scope of particularly preferred embodiments, the means of the present invention are: (a3)C 12- C 24 C to the ester obtained by esterification of fatty acids and benzyl alcohol 1- It contains at least one addition product of C6 alkylene oxide. It is characterized by the following.

[0124] In a further preferred embodiment, the agent of the present invention is characterized by comprising the following: (a3)C 12- C 24 A fatty acid and C selected from the group consisting of benzyl alcohol, phenol, 2-phenylethyl alcohol, and 2-phenoxyethanol. 1- C 12 An addition product of at least one ethylene oxide and / or propylene oxide to an ester obtained by esterification with an aromatic alcohol.

[0125] Regarding further particularly preferred embodiments, the agent of the present invention is characterized by comprising the following: (a3)C 12- C 24 An addition product of at least one ethylene oxide and / or propylene oxide to an ester obtained by esterification of a fatty acid with benzyl alcohol.

[0126] As mentioned earlier, C is particularly well suited. 1-Examples of C6 alkylene oxides include ethylene oxide (1,2-epoxyethane), propylene oxide (1,2-epoxypropane), and butylene oxide (1,2-epoxybutane and 2,3-epoxybutane). Ethylene oxide (1,2-epoxyethane) and propylene oxide (1,2-epoxypropane) are explicitly very particularly preferred. Propylene oxide (1,2-epoxypropane) is most preferred.

[0127] C 12- C 30 Fatty acids and aromatic C 1- C 12 The corresponding addition product of ethylene oxide to an ester with an alcohol (a3) ​​is C 12- C 30 It is formed when a fatty acid itself or an ester already formed from said fatty acid is reacted with ethylene oxide (or 1,2-epoxyethane, CAS number 75-21-8).

[0128] Similarly, C 12- C 30 Fatty acids and C 1- C 12 The corresponding addition product of propylene oxide to an ester with an aromatic alcohol (a3) ​​is C 12- C 30 It is formed when a fatty acid itself or an ester already formed from said fatty acid is reacted with propylene oxide (also known as 1,2-epoxypropane, CAS number 75-56-9 (racemic mixture), 15448-47-2 ((R)-enantiomer, 16088-62-3 (S)-enantiomer)).

[0129] C 12- C 30 When reacting fatty acids with ethylene oxide, first, C 12- C 30Adducts are formed from the carboxylic acid portion of fatty acids and ethylene oxide, forming a *-C(O)-O-CH2-CH2-O-* moiety. This group is also an ester. When 1 mole of ethylene oxide is reacted with 1 mole of fatty acid, on average, a simple adduct with 1 unit of *-CH2-CH2-O-* is formed. However, depending on the molar excess of ethylene oxide used, multiple units of *-CH2-CH2-O-* may be formed. 12- C 30 Multiple adducts can also be formed per mole of fatty acid. To form ester (a3), the adduct is then combined with at least one aromatic C 1- C 12 Further reaction with alcohol. Here, the positions marked with an asterisk indicate bonding to the remaining fatty acid and bonding to the remaining alcohol.

[0130] Similarly, C 12- C 30 When reacting fatty acids with propylene oxide, first, C 12- C 30 Adducts are formed from the carboxylic acid group of fatty acids and propylene oxide, resulting in either the group *-C(O)-O-CH(CH3)-CH2-O-* or the group *-C(O)-O-CH2-CH(CH3)-O-*. A mixture of these two groups is usually obtained in the reaction mixture. Both groups are esters. When 1 mole of propylene oxide is reacted per mole of fatty acid, on average, a simple adduct is formed with a mixture of *-CH(CH3)-CH2-O-* units and *-CH2-CH(CH3)-O-* units. However, depending on the molar excess of propylene oxide used, there may be multiple units of *-CH(CH3)-CH2-O-* and / or *-CH2-CH(CH3)-O-*, which is C 12- C 30 Multiple adducts can also be formed per mole of fatty acid. To form ester (a3), the adduct is then combined with at least one aromatic C 1- C 12It is further reacted with alcohol. Here, the positions marked with an asterisk represent the bonds to the remaining part of the fatty acid and the bonds to the remaining part of the alcohol.

[0131] Furthermore, in principle, it is conceivable to react the fatty acid with a mixture of ethylene oxide and propylene oxide. In this case, a mixture of the above-mentioned adducts is formed. By this method, it is also possible to react with higher alkylene oxides (such as butylene oxide, etc.) and C 12- C 30 fatty acids. 12- C 30 The reaction with fatty acids is also possible.

[0132] The addition product thus prepared results in, for example, an alkoxylated fatty acid ester of the general formula (AFE-I):

Chemical formula

[0133] When using an agent containing at least one ethoxylated fatty acid ester (a3) of the formula (AFE-I), particularly excellent dyeing was obtained with respect to good washing fastness and good rubbing fastness. For this reason, the use of one or more ethoxylated fatty acid esters (a3) of the formula (AFE-I) in the agent of the present invention is particularly preferred.

[0134] In further particularly preferred embodiments, the agent of the present invention is characterized by comprising the following: (a3) At least one alkoxylated fatty acid ester of general formula (AFE-I) [ka] Here, R1 is saturated or unsaturated C 11- C 29 Represents an alkyl group, R2 and R3 are independently hydrogen atoms and C 1- C6 alkyl group, hydroxyl group or C 1- Represents a C6 alkoxy group, n represents a number that is either 0 or 1. m represents an integer from 0 to 6. o represents an integer from 1 to 60, and Q represents the structural unit -O-CH2-CH2-, -O-CH(CH3)-CH2-, or -O-CH2-CH(CH3)-. However, if m is 0, then n is also 0.

[0135] The R1 group is saturated or unsaturated C 11- C 29 Represents an alkyl group. C 11- C 23 An unsaturated alkyl group may contain one or more double bonds, or C 11- C 23 Also called an unsaturated alkenyl group. 11- C 29 The alkyl group may be linear or branched.

[0136] Preferably, R1 is a linear, saturated or unsaturated C 11- C 23 Represents an alkyl group.

[0137] R2 and R3 are hydrogen atoms, C 1- C6 alkyl group, hydroxyl group or C 1-Represents a C6 alkoxy group. Very preferably, R2 and R3 both represent hydrogen atoms.

[0138] The index number n represents a number that is either 0 or 1. Preferably, n represents the number 0.

[0139] The index number m represents an integer from 0 to 6. Preferably, m represents the number 1.

[0140] The index number o represents an integer from 1 to 60. Preferably, o represents an integer from 1 to 30, more preferably from 1 to 20, even more preferably from 1 to 10, and most preferably from 1 to 5.

[0141] Base Q represents the structural unit -O-CH2-CH2-, -O-CH(CH3)-CH2-, or -O-CH2-CH(CH3)-. Particularly preferred, Q represents the structural unit -O-CH(CH3)-CH2- or -O-CH2-CH(CH3)-.

[0142] If o is a number greater than 1, the compound of formula (AFE-I) (or the compound of formula (AFE-II)) contains multiple structural units Q, in which case each of the structural units Q can be selected independently of the other structural units Q.

[0143] Therefore, the preferred agent of the present invention is characterized by comprising the following: (a3) At least one alkoxylated fatty acid ester of general formula (AFE-I): [ka] Here, R1 is saturated or unsaturated C 11- C 29 Represents an alkyl group, R2 and R3 are independently hydrogen atoms and C 1- C6 alkyl group, hydroxyl group or C 1- Represents a C6 alkoxy group, n represents a number that is either 0 or 1. m represents an integer from 0 to 6. o represents an integer from 1 to 60, and Q represents the structural unit -O-CH2-CH2-, -O-CH(CH3)-CH2-, or -O-CH2-CH(CH3)-. However, if m is 0, then n is also 0. Here, if o is greater than 1, each structural unit Q can be selected independently of other structural units Q.

[0144] In summary, particularly favorable results were obtained using the agent of the present invention, which contains the following: (a3) At least one alkoxylated fatty acid ester of general formula (AFE-I), [ka] Here, R1 is saturated or unsaturated C 11- C 29 Represents an alkyl group, R2 and R3 both represent hydrogen atoms. n represents the number 0, m represents the number 1, o represents an integer from 1 to 30, preferably from 1 to 20, more preferably from 1 to 10, and most preferably from 1 to 5. Q represents the structural unit -O-CH(CH3)-CH2- or -O-CH2-CH(CH3)-.

[0145] In a more particularly preferred embodiment, the agent of the present invention is characterized by the following: (a3) At least one alkoxylated fatty acid ester of general formula (AFE-I) [ka] Here, R1 is saturated or unsaturated C 11- C 29 Represents an alkyl group, R2 and R3 both represent hydrogen atoms. n represents the number 0, m represents the number 1, o represents an integer from 1 to 30, preferably from 1 to 20, more preferably from 1 to 10, and most preferably from 1 to 5. Q represents the structural unit -O-CH(CH3)-CH2- or -O-CH2-CH(CH3)-.

[0146] A particularly preferred alkoxylated fatty acid ester of this embodiment also corresponds to the general formula (AFE-II): [ka] Here, R1 is saturated or unsaturated C 11- C 29 Represents an alkyl group, o represents an integer from 1 to 30, preferably from 1 to 20, more preferably from 1 to 10, and most preferably from 1 to 5, and Q represents the structural unit -O-CH(CH3)-CH2- or -O-CH2-CH(CH3)-.

[0147] In a more particularly preferred embodiment, the agent of the present invention is characterized by the following: (a3) Containing at least one alkoxylated fatty acid ester of general formula (AFE-II), [ka] Here, R1 is saturated or unsaturated C 11- C 29 Represents an alkyl group, o represents an integer from 1 to 30, preferably from 1 to 20, more preferably from 1 to 10, and most preferably from 1 to 5, and Q represents the structural unit -O-CH(CH3)-CH2- or -O-CH2-CH(CH3)-.

[0148] Furthermore, if o is greater than 1, each structural unit Q can be selected independently of other structural units Q.

[0149] In the alkoxylated fatty acid ester of general formula (AFE-II), the structural unit Q is arranged such that in the group -O-CH(CH3)-CH2- and / or -O-CH2-CH(CH3)-, the oxygen atom is adjacent to the benzyl group, and each of the units -CH2- or -CH(CH3)- is adjacent to the ester group of -OC(O)-R1.

[0150] One compound that is explicitly very particularly suitable for this type is PPG-3 benzyl ether myristate, also known as α-(1-oxotetradecyl)-ω-(phenylmethoxy)poly[oxy(methyl-1,2-ethanediyl)], which has CAS number 642443-86-5.

[0151] PPG-3 benzyl ether myristate can be purchased, for example, from Croda under the brand name Crodamol STS.

[0152] Furthermore, with respect to a very particular embodiment, the agent of the present invention is (a3) Contains PPG-3 benzyl ether myristate It is characterized by the following.

[0153] Further types, C 12- C 30 Fatty acids and aromatic C 1- C 12 The addition product of ethylene oxide with an alcohol ester (a3) ​​is C 1- In the case of esters with C6 alkylene oxides, the ester is a C6 alkylene oxide having at least one hydroxyl group. 12- C 30 Fatty acids and C 1- C 12 It is obtained by esterification with aromatic alcohols. For example, hemasioleic acid ((9Z,12R)-12-hydroxy-9-octadecenoic acid) can first be esterified with benzyl alcohol, phenol, 2-phenylethyl alcohol, or 2-phenoxyethanol. When these adducts are formed, then C 1-A C6 alkylene oxide is added to the hydroxyl group of castor oil acid.

[0154] 1 mole of carbon per mole of fatty acid 1- When reacting with C6 alkylene oxides, for example, using ethylene oxide as the alkylene oxide, one unit of *-CH2-CH2-O-* can be added to the hydroxyl group of castor oil acid. However, depending on the molar excess of ethylene oxide used, multiple adducts can also be formed that have multiple units of *-CH2-CH2-O-* added to each hydroxyl group of the fatty acid, and / or also have multiple units of *-CH2-CH2-O-* added to each free hydroxyl group of glycerol. 12- C 30 Fatty acids and C 1- C 12 C to esterification with aromatic alcohols 1- These addition products of C6 alkylene oxides also conform to the present invention.

[0155] In the agent of the present invention, an alkoxylated fatty acid ester (a3) ​​in a specific range of amounts is particularly preferred.

[0156] Particularly good results were obtained when the agent contained one or more alkoxylated fatty acid esters (a3) ​​in a total amount of 0.1 to 20.0% by weight, preferably 0.5 to 15.0% by weight, more preferably 1.0 to 10.0% by weight, even more preferably 1.0 to 6.0% by weight, and most preferably 1.0 to 1.8% by weight, based on the total weight of the agent.

[0157] Within the scope of further preferred embodiments, the agent of the present invention is characterized by containing one or more alkoxylated fatty acid esters (a3) ​​in a total amount of 0.1 to 20.0% by weight, preferably 0.5 to 15.0% by weight, more preferably 1.0 to 10.0% by weight, even more preferably 1.0 to 6.0% by weight, and very preferably 1.0 to 1.8% by weight, based on the total weight of the agent.

[0158] In the research leading to the present invention, it was found that the presence of one or more of the aforementioned alkoxylated fatty acid esters (a3) ​​allows the coloring compounds (a2) (especially when they are pigments) to be optimally dispersed in the agent of the present invention. It is believed that pigments thus finely dispersed in the agent can be applied to keratinous materials in the form of very uniform, fine, and resistant films, which means that the friction fastness properties of the resulting coloring are particularly good. Furthermore, this particularly fine dispersion of pigments in the agent is also thought to be the cause of the good wash fastness achievable with the agent of the present invention.

[0159] Therefore, when alkoxylated fatty acid ester (a3) ​​is included in the agent of the present invention as the main dispersing aid or additive, very good results were obtained. Further research will lead to further C 1- It was also shown that this effect can be further enhanced when the C6 alkylene oxide addition product (a4) is added to the composition.

[0160] [Aliphatic C 1- C 24 C to Alkanol (a4) 1- [Addition product of C6 alkylene oxide] The group of substances (a4) that are particularly effective as further dispersion additives is C 1- C 24 C to Alkanol 1- It is an addition product of C6 alkylene oxide.

[0161] In the following, aliphatic C 1- C 24 C to Alkanol 1- The addition product of C6 alkylene oxide (a4) is also referred to as alkoxylated alkanol in its abbreviated form.

[0162] Therefore, within the scope of a particularly preferred embodiment, the agent of the present invention is a4) At least one aliphatic C 1- C 24 C to Alkanol 1- Addition product of C6 alkylene oxide (a4) It is further characterized by including.

[0163] According to the present invention, a suitable C 1- C6 alkylene oxides, as well as preferred and particularly preferred examples thereof, have already been defined in the previous section.

[0164] According to the present invention, C 1- C 24Alkanols are compounds having 1 to 14 carbon atoms and hydroxyl groups. Possible examples include: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, 1-octanol, 2-octanol, 3-octanol, 4-octanol, 1-nonanol, 2-nonanol, 3-nonanol, 4-nonanol, 5-nonanol Dodecanol, 1-decanol, 2-decanol, 3-decanol, 4-decanol, 5-decanol, 1-undecanol, 2-undecanol, 3-undecanol, 4-undecanol, 5-undecanol, 6-undecanol, 1-dodecanol, 2-dodecanol, 3-dodecanol, 4-dodecanol, 5-dodecanol, 6-dodecanol, 1-tridecanol, 2-tridecanol, 3-tridecanol, 4-tridecanol, 5-tridecanol, 6-tridecanol, 7-tridecanol Canol, 1-Tetradecanol, 2-Tetradecanol, 3-Tetradecanol, 4-Tetradecanol, 5-Tetradecanol, 6-Tetradecanol, 7-Tetradecanol, 1-Pentadecanol, 2-Pentadecanol, 3-Pentadecanol, 4-Pentadecanol, 5-Pentadecanol, 6-Pentadecanol, 7-Pentadecanol, 8-Pentadecanol, 1-Hexadecanol, 2-Hexadecanol, 3-Hexadecanol, 4-Hexadecanol, 5-Hexadecanol 6-Hexadecanol, 7-Hexadecanol, 8-Hexadecanol, 1-Heptadecanol, 2-Heptadecanol, 3-Heptadecanol, 4-Heptadecanol, 5-Heptadecanol, 6-Heptadecanol, 7-Heptadecanol, 8-Heptadecanol, 1-Octadecanol, 2-Octadecanol, 3-Octadecanol, 4-Octadecanol, 5-Octadecanol, 6-Octadecanol, 7-Octadecanol, 8-Octadecanol, 9-Octadecanol.

[0165] Aliphatic C is particularly well suited. 1- C24 C to Alkanol 1- The addition product of the C6 alkylene oxide (a4) is a compound of general formula (AA-I): [ka] Here, R4 is saturated or unsaturated C 1- C 24 Represents an alkyl group, P represents the structural unit -O-CH2-CH2-, -O-CH(CH3)-CH2-, or -O-CH2-CH(CH3)-, and s represents an integer between 1 and 60.

[0166] Group R4 is saturated or unsaturated C 1- C 24 Represents an alkyl group. The group R4 may be unsaturated due to the number of carbon atoms of at least two C atoms. Unsaturated C 2- C 24 Alkyl groups may contain one or more double bonds, or C 2- C 24 Also called an alkenyl group. Saturated or unsaturated C 1- C 24 The alkyl group may be linear or branched.

[0167] Particularly preferred is that the R4 group is saturated, unbranched C 1- C 12 This represents an alkyl group. In particular, the remaining R4 is saturated, unbranched carbon. 1- Represents a C6 alkyl group.

[0168] In the compound of formula (AA-I), P represents the structural unit -O-CH2-CH2-, -O-CH(CH3)-CH2-, or -O-CH2-CH(CH3)-. The number of structural units in the compound of formula (AA-I) is determined by the index s. In this case, the structural unit P is oriented such that in each group -O-CH2-CH2-, -O-CH(CH3)-CH2-, and -O-CH2-CH(CH3)-, the oxygen atom is adjacent to the alkyl group R4, and each unit -CH2- or -CH(CH3)- is adjacent to the hydroxyl group -OH.

[0169] If s is greater than 1, multiple structural units P are present in the compound of formula (AA-I). In this case, each structural unit P can be selected independently of the other structural units P.

[0170] The index number s represents an integer from 1 to 60, preferably from 1 to 40, more preferably from 10 to 30, and most preferably from 10 to 20.

[0171] Therefore, within the scope of further particularly preferred embodiments, the agent of the present invention is further characterized by comprising the following: (a4) At least one aliphatic C of formula (AA-I) 1- C 24 - C to Alkanol 1- C 6- Alkylene oxide adduct products [ka] Here, R4 is saturated or unsaturated C 1- C 24 Alkyl alkyl group, preferably C 1- C 12 Alkyl alkyl groups, particularly preferably C 1- Represents a C6 alkyl group, P represents the structural unit -O-CH2-CH2-, -O-CH(CH3)-CH2-, or -O-CH2-CH(CH3)-, and s represents an integer between 1 and 60, preferably between 1 and 40, more preferably between 10 and 30, and most preferably between 10 and 20.

[0172] C 1- C6 alkylene oxide and aliphatic C of formula (AA-i) 1- C 24 A particularly suitable adduct with alkanols is propylene glycol monobutyl ether, also known as PPG-14 butyl ether, with CAS number 9003-13-8. PPG-14 butyl ether is commercially available from Dow under the trade name Ucon Fluid AP.

[0173] Therefore, within the scope of further particularly preferred embodiments, the agent of the present invention is (a4) PPG-14 butyl ether It is further characterized by including.

[0174] It is particularly preferable that the amount of alkoxylated alkanol (a4) in the agent of the present invention be within a specific range.

[0175] Particularly good results were obtained when the agent contained one or more alkoxylated alkanols (a4) in a total amount of 0.1 to 20.0% by weight, preferably 0.2 to 15.0% by weight, more preferably 0.3 to 10.0% by weight, even more preferably 0.4 to 5.0% by weight, and most preferably 0.5 to 3.0% by weight, based on the total weight of the agent.

[0176] Within the scope of further preferred embodiments, the agent of the present invention contains, based on the total weight of the agent, one or more aliphatic C in a total amount of 0.1 to 20.0% by weight, preferably 0.2 to 15.0% by weight, more preferably 0.3 to 10.0% by weight, even more preferably 0.4 to 5.0% by weight, even more preferably 0.5 to 3.0% by weight, and most preferably 0.5 to 1.5% by weight. 1- C 24 C to Alkanol 1- It is characterized by containing the addition product (a4) of a C6 alkylene oxide.

[0177] [Pharmaceutical pH value] The pH value of the agent of the present invention is preferably adjusted to a slightly acidic to alkaline pH value. Most preferably, the agent has an alkaline pH in the range of 3.8 to 11.5, preferably 4.0 to 10.0, more preferably 5.0 to 9.0, and most preferably 6.0 to 8.0.

[0178] Within the scope of further particularly preferred embodiments, the device conforms to the present invention. The agent contains water and has a pH of 3.8 to 11.5, preferably 4.0 to 10.0, more preferably 5.0 to 9.0, and most preferably 6.0 to 8.0.

[0179] To adjust the desired pH, the agent of the present invention may contain at least one acidifying agent and / or alkalizing agent. The pH value for the purposes of the present invention is the pH value measured at a temperature of 22°C.

[0180] As an alkalizing agent, the agent may contain, for example, ammonia, alkanolamines, and / or basic amino acids.

[0181] The alkanolamines usable in the agent of the present invention are C having at least one hydroxyl group. 2- Preferably selected from primary amines having a C6 alkyl base. Preferred alkanolamines are selected from the group made up of the following: 2-aminoethane-1-ol (monoethanolamine), 3-aminopropane-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1-aminopropane-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropane-1-ol, 1-amino-2-methylpropane-2-ol, 3-aminopropane-1,2-diol, 2-amino-2-methylpropane-1,3-diol.

[0182] Particularly preferred alkanolamines for the present invention are selected from 2-aminoethane-1-ol and / or 2-amino-2-methylpropane-1-ol. Therefore, a particularly preferred embodiment is characterized in that the agent of the present invention contains an alkanolamine selected from 2-aminoethane-1-ol and / or 2-amino-2-methylpropane-1-ol as the alkalizing agent.

[0183] For the purposes of the present invention, an amino acid is an organic compound containing at least one protonable amino group and at least one -COOH or -SO3H group in its structure. Preferred amino acids are aminocarboxylic acids, particularly α-(alpha)-aminocarboxylic acids and ω-aminocarboxylic acids, where α-aminocarboxylic acids are especially preferred.

[0184] According to the present invention, a basic amino acid is an amino acid having an isoelectric point pI greater than 7.0.

[0185] Basic α-aminocarboxylic acids contain at least one chiral carbon atom. In relation to the present invention, both possible enantiomers can be used equally as specific compounds or mixtures thereof, particularly as racemates. However, it is particularly advantageous to use the naturally preferred isomer form (usually the L-configuration).

[0186] The basic amino acid is preferably selected from the group formed from arginine, lysine, ornithine, and histidine, and particularly preferably selected from the group formed from arginine and lysine. Therefore, in another particularly preferred embodiment, the agent of the present invention is characterized in that the alkalizing agent is a basic amino acid selected from the group formed from arginine, lysine, ornithine, and / or histidine.

[0187] Furthermore, the product may contain other alkalizing agents, particularly inorganic alkalizing agents. Inorganic alkalizing agents usable according to the present invention are preferably selected from the group formed from sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, sodium metasilicate, potassium silicate, sodium carbonate, and potassium carbonate.

[0188] Particularly preferred alkalizing agents are ammonia, 2-aminoethane-1-ol (monoethanolamine), 3-aminopropane-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1-aminopropane-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropane-1-ol, 1-amino-2-methylpropane-2-ol, 3-aminopropane-1,2-diol, 2-amino-2-methylpropane-1,3-diol, arginine, lysine, ornithine, histidine, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, sodium metasilicate, potassium silicate, sodium carbonate, and potassium carbonate.

[0189] In another very particular embodiment, the method of the present invention is characterized in that the colorant comprises at least one alkalizing agent selected from the group consisting of: ammonia, 2-aminoethane-1-ol (monoethanolamine), 3-aminopropane-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1-aminopropane-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropane-1-ol, 1-amino-2-methylpropane-2-ol, 3-aminopropane-1,2-diol, 2-amino-2-methylpropane-1,3-diol, arginine, lysine, ornithine, histidine, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, sodium metasilicate, potassium silicate, sodium carbonate, and potassium carbonate.

[0190] To adjust the desired pH, the agent of the present invention may include at least one buffer system comprising at least one inorganic or organic acid and at least one salt of said acid.

[0191] Potassium dihydrogen phosphate is a particularly suitable inorganic acid.

[0192] Potassium dihydrogen phosphate has the molecular formula KH2PO4 and CAS number 7778-77-0. It has a molecular weight of 136.09 g / mol. It is highly soluble in water (222 g / l at 20°C) and reacts acidically in water. A 5% aqueous solution of potassium dihydrogen phosphate has a pH of 4.4.

[0193] Another particularly suitable inorganic acid (b2-I) is sodium dihydrogen phosphate. Sodium dihydrogen phosphate has the molecular formula NaH2PO4 and CAS numbers 7558-80-7 (anhydrous), 10049-21-5 (monohydrate), and 13472-35-0 (dihydrate). Anhydrous sodium dihydrogen phosphate has a molecular weight of 119.98 g / mol. Sodium dihydrogen phosphate reacts acidically in aqueous solution.

[0194] A particularly preferred corresponding salt for the two acids mentioned above is dipotassium hydrogen phosphate. Dipotassium hydrogen phosphate has the molecular formula K2HPO4 and CAS numbers 7758-11-4 (anhydrous) and 16788-57-1 (trihydrate). Anhydrous dipotassium hydrogen phosphate has a molecular weight of 174.18 g / mol. Dipotassium hydrogen phosphate reacts with alkaline substances in aqueous solution.

[0195] Furthermore, a particularly preferred salt of the two acids (b2-II) mentioned above is disodium hydrogen phosphate. Disodium hydrogen phosphate has the molecular formula Na2HPO4 and CAS numbers 7558-79-4 (anhydrous), 10028-24-7 (dihydrate), 7782-85-6 (heptahydrate), and 10039-32-4 (dodecahydrate). Anhydrous disodium hydrogen phosphate has a molecular weight of 141.96 g / mol. Disodium hydrogen phosphate reacts alkalinely in aqueous solution.

[0196] [Any other formulation components in the drug] As already described, in addition to components (a1), (a2), (a3), and optionally (a4), which are essential or particularly preferred for the present invention, the agent may further contain any other components.

[0197] As a further optional component, the agent of the present invention may additionally contain at least one fatty component. A suitable fatty component is C 12- C 24 Fatty alcohols, C 12- C 24 Fatty acid triglycerides, C 12- C 24Fatty acid monoglycerides, C 12- C 24 A selection may be made from the group consisting of fatty acid diglycerides and / or hydrocarbons.

[0198] C 12- C 24 Fatty alcohols can be saturated, mono- or polyunsaturated, linear or branched fatty alcohols having 12 to 24 carbon atoms.

[0199] Preferred linear, saturated C 12- C 24 Examples of fatty alcohols include dodecane-1-ol (dodecyl alcohol, lauryl alcohol), tetradecane-1-ol (tetradecyl alcohol, myristyl alcohol), hexadecane-1-ol (hexadecyl alcohol, cetyl alcohol, palmityl alcohol), octadecane-1-ol (octadecyl alcohol, stearyl alcohol), arachidyl alcohol (eicosan-1-ol), heneicosyl alcohol (heneicosan-1-ol), and / or behenyl alcohol (docosane-1-ol).

[0200] Preferred linear, unsaturated fatty alcohols are (9Z)-octadeca-9-en-1-ol (oleyl alcohol), (9E)-octadeca-9-en-1-ol (elaidyl alcohol), (9Z,12Z)-octadeca-9,12-dien-1-ol (linoleyl alcohol), (9Z,12Z,15Z)-octadeca-9,12,15-trien-1-ol (linolenoyl alcohol), gadleyl alcohol ((9Z)-eicosa-9-en-1-ol), arachidone alcohol ((5Z,8Z,11Z,14Z)-eicosa-5,8,11,14-tetraen-1-ol), erucyl alcohol ((13Z)-docosa-13-en-1-ol) and / or brassidyl alcohol ((13E)-docosen-1-ol).

[0201] Preferred examples of branched fatty alcohols are 2-octyl-dodecanol, 2-hexyl-dodecanol, and / or 2-butyl-dodecanol. One or more C in a fairly specific range of amounts. 12- C 24 It was found that using fatty alcohols is highly preferable.

[0202] The agent contains one or more C in a total amount of 2.0 to 50.0% by weight, preferably 3.0 to 30.0% by weight, more preferably 4.0 to 20.0% by weight, even more preferably 5.0 to 15.0% by weight, and most preferably 5.0 to 10.0% by weight, based on the total weight of the agent. 12- C 24 It is particularly preferable if it contains fatty alcohols.

[0203] Furthermore, the agent may contain at least one preservative. The following substances and mixtures thereof can be used as preservatives: Aromatic alcohols, such as phenoxyethanol, benzyl alcohol, phenethyl alcohol, phenoxyisopropanol, etc. Formaldehyde solutions and aldehydes such as paraformaldehyde and glutaraldehyde. Parabens, such as methylparaben, ethylparaben, propylparaben, butylparaben, isobutylparaben 1,2-alkanediols having 5 to 22 carbon atoms in the carbon chain, for example, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-decanediol, 1,2-dodecanediol, 1,2-hexadecanediol, • Formaldehyde-releasing compounds, such as DMDM ​​hydantoin, diazolidinyl urea, • Halogenated compounds, e.g., isothiazolinone, e.g., methylchloroisothiazolinone, chloroisothiazolinone / methylisothiazolinone, triclosan, triclocarbane, iodopropynyl butylcarbamate, 5-bromo-5-nitro-1,3-dioxane, chlorhexidine digluconate, and chlorhexidine acetate, and 2-bromo-2-nitropropane-1,3-diol, methyldibromoglutaronitrile, • Inorganic compounds, such as sulfites, boric acid, and borates, bisulfites, etc. • Cationic substances, such as quaternium-15, benzalkonium chloride, benzatonium chloride, polyaminopropyl biguanide, etc. • Organic acids and their physiologically compatible salts, such as citric acid, lactic acid, acetic acid, benzoic acid, sorbic acid, salicylic acid, dehydroacetic acid, etc. • Active organisms with additional effects, such as zinc pyrithione, piroctonolamine, etc. Antioxidants, such as BHT (butylated hydroxytoluene), BHA (butylated hydroxyanisole), propyl gallate, t-butylhydroquinone, etc. • Complexing agents, such as EDTA and its derivatives, HEDTA and its derivatives, etidronic acid and its salts, etc.

[0204] If necessary, the agent of the present invention may additionally contain at least one surfactant, which is referred to as a surfactant or emulsifier, depending on the field of application: these are preferably selected from anionic, cationic, zwitterionic, amphoteric, and nonionic surfactants and emulsifiers.

[0205] Preferred anionic surfactants are fatty acids, alkyl sulfates, alkyl ether sulfates, and ether carboxylic acids having 10 to 20 carbon atoms in the alkyl group and 16 or fewer glycol ether groups in the molecule. The anionic surfactant is used in an amount of 0.1 to 45% by weight, preferably 1 to 30% by weight, and very preferably 1 to 15% by weight, based on the total amount of the immediately usable agent.

[0206] Preferred zwitterionic surfactants are betaine, N-alkyl-N,N-dimethylammonium glycinate, N-acylaminopropyl-N,N-dimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl-imidazoline. The preferred zwitterionic surfactant is known by the INCI name cocamidopropyl betaine.

[0207] Preferred amphoteric surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkylsarcosine, 2-alkylaminopropionic acid, and alkylaminoacetic acid. Particularly preferred amphoteric surfactants are N-cocoalkylaminopropionates such as cocoacylaminoethylaminopropionate and C 12- C 18 - It is acylsarcosine.

[0208] Preferred nonionic surfactants are alkyl polyglycosides and alkylene oxide adducts of fatty alcohols and fatty acids having 2 to 30 moles of ethylene oxide per mole of fatty alcohol or fatty acid. Formulations with excellent properties can also be obtained when the nonionic surfactant contains a fatty acid ester of ethoxylated glycerol.

[0209] Preferred quaternary ammonium compounds are ammonium halides and imidazolium compounds known by the INCI names quaternium-27 and quaternium-83. Other cationic surfactants usable according to the present invention are quaternary protein hydrolysates. Stearamidopropyldimethylamine, commercially available under the name Tegoamid® S 18, is a compound of the group of amidoamines that is particularly suitable for use in the present invention. Preferred ester quats are quaternary ester salts of fatty acids with triethanolamine, quaternary ester salts of fatty acids with diethanolalkylamine, and quaternary ester salts of fatty acids with 1,2-dihydroxypropyldialkylamine. Cationic surfactants are preferably present in the agent of the present invention in a proportion of 0.05 to 10% by weight based on the total agent.

[0210] The surfactant is preferably used in an amount of 0.1 to 45% by weight, preferably 1 to 30% by weight, and very preferably 1 to 15% by weight, based on the total amount of the agent.

[0211] Furthermore, the compositions of the present invention may additionally contain at least one solvent. Particularly suitable solvents can be selected from the group consisting of 1,2-propanediol, 1,3-propanediol, ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol, 1,2-butylene glycol, dipropylene glycol, ethylene carbonate, propylene carbonate, 2-phenoxyethanol, and benzyl alcohol.

[0212] The solvent is preferably used in a proportion of 0.1 to 45% by weight, preferably 1 to 30% by weight, and very preferably 1 to 15% by weight, based on the total amount of the agent.

[0213] To adjust the desired viscosity or optimal flow behavior, the agent of the present invention may additionally contain at least one polymeric thickener as a further optional component.

[0214] The following are examples of typical polymeric thickeners for aqueous or water-based systems: Acrylamide copolymer, acrylamide / sodium acrylate copolymer, acrylamide / sodium acryloyldimethyl taurate copolymer, acrylate / acetoacetoxyethyl methacrylate copolymer, acrylate / beheneth-25 methacrylate copolymer, acrylate / C10-30 alkyl acrylate crosspolymer, acrylate / ceteth-20 itaconate copolymer, acrylate / ceteth-20 methacrylate copolymer, acrylate / laureth-25 methacrylate copolymer, acrylate / palmes-25 acrylate copolymer, acrylate / palmes-25 itaconate copolymer, acrylate / steareth-50 acrylate copolymer, acrylate / steareth-20 itaconate copolymer, acrylate / steareth-20 methacrylate copolymer, acrylate / stearyl methacrylate copolymer, acrylate Relate / Vinyl Isodecanoate Crosspolymer, Acrylic Acid / Acrylonitrogen Copolymer, Agar, Agarose, Alcaligenes Polysaccharides, Algin, Alginic Acid, Ammonium Acrylate / Acrylonitrogen Copolymer, Ammonium Acrylate Copolymer, Ammonium Acryloyldimethyltaurate / Vinylformamide Copolymer, Ammonium Acryloyldimethyltaurate / VP Copolymer, Ammonium Alginate, Ammonium Polyacryloyldimethyltaurate, Amylopectin, Ascorbyl Methylsilanol Pectinate, Astragalus Gumifer Gum, Attapulgite, Avena Sativa (Oat) Kernel Flour, Bentonite, Butoxychitosan, Salpinia Spinosa Gum, Calcium Alginate, Calcium Carboxymethylcellulose, Calcium Carrageenan, Calcium Carbomer, Calcium Starch Octenylsuccinate, C Stearate 20-40Alkyl, Carbomer, Carboxybutyl Chitosan, Carboxymethyl Chitin, Carboxymethyl Chitosan, Carboxymethyl Dextran, Carboxymethyl Hydroxyethylcellulose, Carboxymethyl Hydroxypropyl Guar, Cellulose Acetate Carboxylate, Cellulose Gum, Ceratonia Silica Gum, Cetyl Hydroxyethylcellulose, Colesterol / HDI / Pullan Copolymer, Colesteryl Hexyl Dicarbamate Pullulan, Thymopsis Tetragonoroba (Guar) Gum, Diglycol / CHDM / Isophthalate Calcium acrylate / SIP copolymer, dihydrogenated tallow benzylmonium hectorite, dimethicone crosspolymer-2, dimethicone propyl PG-betaine, DMPA acrylate / acrylic acid / acrylonitrogen copolymer, ethylene / sodium acrylate copolymer, gelatin, gellan gum, glyceryl alginate, soybean flour, guar hydroxypropyltrimonium chloride, hectorite, hydrated silica, hydrogenated potato starch, hydroxybutyl methylcellulose, hydroxyethyl acrylate / acrylate / acryloyldimethyl taurate sodium Lithium copolymer, hydroxyethylcellulose, hydroxyethyl chitosan, hydroxyethyl ethylcellulose, hydroxypropylcellulose, hydroxypropyl chitosan, hydroxypropyl ethylenediamine carbomer, hydroxypropyl guar, hydroxypropyl methylcellulose, hydroxypropyl methylcellulose stearoxyl ether, hydroxypropyl starch, hydroxypropyl starch phosphate, hydroxypropyl xanthan gum, hydroxystearamide MEA, isobutylene / sodium maleate copolymer, lithium magnesium silicate, lithium magnesium sodium silicate, Macrocystis pyrifera (kelp), magnesium alginate, magnesium aluminum silicate, magnesium silicate, magnesium trisilicate, methoxy PEG-22 / dodecyl glycol copolymer, methylcellulose, methylethylcellulose, methylhydroxyethylcellulose, microcrystalline cellulose, montmorillonite, Moroccan lava clay, natto gum, nonoxynyl hydroxyethylcellulose, octadecene / MA copolymer, pectin,PEG-800, PEG-Crosspolymer, PEG-150 / Decyl Alcohol / SMDI Copolymer, PEG-175 Diisostearate, PEG-190 Distearate, PEG-15 Glyceryl Tristearate, PEG-140 Glyceryl Tristearate, PEG-240 / HDI Copolymer Bis-Decyltetradeceth-20 Ether, PEG-100 / IPDI Copolymer, PEG-180 / Laureth-50 / TMMG Copolymer, PEG-10 / Lauryl Dimethicone Crosspolymer, PEG-15 / Lauryl Dimethicone Crosspolymer PEG-2M, PEG-5M, PEG-7M, PEG-9M, PEG-14M, PEG-20M, PEG-23M, PEG-25M, PEG-45M, PEG-65M, PEG-90M, PEG-115M, PEG-160M, PEG-120 Methyl Glucose Trioleate, PEG-180 / Octoxynol-40 / TMMG Copolymer, PEG-150 Pentaerythrityl Tetrastearate, PEG-4 Rapeseed, PEG-150 / Stearyl Alcohol / SMDI Copolymer, Polyacrylate-3, Polyacrylic Acid, Polycyclopene Tadiene, Polyether-1, Polyethylene / Isopropyl Maleate / MA Copolyol, Polymethacrylic Acid, Polyquaternium-52, Polyvinyl Alcohol, Potassium Alginate, Potassium Aluminum Polyacrylate, Potassium Carbomer, Potassium Carrageenan, Potassium Polyacrylate, Modified Potato Starch, PPG-14 Laureth-60 Hexyl Dicarbamate, PPG-14 Laureth-60 Isophoryl Dicarbamate, PPG-14 Palmes-60 Hexyl Dicarbamate, Propylene Glycol Alginate, PVP / Decencopoly Mar, PVP montmorillonite, root herb gum, ricinoleic acid / adipic acid / AEEA copolymer, sclerotium gum, sodium acrylate / acryloyldimethyl taurate copolymer, sodium acrylate / acrolein copolymer, sodium acrylate / acrylonitrogen copolymer, sodium acrylate copolymer, sodium acrylate / isodecanoate vinyl crosspolymer, sodium acrylate / vinyl alcohol copolymer, sodium carbomer, sodium carboxymethyl chitin, sodium carboxymethyl dextran,Sodium carboxymethyl β-glucan, sodium carboxymethyl starch, sodium carrageenan, sodium cellulose sulfate, sodium cyclodextrin sulfate, sodium hydroxypropyl starch phosphate, sodium isooctylene / MA copolymer, sodium magnesium fluorosilicate, sodium polyacrylate, sodium starch polyacrylate, sodium polyacryloyldimethyl taurate, sodium polymethacrylate, sodium polystyrene sulfonate, sodium silicate aluminate, sodium octenyl succinate starch, sodium stearoyl PG-hydroxyethylcellulose sulfonate, sodium styrene / acrylic acid copolymer, tauri Sodium acrylate / acrylic acid / acrylonitrogen copolymer, potato starch, starch / acrylate / acrylamide copolymer, starch hydroxypropyltrimonium chloride, steareth-60 cetyl ether, steareth-100 / PEG-136 / HDI copolymer, sterlea urea gum, synthetic fluorphlogopite, tamarindus indica seed gum, tapioca starch, TEA-alginate, TEA-carbomer, durum wheat starch, tromethamine acrylate / acrylonitrogen copolymer, tromethamine magnesium aluminum silicate, gellan gum, xanthan gum, yeast β-glucan, yeast polysaccharides, zeamaze (corn) starch.

[0215] The polymeric thickener is preferably used in a proportion of 0.1 to 45% by weight, preferably 1 to 30% by weight, and very preferably 1 to 15% by weight, based on the total amount of the agent.

[0216] Furthermore, the agents of the present invention may also contain other active ingredients, auxiliary agents, and additives, such as: nonionic polymers (vinylpyrrolidone / vinyl acrylate copolymer, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymer, polyethylene glycol and polysiloxane, etc.); cationic polymers (quaternary cellulose ether, polysiloxane having a quaternary group, dimethyldiallylammonium chloride polymer, acrylamide-dimethyldiallylammonium chloride copolymer, diethyl sulfate quaternary dimethylamino-ethyl methacrylate-vinylpyrrolidone copolymer, vinylpyrrolidone-imidazolinium methchloride copolymer and quaternary polyvinyl alcohol, etc.); zwitter and amphoteric polymers (acrylamidopropyltrimethylammonium chloride / acrylate copolymer and octylacrylamide / methyl methacrylate / t-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymer, etc.); anionic polymers (polyacrylic acid, crosslinked polyacrylic acid, vinyl acetate / crotonic acid copolymer) MAR, vinylpyrrolidinone / vinyl acrylate copolymer, vinyl acetate / butyl maleate / isobornyl acrylate copolymer, methyl vinyl ether / maleic anhydride copolymer, acrylic acid / ethyl acrylate / Nt-butylacrylamide terpolymer, etc.); other thickeners (agar, guar gum, alginate, gum arabic, karaya gum, locust bean gum, flaxseed gum, dextran, cellulose derivatives, e.g., methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives) , for example, amylose, amylopectin and dextrin, clays such as bentonite, or fully synthetic hydrocolloids such as polyvinyl alcohol); structuring agents (glucose, maleic acid, lactic acid, etc.); hair conditioning compounds (phospholipids, soy lecithin, egg lecithin and cephalin, as well as silicone oils, etc.); protein hydrolysates (especially elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids, and quaternary protein hydrolysates);Fiber structure improving active ingredients (especially monosaccharides, disaccharides, and oligosaccharides such as glucose, galactose, fructose, fructose, and lactose); defoaming agents (silicone, preferably dimethicone, etc.); dyes for coloring the agent; anti-dandruff active ingredients (piroctone olamine, zinc omazine, crimbazole, etc.); light stabilizers or UV blockers (especially derivatized benzophenone, cinnamic acid derivatives, and triazines); active ingredients (panthenol, pantothenic acid, pantolactone, allantoin, pyrrolidinone carboxylic acid and its salts, bisabolol, etc.); vitamins, provitamins, and vitamin precursors (especially those of groups A, B3, B5, B6, C, E, F, and H). Cholesterol; viscosity improvers (such as sugar esters, polyol esters, or polyol alkyl ethers); fatty acid alkanolamides; swelling and penetrating agents (such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidine, urea, and primary, secondary, and tertiary phosphates); opacifiers (such as latex, styrene / PVP, and styrene / acrylamide copolymers); pearlescent agents (such as ethylene glycol mono- and distearate, and PEG-3 distearate); pigments; fragrances; foaming agents (such as propane-butane mixtures, N2O, dimethyl ether, CO2, and air) and antioxidants.

[0217] The selection of these other substances will be made by experts according to the desired properties of the agent. For further optional components, as well as the amounts of these components used, refer explicitly to the relevant manual known to those skilled in the art, e.g., Kh. Schrader, Grundlagen und Rezepturen der Kosmetika, 2nd edition, Huethig Buch Verlag, Heidelberg, 1989.

[0218] [Moisture content in the preparation] The agents described above are ready-to-use agents that can be applied to keratinous substances. These ready-to-use agents preferably have a high water content. Based on the total weight of the agent, agents containing 50.0 to 98.0% by weight, preferably 60.0 to 90.0% by weight, and especially preferably 70.0 to 90.0% by weight of water were found to be particularly suitable.

[0219] In a further explicitly particularly preferred embodiment, the agent of the present invention is characterized by containing 50.0 to 98.0% by weight, preferably 60.0 to 90.0% by weight, and particularly preferably 70.0 to 90.0% by weight, of water based on the total weight of the agent.

[0220] [Methods for staining keratinous substances] The agents described above can be used effectively in methods for dyeing keratinous substances, especially human hair.

[0221] Therefore, the second subject of the present invention is a method for coloring keratinous substances, particularly human hair, comprising the following steps: (1) A step of applying a coloring agent to a keratinous substance, wherein the coloring agent is an agent as described in detail in the first subject matter description of the present invention. (2) The step of exposing the coloring agent to a keratinous substance, (3) The step of rinsing off the dye.

[0222] In step (1) of the method of the present invention, the agent of the first invention is applied to a keratinous substance (most preferably human hair).

[0223] In step (2) of the method of the present invention, the agent is then allowed to act on the keratinous material after its application. In this regard, different exposure times, for example, from 30 seconds to 60 minutes, are possible.

[0224] However, the main advantage of the staining system according to the present invention is that strong color results can be achieved even in a very short time after a short exposure time. For this reason, it is advantageous if the coating mixture remains on the keratin material for a relatively short period after its application, for only 30 seconds to 15 minutes, preferably 30 seconds to 10 minutes, and particularly preferably 1 to 5 minutes.

[0225] In a further preferred embodiment, the method of the present invention is characterized by the following: (2) Exposure of a keratinous substance to a coloring agent for a period of time ranging from 30 seconds to 15 minutes, preferably 30 seconds to 10 minutes, most preferably 1 to 5 minutes.

[0226] After the coating mixture is applied to the keratin substance, it is finally washed off in step (3) of the process.

[0227] In one embodiment, the application mixture can be washed off with water alone, i.e., without the help of a post-treatment agent or shampoo. In principle, it is also conceivable to use a post-treatment agent or conditioner after step (3).

[0228] [A method for staining keratinous substances, which involves first preparing an agent that can be used immediately.] As previously described, the agent of the first subject matter of the present invention is an immediately applicable agent, which is either provided directly to the user in an immediately applicable form or prepared by mixing various agents immediately before application.

[0229] To ensure particularly fine dispersion of the pigment, it has been found that it is especially preferable to prepare a ready-to-use agent immediately before application by mixing two or three different agents.

[0230] Therefore, in a particularly preferred embodiment, a ready-to-use agent is prepared by mixing at least two different agents, the first of which comprises a mixture of an alkoxylated fatty acid ester (a3) ​​and a color-imparting compound, particularly a pigment (a2). For example, the mixture of the alkoxylated fatty acid ester (a3) ​​and the pigment (a2) may represent a predispersion provided in the form of a concentrate. The second agent comprises at least one amino-functionalized silicone polymer (a1) and may be, for example, a cosmetic carrier formulation containing water. The present invention also applies when the first agent comprising the mixture of the alkoxylated fatty acid ester (a3) ​​and the pigment (a2) is a cosmetic carrier formulation containing water, and the second agent comprising the amino-functionalized silicone polymer (a1) is in the form of a concentrate. The two aforementioned agents are then shaken or stirred together to prepare a ready-to-use agent.

[0231] Furthermore, the present invention also relates to a ready-to-use colorant prepared by mixing three pre-prepared separately agents, wherein the first agent is a predispersion of an alkoxylated fatty acid ester (a3) ​​and a pigment (a2), the second mixture comprises an amino-functionalized silicone polymer (a1), which may be in the form of a concentrate, for example, and the third agent is a water-containing cosmetic carrier formulation which preferably contains at least one alkoxylated alkanol (a4).

[0232] Therefore, a further subject of this application is a method for coloring keratinous materials, particularly human hair, comprising the following steps: (1) A step of providing agent (I), wherein agent (I) is as follows: (a2) at least one pigment, and (a3) at least one C 12- C 30 Fatty acids and C 1- C 12 C to esterification with aromatic alcohols 1- C6 alkylene oxide addition product including, (2) A step of providing agent (II), wherein agent (II) is as follows: (a1) at least one amino-functionalized silicone polymer including, and (3) A step of preparing a coating mixture by mixing agent (I) with agent (II), (4) A step of applying the coating mixture prepared in step (3) to a keratinous substance, (5) A step of exposing the coating mixture applied in step (4) to a keratinous substance; and (6) The step of rinsing off the coating mixture with water, Here, components (a1), (a2), and (a3) ​​have already been described in detail in the description of the first subject matter of the present invention.

[0233] In connection with this embodiment, optionally additionally applicable alkoxylated alkanols (a4) may be present, for example, in agent (I) and / or agent (II).

[0234] Depending on the selected pH, the storage stability of aminosilicone (a3) ​​may decrease in an aqueous environment. In such cases, it may be advantageous to use the amino-functionalized silicone polymer (a3) ​​in a separate agent and mix both components (a1) and (a2) with the aminosilicone (a3) ​​together with the base formulation immediately before use. In this case, at least three different agents are mixed together to produce a ready-to-use colorant.

[0235] Therefore, a method for dyeing keratinous substances, particularly human hair, comprising the following steps is especially preferred: (1) A step of providing agent (I), wherein agent (I) is as follows: (a2) at least one pigment, and (a3) at least one C 12- C 30 Fatty acids and C 1- C 12 C to esterification with aromatic alcohols 1- C6 alkylene oxide addition product including, (2) A step of providing agent (II), wherein agent (II) is as follows: (a1) at least one amino-functionalized silicone polymer including, and (3) A step of providing agent (III), wherein agent (III) is as follows: (a4) At least one aliphatic C 1- C 24 C to Alkanol 1- Addition product of C6 alkylene oxide (a4) including, and (4) A step of preparing a coating mixture by mixing agent (I) with agent (II) and optionally agent (III), (5) A step of applying the coating mixture prepared in step (4) to a keratinous substance, (6) A step of exposing the coating mixture applied in step (5) to a keratinous substance; and (7) The step of rinsing off the coating mixture with water. Here, components (a1), (a2), (a3), and (a4) have already been described in detail in the description of the first subject matter of the present invention.

[0236] In relation to this embodiment, agent (I) represents a preliminary dispersion of pigment (a2) in an alkoxylated fatty acid ester (a3), which may be in the form of a concentrate, for example. Agent (II) is also preferably a concentrate containing an amino-functionalized silicone polymer (a1).

[0237] Next, before application, the two agents or concentrates (I) and (II) are mixed with the carrier formulation (III). In this embodiment, the cosmetic carrier formulation or agent (III) contains an alkoxylated alkanol (a4).

[0238] The order of mixing is arbitrary. Therefore, agents (I) and (II) can be mixed first, and then the mixture can be mixed with agent (III). Similarly, agents (II) and (III) can be mixed first, and then the mixture can be mixed with agent (I). Alternatively, all three agents (I), (II), and (III) can be added together and then mixed by first permeation or stirring.

[0239] The carrier formulation contains water and preferably has a high water content. Any further applicable components of the first invention may also be included in the carrier formulation.

[0240] With regard to further preferred embodiments of the method of the present invention, the provisions described with respect to the agent of the present invention will be applied mutatis mutandis. The initial disclosures of this specification include at least the following aspects: [1] (a1) at least one amino-functionalized silicone polymer, and (a2) at least one color-imparting compound, and (a3) at least one C 12- C 30 Fatty acids and C 1- C 12 C to esterification with aromatic alcohols 1- C 6 Alkylene oxide adduct products A keratinous substance containing, especially an agent for dyeing human hair. [2] The agent according to [1], characterized by comprising at least one amino-functionalized silicone polymer (a1) having at least one secondary amino group. [3] Formula (Si-amino): JPEG0007874633000024.jpg8079 [In the formula, ALK1 and ALK2 independently form linear or branched C 1- C 20 [Represents a divalent alkylene group] The agent according to any one of [1] to [2], characterized by comprising at least one amino-functionalized silicone polymer (a1) having at least one structural unit of . [4] Equations (Si-I) and (Si-II): TIFF0007874633000025.tif87148 The agent according to any one of [1] to [3], characterized by comprising at least one amino-functionalized silicone polymer (a1) containing the structural unit of . [5] The agent according to any one of [1] to [4], characterized in that it contains 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 preferably 0.4 to 2.5% by weight, based on the total weight of the agent. [6] The agent according to any one of [1] to [5], characterized by comprising at least one coloring compound (a2) selected from the group consisting of pigments, direct dyes, photochromic dyes and thermochromic dyes. [7] The agent according to any one of [1] to [6], characterized by comprising at least one coloring compound (a2) selected from the group of inorganic pigments, preferably selected from the group of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, complex metal cyanides, metal sulfates, and bronze pigments, and / or colored mica or mica-based pigments coated with at least one metal oxide and / or metal oxychlorides. [8] Preferably, a blue pigment having color index numbers CI42090, CI69800, CI69825, CI73000, CI74100, CI74160; a yellow pigment having color index numbers CI11680, CI11710, CI15985, CI19140, CI20040, CI21100, CI21108, CI47000, CI47005; a green pigment having color index numbers CI61565, CI61570, CI74260; and a pigment having color index numbers CI11725, CI15510, CI45370, CI71105. The agent according to any one of [1] to [7], characterized by comprising at least one coloring compound (a2) selected from the group of organic pigments, which is selected from the group consisting of an orange pigment and a red pigment having color index numbers CI12085, CI12120, CI12370, CI12420, CI12490, CI14700, CI15525, CI15580, CI15620, CI15630, CI15800, CI15850, CI15865, CI15880, CI17200, CI26100, CI45380, CI45410, CI58000, CI73360, CI73915, and / or CI75470. [9] The agent according to any one of [1] to [8], characterized in that it contains one or more pigments (a2) 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 very preferably 0.25 to 1.5% by weight, based on the total weight of composition (a).

[10] (a3) ​​at least one C 12- C 24 A fatty acid and C selected from the group consisting of benzyl alcohol, phenol, 2-phenylethyl alcohol and 2-phenoxyethanol, very preferably selected from the group consisting of benzyl alcohol. 1- C 12 C to the ester obtained by esterification with aromatic alcohols 1- C 6 Alkylene oxide adduct products The agent according to any one of [1] to [9], characterized by containing the following:

[11] (a3) ​​General formula (AFE-I): TIFF0007874633000026.tif52144 [In the formula, R 1 C is saturated or unsaturated 11- C 29 Represents an alkyl group, R 2 、R 3 These are, independently, hydrogen atoms, C 1- C 6 Alkyl group, hydroxyl group or C 1- C 6 Represents an alkoxy group, n represents a number that is either 0 or 1. m represents an integer from 0 to 6. o represents an integer from 1 to 60, and Q is -O-CH 2 -CH 2 -, -O-CH(CH 3 )-CH 2 -, or -O-CH 2 -CH(CH 3 )- represents a structural unit, However, if m is 0, then n is also 0. at least one alkoxylated fatty acid ester The agent according to any one of [1] to

[10] , characterized by containing the following:

[12] (a3) ​​At least one alkoxylated fatty acid ester of general formula (AFE-I) A feature comprising, where, R 1 C is saturated or unsaturated 11- C 29 Represents an alkyl group, R 2 、R 3 Both represent a hydrogen atom, n represents the number 0, m represents the number 1, o represents an integer from 1 to 30, preferably from 1 to 20, more preferably from 1 to 10, and most preferably from 1 to 5. Q is a structural unit -O-CH(CH 3 )-CH 2 -or-O-CH 2 -CH(CH 3 )-is, The agent described in

[11] .

[13] The agent according to any one of [1] to

[12] , characterized in that it contains one or more alkoxylated fatty acid esters (a3) ​​in a total amount of 0.1 to 20.0% by weight, preferably 0.5 to 15.0% by weight, more preferably 1.0 to 10.0% by weight, even more preferably 1.0 to 6.0% by weight, and most preferably 1.0 to 1.8% by weight, based on the total weight of the agent.

[14] a4) At least one aliphatic C 1- C 24 C to Alkanol 1- C 6 It contains an alkylene oxide addition product (a4). A drug characterized by any of the following, as described in [1] to

[13] .

[15] (a4) Formula (AA-I): TIFF0007874633000027.tif3377 [Here, R 4 C is saturated or unsaturated 1- C 24 Alkyl alkyl group, preferably C 1- C 12 Alkyl alkyl groups, particularly preferably C 1- C 6 Represents an alkyl group, P is a structural unit -O-CH 2 -CH 2 -, -O-CH(CH 3 )-CH 2 -, or -O-CH 2 -CH(CH 3 )- represents and [s represents an integer between 1 and 60, preferably between 1 and 40, more preferably between 10 and 30, and most preferably between 10 and 20] aliphatic C 1- C 24 To Alkanol, C 1- C 6 It contains at least one addition product of alkylene oxide. The agent according to any one of [1] to

[14] , characterized by containing the following:

[16] Based on the total weight of the agent, one or more aliphatic C in a total amount of 0.1 to 20.0% by weight, preferably 0.2 to 15.0% by weight, more preferably 0.3 to 10.0% by weight, even more preferably 0.4 to 5.0% by weight, even more preferably 0.5 to 3.0% by weight, and most preferably 0.5 to 1.5% by weight. 1- C24 C to Alkanol 1- C 6 The agent according to any one of [1] to

[15] , characterized by containing an addition product (a4) of an alkylene oxide.

[17] The agent according to any one of [1] to

[16] , characterized in that it contains water and has a pH of 3.8 to 11.5, preferably 4.0 to 10.0, more preferably 5.0 to 9.0, and most preferably 6.0 to 8.0.

[18] The following steps: (1) A step of applying a coloring agent described in any of [1] to

[17] to a keratinous substance, (2) The step of exposing the coloring agent to a keratinous substance, (3) Step to rinse off the dye A method for dyeing keratinous substances, particularly human hair, including keratinous substances. [Examples]

[0241] [1. Formulation] The following formulations were prepared (unless otherwise specified, all data are in weight %):

[0242] [Table 1]

[0243] First, a cream base was prepared from the specified ingredients. Then, specific additives were added to the cream base.

[0244] In the formulation of Example 1, only a portion of the water was added as an additive to the cream base.

[0245] In the formulation of Example 2, water, PPG-3 benzyl ether myristate (a3), and the pigment Unipure Red LC 3079 (a2) were successively added to the cream base as additives.

[0246] In the formulations of Examples 3 and 4, water and PPG-14 butyl ether (a4) were added to the cream base as additives.

[0247] In formulations 1, 3, and 4 of the examples, the pigment Unipure Red LC 3079 (a2) and PPG-3 benzyl ether myristate (a3) ​​were mixed separately to form a predispersion. This predispersion was then incorporated into a cream base.

[0248] In the final step, the aminosilicone DOWSIL AP-8568 aminofluid (a1) was added to all four formulations 1-4.

[0249] [2. Application] First, hair strands (Kerling Euronaturhaar white) were colorimetrically measured using a Datacolor Spectraflash 450 type colorimeter.

[0250] The formulations of Examples 1-4 were applied as hair colorants as follows: After preparation, each agent was applied to hair strands (Kerling, Euronatural hair white, liquid ratio: 1 g of agent per 1 g of hair strand (E1)). The agents were left to stand for 3 minutes. Subsequently, the hair strands were thoroughly washed with water (1 minute), dried, and then colorimetric measurements were taken using a Datacolor Spectraflash 450 type colorimeter.

[0251] The ΔE value used to evaluate color intensity is derived from the L*a*b* colorimetric values ​​measured for each strand portion as follows: ΔE=[(L i -L0) 2 +(a i -a0) 2 +(b i -b0)] 1 / 2 L0, a0, and b0 = Measurements of the strand before staining L i a i and b i = Measurement of strand after staining The larger this ΔE value, the higher the color intensity (= better).

[0252] Ten trained individuals each evaluated dyed hair strands based on their texture. Hair texture was scored from 1 to 6 (1: very poor texture (rough, brittle, dull), 6: very good texture (smooth, soft, well-groomed)).

[0253] Dyed hair strands were evaluated for their friction fastness. To assess friction fastness, the hair strands were subjected to standardized mechanical abrasion and then again measured using colorimetric analysis. The ΔE used to evaluate friction fastness was derived from the L*a*b* colorimetric values ​​measured for each strand portion as follows: ΔE=[(L i -L0) 2 +(a i -a0) 2 +(b i -b0)] 1 / 2 L0, a0, and b0 = Measurement values ​​of the strand after staining. L i a i and b i =Measurements of strands after staining and mechanical loading The larger this ΔE value, the greater the color shift caused by wear, which in turn indicates lower frictional fastness.

[0254] After dyeing and drying, each strand was manually washed three times. In each wash, each strand was moistened and a commercially available shampoo (Schwarzkopf, Schauma 7 herbs) was massaged into the strand for 25 seconds (0.25 g of shampoo per gram of hair). The strand was then rinsed with lukewarm tap water for 30 seconds and dried. After the completion of the three washes, each strand was again colorimetrically analyzed.

[0255] The ΔE used to evaluate wash fastness is derived from the measured L*a*b* colorimetric values ​​as follows: ΔE=[(L i -L0) 2 +(a i -a0) 2+(b i -b0)] 1 / 2 L0, a0, and b0 = Measurement values ​​of the stained strand after staining and before washing. L i a i and b i =Measurements of dyed strands after 3 washes The larger this ΔE value, the greater the color shift caused by washing, which means that the washing fastness is low.

[0256] The following results were obtained:

[0257] [Table 2]

Images