EP3897562A1 - Agent pour colorer les cheveux contenant au moins un composé de silicium organique i - Google Patents

Agent pour colorer les cheveux contenant au moins un composé de silicium organique i

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Publication number
EP3897562A1
EP3897562A1 EP19783250.4A EP19783250A EP3897562A1 EP 3897562 A1 EP3897562 A1 EP 3897562A1 EP 19783250 A EP19783250 A EP 19783250A EP 3897562 A1 EP3897562 A1 EP 3897562A1
Authority
EP
European Patent Office
Prior art keywords
agent
group
coloring
alkyl group
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP19783250.4A
Other languages
German (de)
English (en)
Inventor
Juergen Schoepgens
Torsten LECHNER
Marc NOWOTTNY
Gabriele Weser
Ulrike Schumacher
Claudia Kolonko
Caroline KRIENER
Carsten MATHIASZYK
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP3897562A1 publication Critical patent/EP3897562A1/fr
Pending legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
    • A61K8/898—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing nitrogen, e.g. amodimethicone, trimethyl silyl amodimethicone or dimethicone propyl PG-betaine
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
    • A61K8/585—Organosilicon compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/10—Preparations for permanently dyeing the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/42—Colour properties
    • A61K2800/43—Pigments; Dyes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/88—Two- or multipart kits
    • A61K2800/884—Sequential application

Definitions

  • the present application relates to an agent for dyeing keratinous material, in particular human hair, which contains in a cosmetic carrier (a) at least one special organic silicon compound, and (b) at least one coloring compound.
  • the invention further relates to a multi-component packaging unit (kit-of-parts) for dyeing keratinous material, in particular human hair, which, separately from one another, comprises agents (I), (II) and (III) in three different containers, the Agent (I) which contains at least one organic silicon compound (a) and the at least one coloring compound (b) either in agent (II) together with water and / or in agent (III) together with at least one film-forming, hydrophilic polymer (c) is included.
  • the invention also relates to processes for dyeing keratinous material using the agents described and processes for producing the organic silicon compound (a).
  • Oxidation dyes are usually used for permanent, intensive dyeings with good fastness properties and good gray coverage.
  • Such colorants usually contain oxidation dye precursors, so-called developer components and coupler components, which form the actual dyes with one another under the influence of oxidizing agents, such as hydrogen peroxide.
  • Oxidation dyes are characterized by very long-lasting dyeing results.
  • color pigments are generally understood to mean insoluble, color-imparting substances. These are undissolved in the form of small particles in the dye formulation and are only deposited on the outside of the hair fibers and / or the skin surface. For this reason, they can usually be removed without leaving any residue by washing them with detergent-containing detergents.
  • Various products of this type are available on the market under the name of hair mascara. If the user desires particularly long-lasting dyeings, the use of oxidative coloring agents has so far been his only option. However, despite numerous attempts to optimize the oxidative hair coloring, an unpleasant smell of ammonia or amine cannot be completely avoided. The hair damage still associated with the use of the oxidative colorants also has a disadvantageous effect on the hair of the user.
  • EP 2168633 B1 is concerned with the task of producing long-lasting hair colorations using pigments.
  • the document teaches that when a combination of pigment, organic silicon compound, hydrophobic polymer and a solvent is used, dyeings can be produced on hair which are particularly resistant to shampooing.
  • the fastness to washing should be outstanding, but the use of the oxidation dye precursors normally used for this purpose should be avoided.
  • a technology was sought which made it possible to fix the coloring compounds known from the prior art (such as, for example, pigments and direct dyes) to the hair in an extremely permanent manner.
  • a sufficiently high storage stability of the formulations should be ensured.
  • the production process of the formulations should also be simplified or optimized.
  • a first object of the present invention is therefore an agent for coloring keratinous material, in particular human hair, containing
  • R2 independently of one another for a hydrogen atom, a Ci-C6-alkyl group, a hydroxy-Ci-C6-alkyl group, a C2-C6-alkenyl group, an amino-Ci-C6-alkyl group, an amino-Ci-C6 -alkyl- amino-Ci-C6-alkyl group or a group of formula (III),
  • L for a linear or branched, divalent alkylene group, arylene group, saturated cycloaliphatic group, arylene alkylene group, alkylene arylene group, alkylene arylene alkylene group or arylene alkylene arylene group each having up to 30 carbon atoms or a hetero derivative thereof in which 1 to 4 carbon atoms are replaced by O, S or NR1, preferably a linear or branched C1-6 alkylene group, particularly preferably a linear Ci, C2 or C3 alkylene group,
  • - L ' for a linear or branched, divalent alkylene group, arylene group, saturated cycloaliphatic group, arylene alkylene group, alkylene arylene group, alkylene arylene alkylene group or arylene alkylene arylene group each having up to 30 carbon atoms or a hetero derivative thereof in which 1 to 4 carbon atoms are replaced by O, S or NH , preferably a linear or branched C1-6 alkylene group, particularly preferably a linear Ci, C2 or C3 alkylene group,
  • R3 and R5 independently represent a hydrogen atom or a Ci-C6-alkyl group, preferably a Ci-C2-alkyl group,
  • R4 and R ⁇ independently represent a Ci-C6-alkyl or a C2-C6-alkenyl group
  • - a and b each independently represent an integer from 2 to 3, preferably 3, and
  • - c is 0 or 1;
  • R7 stands for a linear or branched CiC-12-alkyl group, CiC-12-alkoxy group, hydroxy-CiC-12-alkyl group or C2-C12 alkenyl group, preferably for a linear Ci-C6-alkyl, Ci-C6-alkoxy or C2-C6-alkenyl group, more preferably Ci-C2-alkyl group,
  • Re represents a hydrogen atom or a Ci-C6-alkyl group, preferably a Ci-C2-alkyl group,
  • R9 represents a Ci-C6-alkyl or a C2-C6-alkenyl group
  • (b) at least one coloring compound preferably from the group of the photochromic dyes, thermochromic dyes, pigments and / or the substantive dyes.
  • the use of the organic silicon compounds (a) according to the invention led to formulations with excellent storage stability.
  • a very resistant film could be produced on the keratinic material using the organic silicon compounds (a) according to the invention. For this reason, extremely genuine dyeings with good resistance to shampooing were obtained on the keratinous material.
  • Keratinous material means hair, skin, nails (such as fingernails and / or toenails). Wool, furs and feathers also fall under the definition of keratinous material.
  • Keratinous material is preferably understood to mean human hair, human skin and human nails, in particular fingernails and toenails. Keratinous material is particularly preferably understood to mean human hair.
  • the agents according to the invention contain the compounds (a) and (b) essential to the invention in a cosmetic carrier.
  • the agents according to the invention can preferably contain the compounds (a) and (b) according to the invention in separate containers.
  • the formulations in these containers which contain the compound (a) or (b) can each be formulated differently, i.e. also contain different cosmetic carriers.
  • the formulations contained in the various containers can then be mixed or combined before or during use.
  • only one of the two compounds can be pre-formulated with a cosmetic carrier and the other, if necessary at all, only be combined with a suitable carrier or the other compound pre-formulated with the carrier before use.
  • the two compounds are only mixed when used or together with a cosmetic carrier.
  • agent for coloring keratinous material thus refers both to agents in which the components (a) and (b) are spatially separated from one another and to the ready-to-use agents in which the components (a) and (b) can be used both in a mixture with one another and, if appropriate, further components or further separately or in each case in a mixture with other components.
  • agents in the form of kits and their use, or methods of using them are described in detail herein.
  • the carriers used in the use are, for example, suitable aqueous or aqueous-alcoholic carriers.
  • suitable aqueous or aqueous-alcoholic carriers are, for example, creams, emulsions, gels or also surfactant-containing foaming solutions, such as shampoos, foam aerosols, foam formulations or other preparations which are suitable for use on the hair.
  • the cosmetic carrier is preferably water-containing, which means that the carrier - based on its weight - contains at least 2% by weight of water.
  • the water content is preferably above 5% by weight, more preferably above 10% by weight and even more preferably above 15% by weight.
  • the cosmetic carrier can also be aqueous-alcoholic.
  • aqueous-alcoholic solutions are to be understood as meaning aqueous solutions containing 2 to 70% by weight of a C 1 -C 4 -alcohol, in particular ethanol or isopropanol.
  • the agents according to the invention can additionally contain further organic solvents, such as methoxybutanol, benzyl alcohol, ethyl diglycol or 1,2-propylene glycol. All water-soluble organic solvents are preferred.
  • the compounds (a) are not prepared, stored and / or transported in a pre-formulated form in an aqueous or water-containing carrier, but rather the contact with water, for example in the form of a carrier, only takes place shortly before or during use in order to achieve a Avoid premature crosslinking / condensation of the silanes. Accordingly, the preceding discussion of the carriers relates in particular to those carriers which are used in the use of the agents, but not the carriers in which the components of the agents are stored and transported.
  • agent for coloring is used in the context of this invention for a coloring of the keratin material, in particular the hair, caused by the use of coloring compounds, such as, for example, thermochromic and photochromic dyes, pigments, mica and / or direct dyes.
  • coloring compounds such as, for example, thermochromic and photochromic dyes, pigments, mica and / or direct dyes.
  • the aforementioned coloring compounds are deposited in a particularly homogeneous and smooth film on the surface of the keratin material or diffuse into the keratin fiber.
  • the film is formed in situ by oligomerization or polymerization of the organic silicon compound or compounds, and by the interaction of the coloring compound and the organic silicon compound and optionally further components, such as, for example, a film-forming, hydrophilic polymer.
  • the agents according to the invention contain at least one organic silicon compound which can be obtained by partial condensation under reduced pressure of at least one aminosilane (a1) of the formula (I),
  • R 2 independently of one another for a hydrogen atom, a Ci-C6-alkyl group, a hydroxy-Ci-C6-alkyl group, a C 2 -C6 alkenyl group, an amino-Ci-C6-alkyl group, an amino-Ci -C6-alkylamino-Ci-C6-alkyl group or a group of the formula (III),
  • L for a linear or branched, divalent alkylene group, arylene group, saturated cycloaliphatic group, arylene alkylene group, alkylene arylene group, alkylene arylene alkylene group or arylene alkylene arylene group each having up to 30 carbon atoms or a hetero derivative thereof in which 1 to 4 carbon atoms are replaced by O, S or NRi, preferably a linear or branched C 1 -6 alkylene group, particularly preferably a linear Ci, C 2 - or C 3 alkylene group,
  • - L ' for a linear or branched, divalent alkylene group, arylene group, saturated cycloaliphatic group, arylene alkylene group, alkylene arylene group, alkylene arylene alkylene group or arylene alkylene arylene group each having up to 30 carbon atoms or a hetero derivative thereof in which 1 to 4 carbon atoms are replaced by O, S or NH , preferably a linear or branched C 1 -6 alkylene group, particularly preferably a linear Ci, C 2 - or C 3 alkylene group,
  • R3 and R5 independently represent a hydrogen atom or a C 1 -C 6 -alkyl group, preferably a C 1 -C 2 -alkyl group,
  • R 4 and R ⁇ independently represent a Ci-C6-alkyl or a C 2 -C6-alkenyl group
  • - a and b each independently represent an integer from 2 to 3, preferably 3, and
  • - c is 0 or 1;
  • R7 represents a linear or branched CiC- 12 alkyl group, CiC- 12 alkoxy group, hydroxy-CiC- 12 alkyl group or C 2 -C 12 alkenyl group, preferably a linear Ci-C6-alkyl, Ci-C6- Alkoxy or C 2 -C 6 alkenyl group, more preferably Ci-C 2 alkyl group,
  • Re represents a hydrogen atom or a C 1 -C 6 -alkyl group, preferably a C 1 -C 2 -alkyl group,
  • R9 represents a C 1 -C 6 -alkyl or a C 2 -C 6 -alkenyl group
  • Organic silicon compounds which are also referred to alternatively as organosilicon compounds, are compounds which either have a direct silicon-carbon bond (Si-C) or in which the carbon is attached to the silicon via an oxygen, nitrogen or sulfur atom. Atom is attached.
  • the organic silicon compounds according to the invention are compounds which contain at least two silicon atoms, preferably three or more.
  • the organic silicon compounds (a) according to the invention are obtainable by partial condensation of the silanes described herein and are also referred to herein as “precondensates” or “partial condensates”, since they usually consist of at least two monomeric units of the formula (I) or at least one monomeric unit of the formula (I) and a monomeric unit of the formula (II) which have been joined together by means of a condensation reaction.
  • precondensates or “partial condensates”
  • partial condensates also refers to the fact that the organic silicon compounds (a) each comprise one or more hydroxyl groups or hydrolyzable groups per molecule, i.e. are only partially condensed so that they can be further condensed / crosslinked when actually used for coloring.
  • the hydrolyzable group or groups is preferably a C 1 -C 6 -alkoxy group, in particular an ethoxy group or a methoxy group. It is preferred if the hydrolyzable group is attached directly to the silicon atom. If, for example, the hydrolyzable group is an ethoxy group, the organic silicon compound preferably contains a structural unit R’R “R” ′′ Si-O-CH2-CH3. The residues R ', R "and R"' represent the three remaining free valences of the silicon atom.
  • the organic silicon compounds (a) contain at least 3 or 4 groups of amino groups of the formulas -NH, -NH2 or -NR1R2. This ensures that sufficient adhesion is obtained on the surface of the keratinous materials.
  • Examples of a C 1 -C 6 -alkyl group are the groups methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl and t-butyl, n-pentyl and n-hexyl. Propyl, ethyl and methyl are preferred alkyl radicals.
  • Examples of a C2-C6 alkenyl group are vinyl, allyl, but-2-enyl, but-3-enyl and isobutenyl, preferred C2-C6 alkenyl radicals are vinyl and allyl.
  • a hydroxy-Ci-C6-alkyl group are a hydroxymethyl, a 2-hydroxyethyl, a 2-hydroxypropyl, a 3-hydroxypropyl, a 4-hydroxybutyl group, a 5-hydroxypentyl and a 6-hydroxyhexyl group; a 2-hydroxyethyl group is particularly preferred.
  • Examples of an amino-Ci-C6-alkyl group and an amino-Ci-C6-alkyl-amino-Ci-C6-alkyl group are groups of the formula - (CH2) o-NH2 and - (CH2) o-NH- (CH2) P -NH2, where o and p are each 1, 2, 3, 4, 5 or 6, preferably 2 or 3, more preferably 2.
  • the 2-aminoethyl group and the 2-aminoethyl-2-aminoethyl group (NH2- (CH2) 2-NH- (CH2) 2-) are particularly preferred.
  • the divalent groups for L and L 'each comprise up to 20 carbon atoms, preferably up to 20 carbon atoms, more preferably up to 12 carbon atoms, for example 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms.
  • a linear divalent Ci-C3o-alkylene group include, but are not limited to, the methylene group (-CH2-), the ethylene group (-CH2-CH2-), the n-propylene group (-CH2-CH2-CH2- ) and the n-butylene group (-CH2-CH2-CH2-CH2-).
  • the propylene group (-CH2-CH2-CH2-) is particularly preferred.
  • divalent alkylene groups can also be branched.
  • Examples of branched, divalent C3-C3o-alkylene groups are (-CH2-CH (CH3) -), (-CH2-CH (CH3) - CH2-), (-CH2-CH (CH 3 ) -CH2-CH 2 - ) and (-CH2-C (CH 3 ) 2-CH2-CH 2 -).
  • Examples of a divalent arylene group include, but are not limited to, 1,4-phenylene, 1,3-phenylene and 1,2-phenylene (each -C6H4-).
  • saturated cycloaliphatic groups are 1,4-cyclohexylene and 1,3-cyclopentylene.
  • Arylenealkylenearylene groups result from a combination of the alkylene and arylene groups described above. Examples include, but are not limited to, ethylene-p-phenylene (-CH 2 - CH2-C6H4-), p-phenylene-ethylene (-C6H4 - CH2-CH2-), ethylene-p-phenylene-ethylene
  • Heteroderivatives of the above groups include, but are not limited to, ethylaminoethyl, ethylaminopropyl, ethyl 3-aminoisobutyl, propylaminopropyl, hexylaminomethyl, ethylaminoundecyl, oxypropylaminopropyl, ethyl 2-aminoethyl-3-aminopropyl, ethylthiopropyl, ethoxypropyl and ethoxypropyl. It is preferred that in the hetero-derivatives of the groups mentioned 1 or 2 carbon atoms, preferably only 1 carbon atom, is replaced by O, S or NR1. In various preferred embodiments, NR1 in these hetero derivatives is preferably NH or N-C1-6 alkyl.
  • organic silicon compounds (a) are preferably obtainable by partial condensation of aminosilanes (a1) of the formula (I).
  • the radicals R 1 and R 2 independently of one another represent a hydrogen atom or a C 1 -C 6 -alkyl group, in particular methyl or ethyl. With particular preference at least one of the radicals R 1 and R 2 very particularly preferably both represents a hydrogen atom.
  • the other preferably represents a Ci-C6-alkyl group or an amino-Ci-C6-alkyl group / an amino-Ci-C6-alkyl-amino-Ci-C6-alkyl - Group, particularly preferably methyl, ethyl, 2-aminoethyl or 2-aminoethyl-2-aminoethyl.
  • Ri preferably represents a hydrogen atom, a Ci-C6-alkyl group, a hydroxy-Ci-C6-alkyl group, a C 2 -C6 alkenyl group or an amino-Ci-C6-alkyl group and R 2 stands for a grouping of the formula (III), b, L ', R5 and R6 preferably being identical to a, L, R 3 and R 4 .
  • the linker -L- which preferably represents a linear or branched, divalent Ci-C 2 o-alkylene group.
  • -L- is particularly preferably a linear, divalent Ci-C 2 o-alkylene group. More preferably, -L- stands for a linear divalent Ci-C6-alkylene group.
  • -L- is particularly preferably a methylene group (-CH2-), an ethylene group (-CH2-CH2-), a propylene group (-CH2-CH2-CH2-) or a butylene group (-CH 2 -CH 2 -CH 2 - CH 2 -).
  • L very particularly preferably represents a propylene group (-CH 2 -CH 2 -CH 2 -). Also preferred are branched divalent C3-C 2 o-alkylene groups, especially dimethylbutyl (3,3-dimethylbutyl).
  • R 1, R 2 both represent a hydrogen atom and L represents a linear, divalent Ci-C6-alkylene group, preferably a propylene group (-CH 2 - CH2-CH2-) or an ethylene group (-CH2- CH2-).
  • the radical R3 stands for a hydrogen atom or a Ci-C6-alkyl group
  • the radical R 4 stands for a Ci-C6-alkyl or C 2 - 6-alkenyl group.
  • R3 particularly preferably represents a C 1 -C 6 -alkyl group, in particular a methyl group or an ethyl group.
  • a is preferably 3. If a is 2, then R 4 is preferably methyl, ethyl or vinyl.
  • R3 and Rs if present, do not represent a hydrogen atom.
  • the alkoxysilanes are generally preferred over the silanoias.
  • the aforementioned aminosilanes are commercially available.
  • (3-aminopropyl) trimethoxysilane can be purchased from Sigma-Aldrich.
  • (3-Aminopropyl) triethoxysilane is also commercially available from Sigma-Aldrich.
  • Bis (trimethoxysilylpropyl) amine with CAS number 82985-35-1 can be purchased, for example, from Sigma-Aldrich.
  • Bis [3- (triethoxysilyl) propyl] amine with the CAS number 13497-18-2 can be purchased, for example, from Sigma-Aldrich.
  • N-Methyl-3- (trimethoxysilyl) -N- [3- (trimethoxysilyl) propyl] -1-propanamine is alternatively also referred to as bis (3-trimethoxysilylpropyl) -N-methylamine and can be purchased commercially from Sigma-Aldrich or Fluorochem .
  • R7 represents 12 alkyl
  • C 1 is a linear or branched CIC - C 2 alkoxy, hydroxy-alkyl CIC 12 or C 2 -C 12 alkenyl group, preferably a linear Ci-C6-alkyl, Ci-C6-alkoxy or C 2 -C6-alkenyl group, such as, for example, methyl, ethyl, propyl, butyl, methoxy, ethoxy and vinyl, more preferably Ci-C 2 -alkyl group, ie Methyl or ethyl.
  • Re represents a hydrogen atom or a C 1 -C 6 -alkyl group, preferably a C 1 -C 6 -alkyl group, methyl and ethyl being particularly preferred. In various embodiments, it may be preferred that no Rs is hydrogen.
  • R9 represents a C 1 -C 6 -alkyl or a C 2 -C 6 -alkenyl group, in particular methyl, ethyl or vinyl.
  • d is preferably 3. This is also particularly preferred when R7 is an alkoxy group.
  • Rs particularly preferably represents a C 1 -C 6 -alkyl group, in particular a methyl group or an ethyl group.
  • R9 is preferably methyl, ethyl or vinyl, more preferably methyl or ethyl, more preferably methyl.
  • the silane (a2) comprises a compound of the formula (II), where d is 3 and R7 and Rs are each methyl or ethyl.
  • an agent according to the invention is characterized in that, in addition to the aminosilane of the formula (I), a silane of the formula (II) is used for the preparation of the at least one organic silicon compound (a), this preferably being selected from the group consisting of
  • Tetramethyl orthosilicate Tetramethyl orthosilicate.
  • the trialkoxysilanes mentioned are particularly preferred.
  • a plurality of aminosilanes (a1) of the formula (I) and / or a plurality of silanes (a2) of the formula (II) are used.
  • the mass ratio of all compounds of the formula (I) to all compounds of the formula (II) is preferably 5: 1 to 1:20, more preferably 1: 1 to 1:10, more preferably 1: 2 to 1: 5.
  • the molar ratio of all compounds of the formula (I) to all compounds of the formula (II) is preferably 2: 1 to 1:30, more preferably 1: 1 to 1:20, more preferably 1: 2 to 1:10.
  • the organic silicon compounds (a) are produced by a condensation reaction of the aminosilanes (a1) with one another or with the silanes (a2).
  • the condensation is a partial condensation, whereby “partial condensation” in this context means that not all condensable groups react with one another, so that the resulting organic silicon compound per molecule still has on average at least one hydrolyzable / condensable group.
  • the average number of condensable / hydrolyzable groups per molecule is preferably at least 1.5, more preferably at least 2.
  • the quotient from the molar ratio of Si / hydrolyzable group (in particular alkoxy group) in the molecule / oligomer produced is at least 0.3. preferably at least 0.5, more preferably at least 0.7, for example at least 1.
  • Organic silicon compounds a) according to the invention have, for example, a hydrolyzable group / alkoxy group content of, for example, 5 to 30% by weight.
  • Organic silicon compounds a) according to the invention can be chain-like or cyclic. In particular, they are mixtures of chain and / or cyclic oligomers.
  • the degree of oligomerization is typically 2 to 30, i.e. the organic silicon compounds a) according to the invention consist of 2 to 30 monomeric units which are derived from the compounds a1 and, if used, also a2, preferably 3 to 20 units.
  • the number of remaining condensable / hydrolyzable groups can be controlled in particular via the hydrolysis conditions.
  • the aminosilanes (a1) and the silanes (a2) which are preferably alkoxysilanes, in particular methoxy or ethoxysilanes, are preferably hydrolyzed with water in a first step.
  • the water is used in a substoichiometric amount, ie an amount that is less than the amount that is theoretically would be necessary to hydrolyze all the hydrolyzable groups present on the Si atoms, ie in particular the alkoxysilane groups.
  • the amount of water used for this is preferably at least 10% below the stoichiometric amount necessary for complete hydrolysis, preferably at least 20% below.
  • the amount of water used for the hydrolysis is particularly preferably 0.2 to 2.5 mol of water per 1 mol of Si, preferably 0.4 to 2.0 mol of water per 1 mol of Si, more preferably 0.6 to 1.6 mol or 0.7 to 1.6 mol or 0.8 to 1.3 mol or 0.8 to 1.2 mol or 0.85 to 1.0 mol water per 1 mol Si.
  • the hydrolyzable groups on the Si atoms are hydrolyzed and, if they are alkoxy groups, the corresponding alcohols are split off. Si-OH groups remain on the silicon, which in the next step can react with one another in a condensation reaction, ie with elimination of water.
  • the water can be added continuously, in portions or directly as a total for the hydrolysis reaction.
  • the addition is preferably carried out to the silanes (a1) and optionally (a2), in particular with stirring.
  • the reaction vessel can be cooled or the amount and rate of water added can be adjusted. Depending on the amount of silanes used, the addition and reaction can take place over a period of 2 minutes to 72 hours. In preferred embodiments, the water is added continuously.
  • the temperature during the hydrolysis not exceed 75 ° C., preferably 60 ° C., more preferably 50 ° C.
  • the temperature during the hydrolysis reaction and optionally also during the subsequent condensation reaction is preferably in the range from 10 to 75 ° C., preferably 20 to 60 ° C.
  • the hydrolysis reaction is carried out under a protective gas, for example nitrogen, or it is otherwise ensured that the reaction mixture does not come into contact with additional moisture, such as, for example, atmospheric moisture.
  • a protective gas for example nitrogen
  • the reaction is therefore preferably carried out in a reaction vessel which is closed to the ambient atmosphere or in the absence of moisture.
  • the hydrolysis reaction is followed by a condensation reaction in which the Si-O-Si bonds are formed.
  • the speed of the reaction is fast enough that hydrolysis and condensation (precondensation) run almost in parallel.
  • the condensation reaction (partial condensation) takes place under reduced pressure, around the alcohols formed (in the case of alkoxysilanes used) and possibly also water formed from the reaction mixture by distillation to remove and convert into the gas phase. This suppresses the back reaction and shifts the equilibrium of the reaction to the condensate side.
  • the reduced pressure is preferably achieved by vacuum distillation, in which the reaction mixture has reduced pressure, typically up to a maximum of 800 mbar.
  • the volatile alcohols and possibly also water are condensed and collected in a receiver as a liquid distillate.
  • the distillation can optionally be carried out with cooling of the volatile alcohols / water by means of a cooler.
  • the reduced pressure can be generated using conventional methods known in the art, typically using a vacuum pump.
  • silanes (a1) and (a2) are predominantly, i.e. at least 50, preferably at least 75% by weight, almost exclusively, i.e. at least 90, preferably 95% by weight, or exclusively those which carry methoxysilane or ethoxysilane groups, in particular di- and trimethoxy- and ethoxysilanes, particularly preferably trimethoxy- or triethoxysilanes.
  • production takes place in a two- or multi-stage process, in which in a first step the hydrolysis is carried out by adding substoichiometric amounts of water, either continuously, in stages or in one, under normal pressure. Only after the amount of water has been added, preferably completely, is reduced pressure applied in a subsequent step and the alcohols formed are removed by means of vacuum distillation.
  • vacuum distillation is preferably carried out after at least 50% by weight of the planned total amount of water, preferably at least 70, 80, 90, 95 or 100% by weight of the water, preferably continuously.
  • the vacuum distillation can also take place simultaneously with the hydrolysis.
  • the pressure is reduced before the water is added, at the start of the addition or after 5-20% by weight of the planned total amount of water has been added.
  • the condensation reaction at reduced pressure can be carried out at elevated temperature.
  • the reaction vessel can be actively heated.
  • the temperature can be adjusted such that the alcohols released in the condensation reaction can evaporate and be removed at the reduced pressure applied.
  • the temperature is not more than 75 ° C., preferably not more than 60 ° C. It may further be preferred that the reaction mixture is not actively heated and that any increase in temperature above ambient temperature is only brought about by the exothermic nature of the hydrolysis.
  • the reaction can also take place in the presence of solvents, ie in particular alcohols such as methanol or ethanol. These will then usually used in 0.1 to 5 times the amount by weight based on the silanes used and then removed by distillation.
  • solvents ie in particular alcohols such as methanol or ethanol.
  • the reaction under reduced pressure yields a product that contains less than 5%, preferably less than 2%, more preferably less than 1% by weight of free alcohols (from the hydrolysis reaction).
  • the water content of the product is preferably less than 1% by weight, more preferably less than 0.1% by weight and very particularly preferably less than 0.01% by weight.
  • the organic silicon compounds (a) are reactive compounds.
  • the agent according to the invention - based on its total weight - contains one or more organic silicon compounds (a) in a total amount of 0.1 to 20.0% by weight, preferably 0.2 to 15 , 0 wt .-% and particularly preferably 0.2 to 2.0 wt .-% contains.
  • These quantitative data relate to the total weight of a ready-to-use mixture or - if this is used in the form of separate formulations - to the total weight of the particular formulation used for coloring the keratinous material.
  • all quantities used herein in the context of the agent according to the invention according to the first aspect of the invention i.e. not the multi-component kit, the above meaning.
  • At least one organic silicon compound (a) in the agent according to the invention which is obtained by partial condensation of monomeric aminotrialkoxysilanes (a1) with a silane group, i.e. one silicon atom per molecule, and monomeric trialkoxysilanes (a2) are available.
  • a1 aminopropyltri (m) ethoxysilane as component (a1) in combination with an alkyltrialkoxysilane, for example alkyltri (m) ethoxysilane, in particular Ci-3-alkyltri (m) ethoxysilane as component (a2), in order to use the organic silicon compound (a) to get.
  • the agents according to the invention contain at least one coloring compound.
  • This is preferably selected from the group of photochromic dyes, thermochromic dyes, pigments and / or direct dyes, particularly preferably from pigments and / or direct dyes.
  • Pigments in the sense of the present invention are understood to mean coloring compounds which, at 25 ° C. in water, have a solubility of less than 0.5 g / L, preferably less than 0.1 g / L, even more preferably less than 0, Own 05 g / L.
  • Water solubility can be achieved, for example, using the method described below: 0.5 g of the pigment is weighed out in a beaker. A stir fish is added. Then a liter of distilled water is added. This mixture is stirred on a magnetic stirrer for heated to 25 ° C for one hour. If undissolved constituents of the pigment are still visible in the mixture after this period, the solubility of the pigment is below 0.5 g / L.
  • the mixture is filtered. If a portion of undissolved pigments remains on the filter paper, the solubility of the pigment is below 0.5 g / L.
  • Suitable color pigments can be of inorganic and / or organic origin.
  • an agent according to the invention is characterized in that it (b) contains at least one coloring compound from the group of inorganic and / or organic pigments.
  • Preferred color pigments are selected from synthetic or natural inorganic pigments.
  • Inorganic color pigments of natural origin can be made, for example, from chalk, ocher, umber, green earth, burnt terra di Siena or graphite.
  • black pigments such as B. iron oxide black, colored pigments such.
  • B. ultramarine or iron oxide red and fluorescent or phosphorescent pigments can be used.
  • Colored metal oxides, hydroxides and oxide hydrates, mixed phase pigments, sulfur-containing silicates, silicates, metal sulfides, complex metal cyanides, metal sulfates, chromates and / or molybdates are particularly suitable.
  • Particularly preferred color pigments are black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and brown iron oxide (CI 77491), manganese violet (CI 77742), ultramarine (sodium aluminum sulfosilicate, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI77289 ), Iron blue (Ferric Ferrocyanide, CI77510) and / or Carmine (Cochineal).
  • Colored pearlescent pigments are also particularly preferred according to the invention from the group of pigments. These are usually based on mica and / or mica and can be coated with one or more metal oxides. Mica is one of the layered silicates. The most important representatives of these silicates are muscovite, phlogopite, paragonite, biotite, lepidolite and margarite. To produce the pearlescent pigments in conjunction with metal oxides, the mica, predominantly muscovite or phlogopite, is coated with a metal oxide.
  • synthetic mica coated with one or more metal oxides can also be used as pearlescent pigment.
  • Particularly preferred pearlescent pigments are based on natural or synthetic mica (mica) and are coated with one or more of the aforementioned metal oxides.
  • the color of the respective pigments can be varied by varying the layer thickness of the metal oxide (s).
  • an agent according to the invention is characterized in that it (b) contains at least one coloring compound from the group of pigments, which is selected from the group of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, complex metal cyanides, metal sulfates , Bronze pigments and / or from coloring compounds based on mica or mica, which are coated with at least one metal oxide and / or a metal oxychloride.
  • an agent according to the invention is characterized in that it (b) contains at least one coloring compound which is selected from pigments based on mica or mica, which are mixed with one or more metal oxides from the group consisting of titanium dioxide (CI 77891), black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and / or brown iron oxide (CI 77491, CI 77499), manganese violet (CI 77742), ultramarine (sodium aluminum sulfosilicate, CI 77007, Pigment Blue 29), chromium oxide hydrate ( CI 77289), chromium oxide (CI 77288) and / or iron blue (Ferric Ferrocyanide, CI 77510) are coated.
  • CI 77891 titanium dioxide
  • CI 77499 black iron oxide
  • CI 77492 yellow iron oxide
  • red and / or brown iron oxide CI 77491, CI 77499
  • manganese violet CI 77742
  • ultramarine sodium aluminum s
  • color pigments are commercially available, for example, under the trade names Rona®, Colorona®, Xirona®, Dichrona® and Timiron® from Merck, Ariabel® and Unipure® from Sensient, Prestige® from Eckart Cosmetic Colors and Sunshine® available from Sunstar.
  • Color pigments with the trade name Colorona® are particularly preferred
  • color pigments with the trade name Unipure® are, for example:
  • the agent according to the invention can also (b) contain one or more coloring compounds from the group of organic pigments
  • the organic pigments according to the invention are correspondingly insoluble, organic dyes or color varnishes which, for example, from the group of nitroso, nitro, azo, xanthene, anthraquinone, isoindolinone, isoindoline, quinacridone, perinone, perylene -, Diketo-pyrrolopyorrol, indigo, thioindido, dioxazine and / or triarylmethane compounds can be selected.
  • Particularly suitable organic pigments are, for example, carmine, quinacridone, phthalocyanine, sorghum, blue pigments with the color index numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with the color index numbers CI 1 1680, CI 1 1710, CI 15985, CI 19140, CI 20040, CI 21 100, CI 21108, CI 47000, CI 47005, green pigments with the color index numbers CI 61565, CI 61570, CI 74260, orange pigments with the color index numbers CI 1 1725, CI 15510 , CI 45370, CI 71 105, red pigments with the color index numbers CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800
  • an agent according to the invention is characterized in that it (b) contains at least one coloring compound from the group of organic pigments which is selected from the group consisting of carmine, quinacridone, phthalocyanine, sorghum, blue pigments with the color Index numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with the color index numbers CI 1 1680, CI 1 1710, CI 15985, CI 19140, CI 20040, CI 21 100, CI 21108 , CI 47000, CI 47005, green pigments with the Color Index numbers CI 61565, CI 61570, CI 74260, orange pigments with the Color Index numbers CI 1 1725, CI 15510, CI 45370, CI 71 105, red pigments with the Color Index Numbers CI 12085, CI 12120, CI 12370, CI 12420, CI
  • the organic pigment can also be a colored lacquer.
  • color lacquer is understood to mean particles which comprise a layer of absorbed dyes, the unit consisting of particles and dye being among the abovementioned. Conditions is insoluble.
  • the particles can be, for example, inorganic substrates, which can be aluminum, silica, calcium borosilicate, calcium aluminum borosilicate or aluminum.
  • the alizarin color lacquer can be used as the color lacquer.
  • the use of the aforementioned pigments in the agent according to the invention is particularly preferred. It is further preferred if the pigments used have a certain particle size. This particle size leads on the one hand to a uniform distribution of the pigments in the polymer film formed and on the other hand avoids a rough feeling of hair or skin after the application of the cosmetic agent. It is therefore advantageous according to the invention if the at least one pigment has an average particle size D 50 of 1.0 to 50 pm, preferably 5.0 to 45 pm, preferably 10 to 40 pm, in particular 14 to 30 pm.
  • the average particle size Dso can be determined, for example, using dynamic light scattering (DLS).
  • the pigment or pigments (b) can be used in an amount of 0.001 to 20% by weight, in particular 0.05 to 5% by weight, in each case based on the total weight of the agent according to the invention.
  • the agents according to the invention can also contain one or more substantive dyes as color-imparting compounds (b).
  • Direct dyes are dyes that are applied directly to the hair and do not require an oxidative process to form the color. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones, triarylmethane dyes or indophenols.
  • the substantive dyes for the purposes of the present invention have a solubility in water (760 mmHg) at 25 ° C. of more than 0.5 g / L and are therefore not to be regarded as pigments.
  • the direct dyes preferably have a solubility in water (760 mmHg) at 25 ° C. of more than 1.0 g / l.
  • the direct dyes within the meaning of the present invention particularly preferably have a solubility in water (760 mmHg) at 25 ° C. of more than 1.5 g / l.
  • Direct dyes can be divided into anionic, cationic and nonionic direct dyes.
  • an agent according to the invention is characterized in that it contains at least one anionic, cationic and / or nonionic direct dye as the color-imparting compound (b).
  • an agent according to the invention is characterized in that (b) it contains at least one anionic, cationic and / or nonionic direct dye.
  • Suitable cationic direct dyes are, for example, Basic Blue 7, Basic Blue 26, 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 Basic Red 76
  • Nonionic nitro and quinone dyes and neutral azo dyes can be used as nonionic direct dyes.
  • Suitable nonionic direct dyes are those under the 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 1 1, HC Red 13, HC Red BN, HC Blue 2, HC Blue 1 1, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9 known compounds , and 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-amin
  • 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-1,4,4 naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitro-benzoic acid and 2-chloro-6-ethylamino-4-nitrophenol.
  • agents which contain (b) at least one anionic substantive dye in particular with agents which contain (b) at least one anionic substantive dye, colorations with a particularly high color intensity can be produced.
  • an agent according to the invention is therefore characterized in that it (b) contains at least one anionic direct dye.
  • Anionic direct dyes are also known as acid dyes.
  • Acid dyes are to be understood as direct dyes which have at least one carboxylic acid group (- COOH) and / or one sulfonic acid group (-SO3H). Depending on the pH, the protonated forms (-COOH, -SO3H) of the carboxylic acid or sulfonic acid groups are in equilibrium with their deprotonated forms (-COO, -SO3). The proportion of protonated forms increases with decreasing pH. If direct dyes are used in the form of their salts, the carboxylic acid groups or sulfonic acid groups are in deprotonated form and are neutralized with appropriate stoichiometric equivalents of cations in order to maintain electroneutrality. Acid dyes according to the invention can also be used in the form of their sodium salts and / or their potassium salts.
  • the acid dyes for the purposes of the present invention have a solubility in water (760 mmHg) at 25 ° C. of more than 0.5 g / L and are therefore not to be regarded as pigments.
  • the acid dyes preferably have a solubility in water (760 mmHg) at 25 ° C. of more than 1.0 g / l.
  • alkaline earth metal salts such as calcium salts and magnesium salts
  • aluminum salts of acid dyes often have a lower solubility than the corresponding alkali metal salts. If the solubility of these salts is below 0.5 g / L (25 ° C, 760 mmHg), they do not fall under the definition of a direct dye.
  • An essential feature of the acid dyes is their ability to form anionic charges, the carboxylic acid or sulfonic acid groups responsible for this usually being linked to different chromophore systems.
  • Suitable chromophoric systems can be found, for example, in the structures of nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinone dyes, triarylmethane dyes, xanthene dyes, rhodamine dyes, oxazine dyes and / or indophenol dyes.
  • a means for coloring keratinous material which is characterized in that it (b) contains at least one anionic substantive dye which is selected from the group of the nitrophenylenediamines, the nitroaminophenols, the azo dyes, the anthraquinone dyes, the triarylmethane dyes, the xanthene dyes, the rhodamine dyes, the oxazine dyes and / or the indophenol dyes , wherein the dyes from the aforementioned group each have 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 (-SOsNa) and / or a potassium sulfonate group (- SO3K).
  • anionic substantive dye which is selected from the group of the nitrophenylenediamines, the nitroa
  • one or more compounds from the following group can be selected as particularly suitable acid dyes: Acid Yellow 1 (D&C Yellow 7, Citronin A, Ext. D&C Yellow No. 7, Japan Yellow 403, CI 10316, COLIPA n ° B001), Acid Yellow 3 (COLIPA n °: C 54, D&C Yellow N ° 10, Quinoline Yellow, E104, Food Yellow 13), Acid Yellow 9 (CI 13015), Acid Yellow 17 (CI 18965), Acid Yellow 23 (COLIPA n ° C 29, Covacap Jaune W 1 100 (LCW), Sicovit Tartrazine 85 E 102 (BASF), Tartrazine, Food Yellow 4, Japan Yellow 4, FD&C Yellow No.
  • Acid Yellow 1 D&C Yellow 7, Citronin A, Ext. D&C Yellow No. 7, Japan Yellow 403, CI 10316, COLIPA n ° B001
  • Acid Yellow 3 (COLIPA n °: C 54, D&C Yellow N ° 10, Quinoline Yellow, E104, Food Yellow 13), Acid Yellow 9 (CI 130
  • 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 ° C015), Acid Orange 10 (Cl 16230; Orange G sodium salt), Acid Orange 1 1 (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 ORANGE 24 ; Japan Brown 201; D & C Brown No.1), Acid R ed 14 (C.I.
  • Acid Red 18 (E124, Red 18; CI 16255), Acid Red 27 (E 123, CI 16185, C-Rot 46, Echtrot D, FD&C Red Nr.2, Food Red 9, Naphtholrot S), Acid Red 33 (Red 33, Fuchsia Red, D&C Red 33, CI 17200), Acid Red 35 (CI Cl18065), Acid Red 51 (CI 45430, Pyrosin B, Tetraiodfluorescein, Eosin J, Lodeosin), Acid Red 52 (CI 45100, Food Red 106, Solar Rhodamine B, Acid Rhodamine B, Red n ° 106 Pontacyl Brilliant Pink), Acid Red 73 (CI CI 27290), Acid Red 87 (Eosin, CI 45380), Acid Red 92 (COLIPA n ° C53, CI 45410), Acid Red 95 (CI 45425, Erythtosine, Simacid Erythrosine Y), Acid Red 184 (CI 15685), Acid Red
  • Acid Green 50 (Brillantklare indispensable BS, Cl 44090, Acid Brilliant Green BS, E 142), Acid Black 1 (Black n ° 401, Naphthalene Black 10B, Amido Black 10B, CI 20 470, COLIPA n ° B15), Acid Black 52 (CI 1571 1), Food Yellow 8 (CI 14270), Food Blue 5, D&C Yellow 8, D&C Green 5, D&C Orange 10, D&C Orange 1 1, D&C Red 21, D&C Red 27, D&C Red 33, D&C Violet 2 and / or D&C Brown 1.
  • the water solubility of the anionic direct dyes can be determined, for example, in the following way. 0.1 g of the anionic direct dye is placed in a beaker. A stir fish is added. Then 100 ml of water are added. This mixture is heated to 25 ° C. with stirring on a magnetic stirrer. It is stirred for 60 minutes. The aqueous mixture is then assessed visually. If there are still undissolved residues, the amount of water is increased - for example in increments of 10 ml. Water is added until the amount of dye used has completely dissolved. If the dye-water mixture cannot be assessed visually due to the high intensity of the dye, the mixture is filtered.
  • the solubility test is repeated with a higher amount of water. If 0.1 g of the anionic direct dye dissolves in 100 ml of water at 25 ° C., the solubility of the dye is 1.0 g / L.
  • Acid Yellow 1 is called 8-hydroxy-5,7-dinitro-2-naphthalenesulfonic acid disodium salt and has a solubility in water of at least 40 g / L (25 ° C).
  • Acid Yellow 3 is a mixture of the sodium salts of mono- and sisulfonic acids of 2- (2-quinolyl) -1 H-indene-1, 3 (2H) -dione and has a water solubility of 20 g / L (25 ° C).
  • Acid Yellow 9 is the disodium salt of 8-hydroxy-5,7-dinitro-2-naphthalenesulfonic acid, its water solubility is above 40 g / L (25 ° C).
  • Acid Yellow 23 is the trisodium salt of 4,5-dihydro-5-oxo-1- (4-sulfophenyl) -4 - ((4-sulfophenyl) azo) - 1 H-pyrazole-3-carboxylic acid and is good at 25 ° C Water soluble.
  • Acid Orange 7 is the sodium salt of 4 - [(2-hydroxy-1-naphthyl) azo] benzenesulfonate. Its water solubility is more than 7 g / L (25 ° C).
  • Acid Red 18 is the trinate salt of 7-hydroxy-8 - [(E) - (4-sulfonato-1-naphthyl) diazenyl)] - 1, 3-naphthalenedisulfonate and has a very high water solubility of more than 20 wt. %.
  • Acid Red 33 is the diantrium salt of 5-amino-4-hydroxy-3- (phenylazo) -naphthalene-2,7-disulphonate, its water solubility is 2.5 g / L (25 ° C).
  • Acid Red 92 is the disodium salt of 3,4,5,6-tetrachloro-2- (1, 4,5,8-tetrabromo-6-hydroxy-3-oxoxanthene-9-yl) benzoic acid, its water solubility with more than 10 g / L is specified (25 ° C).
  • Acid Blue 9 is the disodium salt of 2 - ( ⁇ 4- [N-ethyl (3-sulfonatobenzyl] amino] phenyl ⁇ ⁇ 4 - [(N-ethyl (3-sulfonatobenzyl) imino] -2,5-cyclohexadien-1- ylidene ⁇ methyl) -benzenesulfonate and has a water solubility of more than 20 wt .-% (25 ° C).
  • a very particularly preferred agent according to the invention is therefore characterized in that it (b) contains at least one anionic direct dye from the group consisting of 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 1 1, Acid Orange 15, Acid Orange 20, Acid Orange 24, Acid Red 14, Acid Red, Acid Red 27, Acid Red 33, Acid Red 35 , Acid Red 51, Acid Red 52, Acid Red 73, Acid Red 87, Acid Red 92, Acid Red 95, Acid Red 184, Acid Red 195, Acid Violet 43, Acid Violet 49, Acid Violet 50, Acid Blue 1, Acid Blue 3, Acid Blue 7, Acid Blue 104, Acid Blue 9, Acid Blue 62, Acid Blue 74, Acid Blue 80, Acid Green 3, Acid Green 5, Acid Green 9, Acid Green 22, Acid Green 25, Acid Green 50 , Acid Black 1, Acid Black 52, Food Yellow 8, Food Blue 5, D&C Yellow 8, D&C Green 5, D&C Orange 10, D&C Orange 1 1, D&C Red 21, D&C Red 27, D&C Red 33, D&C Violet 2 and
  • the direct dye or dyes in particular the anionic direct dyes, can be used in various amounts in the agent according to the invention, depending on the desired color intensity. Particularly good results could be obtained if the agent according to the invention, based on its total weight, had one or more substantive dyes (b) in a total amount of 0.01 to 10.0% by weight, preferably 0.1 to 8.0 % By weight, more preferably from 0.2 to 6.0% by weight and very particularly preferably from 0.5 to 4.5% by weight.
  • an agent according to the invention is characterized in that, based on its total weight, it contains one or more direct dyes (b) in a total amount of from 0.01 to 10.0% by weight, preferably from 0.1 to 8.0% by weight, more preferably from 0.2 to 6.0% by weight and very particularly preferably from 0.5 to 4.5% by weight.
  • an agent according to the invention is characterized in that, based on its total weight, it contains one or more anionic direct dyes (b) in a total amount of 0.01 to 10.0% by weight, preferably 0.1 to 8.0% by weight, more preferably from 0.2 to 6.0% by weight and very particularly preferably from 0.5 to 4.5% by weight.
  • Thermochromic dyes can also be used.
  • Thermochromism contains the property of a material to change its color reversibly or irreversibly depending on the temperature. This can be done by changing the intensity and / or the maximum wavelength.
  • Photochromism includes the property of a material to change its color reversibly or irreversibly depending on the irradiation with light, in particular UV light. This can be done by changing the intensity and / or the maximum wavelength.
  • the agents according to the invention can additionally contain at least one film-forming polymer as third ingredient (c).
  • This polymer can be present in a further separate formulation, which is spatially separated from the formulations of the ingredients (a) and (b), or can be pre-formulated together with the coloring compound (b).
  • Polymers are understood to mean macromolecules with a molecular weight of at least 1000 g / mol, preferably of at least 2500 g / mol, particularly preferably of at least 5000 g / mol, which consist of identical, repeating organic units.
  • the polymers of the present invention can be synthetically produced polymers which are produced by polymerizing one type of monomer or by polymerizing different, structurally different types of monomers. If the polymer is polymerized by a Manufactured monomer types, one speaks of homopolymers. If structurally different types of monomers are used in the polymerization, the resulting polymer is referred to as a copolymer.
  • the maximum molecular weight of the polymer depends on the degree of polymerization (number of polymerized monomers) and the batch size and is also determined by the polymerization method. For the purposes of the present invention, it is preferred if the maximum molecular weight of the film-forming, hydrophobic polymer (c) is not more than 10 7 g / mol, preferably not more than 10 ® g / mol and particularly preferably not more than 10 5 g / mol is.
  • a hydrophilic polymer is understood to mean a polymer which has a solubility in water at 25 ° C. (760 mmHg) of more than 1% by weight, preferably of more than 2% by weight.
  • a hydrophobic polymer is understood to mean a polymer which has a solubility in water at 25 ° C. (760 mmHg) of less than 1% by weight.
  • the water solubility of the film-forming polymer can be determined, for example, in the following way. 1.0 g of the polymer are placed in a beaker. Make up to 100 g with water. A stirred fish is added and the mixture is heated to 25 ° C. with stirring on a magnetic stirrer. It is stirred for 60 minutes. The aqueous mixture is then assessed visually. A completely dissolved polymer appears macroscopically homogeneous. If the polymer-water mixture cannot be assessed visually due to the high turbidity of the mixture, the mixture is filtered. If no undissolved polymer remains on the filter paper, the solubility of the polymer is more than 1% by weight, if undissolved polymer remains, the solubility of the polymer is less than 1% by weight.
  • a film-forming polymer is understood to mean a polymer which is capable of forming a film on a substrate, for example on a keratinous material or a keratinic fiber.
  • the formation of a film can be demonstrated, for example, by viewing the keratin material treated with the polymer under a microscope.
  • Nonionic, anionic and cationic polymers can be used as film-forming polymers.
  • the polymers of the acrylic acid type, the polyurethanes, the polyesters, the polyamides, the polyureas, the cellulose polymers, the nitro-cellulose polymers, the silicone polymers, the polymers of the acrylamide type and the polyisoprene can be mentioned .
  • Highly suitable film-forming, hydrophobic polymers are, for example, polymers from the group of copolymers of acrylic acid, copolymers of methacrylic acid, homopolymers or copolymers of acrylic acid esters, homopolymers or copolymers of methacrylic acid esters, the homopolymers or copolymers of acrylic acid amides, the homopolymers or copolymers of methacrylic acid amides, the copolymers of vinyl pyrrolidone, the copolymers of vinyl alcohol, the copolymers of vinyl acetate, the homopolymers or copolymers of ethylene, the homopolymers or copolymers of propylene, the homopolymers or copolymers Styrens, polyurethanes, polyesters and / or polyamides.
  • Suitable film-forming, hydrophilic polymers can be selected, for example, from the group of the polyvinylpyrrolidone (co) polymers, the polyvinyl alcohol (co) polymers, the vinyl acetate (co) polymers, the carboxyvinyl (co) polymers, the acrylic acid (co) Polymers, the methacrylic acid (co) polymers, the natural gums, the polysaccharides and / or the acrylamide (co) polymers can be selected.
  • Polyvinylpyrrolidone (PVP) and / or a copolymer containing vinylpyrrolidone, for example, can be used as the film-forming hydrophilic polymer.
  • an agent according to the invention contains at least one film-forming, hydrophilic polymer which is selected from the group consisting of polyvinylpyrrolidone (PVP) and the copolymers of polyvinylpyrrolidone.
  • PVP polyvinylpyrrolidone
  • Polyvinylpyrrolidone as a film-forming, hydrophilic polymer (c) can be easily and easily dissolved in water and also keeps large quantities of pigments stable in dispersion over a long period of time.
  • the wash fastness of the dyeings, which can be obtained with formulations containing PVP, is also very good.
  • polyvinylpyrrolidones are available for example under the name Luviskol K from BASF SE, in particular Luviskol ® K 90 or Luviskol ® K 85 from BASF SE.
  • PVP K30 which is sold by Ashland (ISP, POI Chemical), can also be used as another explicitly particularly suitable polyvinylpyrrolidone (PVP).
  • PVP K 30 is a polyvinylpyrrolidone which is very soluble in cold water and has the CAS number 9003-39-8.
  • the molecular weight of PVP K 30 is approx. 40,000 g / mol.
  • polyvinylpyrrolidones are the substances known under the trade names LUVITEC K 17, LUVITEC K 30, LUVITEC K 60, LUVITEC K 80, LUVITEC K 85, LUVITEC K 90 and LUVITEC K 115 and available from BASF.
  • film-forming hydrophilic polymers (c) from the group of copolymers of polyvinylpyrrolidone, which likewise lead to good and washable color results.
  • the storage stability of the formulations which contain one or more copolymers of polyvinylpyrrolidone (c) is also very good.
  • Especially suitable film-forming, hydrophilic polymers Vinylester vinylpyrrolidone copolymers can be mentioned, as they are sold for example under the trademark Luviskol ® (BASF) in this context. Luviskol ® VA 64 and Luviskol ® VA 73, each vinylpyrrolidone / vinyl acetate copolymers, are particularly preferred nonionic polymers.
  • styrene / VP copolymer and / or a vinylpyrrolidone-vinyl acetate copolymer and / or a VP / DMAPA acrylates copolymer and / or a VP / vinyl caprolactam / DMAPA acrylates copolymer are very particularly preferably used in the cosmetic compositions .
  • Vinylpyrrolidone-vinyl acetate copolymers are marketed by BASF SE under the name Luviskol® VA.
  • a VP / vinyl caprolactam / DMAPA acrylate copolymer is sold, for example, under the trade name Aquaflex® SF-40 by Ashland Inc.
  • a VP / DMAPA acrylate copolymer for example, is sold by Ashland under the name Styleze CC-10 and is a highly preferred copolymer containing vinylpyrrolidone.
  • copolymers of polyvinylpyrrolidone (c) which can also be mentioned are the copolymers which, by reacting N-vinylpyrrolidone with at least one further monomer from the group consisting of V-vinylformamide, vinyl acetate, ethylene, propylene, acrylamide, vinylcaprolactam, vinylcaprolactone and / or vinyl alcohol can be obtained.
  • an agent (c) according to the invention contains at least one film-forming, hydrophilic polymer which is selected from the group consisting of polyvinylpyrrolidone (PVP), vinylpyrrolidone / vinyl acetate copolymers, vinylpyrrolidone / styrene copolymers,
  • PVP polyvinylpyrrolidone
  • vinylpyrrolidone / vinyl acetate copolymers vinylpyrrolidone / styrene copolymers
  • Vinylpyrrolidone / vinylcaprolactam copolymers vinylpyrrolidone / vinylformamide copolymers and / or vinylpyrrolidone / vinyl alcohol copolymers.
  • Another suitable copolymer of vinyl pyrrolidone is the polymer known under the INCI name maltodextrin / VP copolymer.
  • a nonionic, film-forming, hydrophilic polymer is used as the film-forming, hydrophilic polymer.
  • an agent according to the invention is characterized in that it (c) contains at least one nonionic, film-forming, hydrophilic polymer.
  • a nonionic polymer is understood to mean a polymer which, in a protic solvent, such as water, does not carry structural units with permanent cationic or anionic groups under standard conditions, which are caused by counterions must be compensated for while maintaining electronic neutrality.
  • Cationic groups include, for example, quaternized ammonium groups, but no protonated amines.
  • Anionic groups include, for example, carboxyl and sulfonic acid groups.
  • the agents contain as nonionic, film-forming, hydrophilic polymer at least one polymer that is selected from the group consisting of
  • Carbon atoms in particular from N-vinylpyrrolidone and vinyl acetate,
  • copolymers of N-vinylpyrrolidone and vinyl acetate are used, it is again preferred if the molar ratio of the structural units contained in the monomer N-vinylpyrrolidone to the structural units in the polymer contained in the monomer vinyl acetate is in the range from 20 to 80 to 80 to 20, in particular from 30 to 70 to 60 to 40.
  • Suitable copolymers of vinyl pyrrolidone and vinyl acetate are available, for example, from BASF SE under the trademark Luviskol® VA 37, Luviskol® VA 55, Luviskol® VA 64 and Luviskol® VA 73.
  • Another particularly preferred polymer is selected from the polymers with the INCI name VP / methacrylamide / vinyl imidazole copolymer, which are available, for example, from BASF SE under the trade name Luviset Clear.
  • Another preferred nonionic, film-forming, hydrophilic polymer is a copolymer of N-vinylpyrrolidone and N, N-dimethylaminopropyl methacrylamide, which, for example, with the INCI name VP / DMAPA Acrylates Copolymer z. B. is sold under the trade name Styleze® CC 10 by the company ISP.
  • a cationic polymer that can be used according to the invention is the copolymer of N-vinylpyrrolidone, N-vinylcaprolactam, N- (3-dimethylaminopropyl) methacrylamide and 3- (methacryloylamino) propyl-lauryl-dimethylammonium chloride (INCI name: Polyquaternium-69), which is used, for example, under the Trade name AquaStyle ® 300 (28-32 wt .-% active substance in ethanol-water mixture, molecular weight 350,000) is sold by the company ISP.
  • AquaStyle ® 300 28-32 wt .-% active substance in ethanol-water mixture, molecular weight 350,000
  • Vinylpyrrolidone-vinylimidazolium methochloride copolymers as are offered under the names Luviquat ® FC 370, FC 550 and the INCI name Polyquaternium-16 as well as FC 905 and HM 552, Vinylpyrrolidone-vinylcaprolactam-acrylate terpolymers, such as those offered with acrylic acid esters and acrylic acid amides as the third monomer building block, for example under the name Aquaflex ® SF 40.
  • Polyquaternium-1 1 is the reaction product of diethyl sulfate with a copolymer of
  • Vinyl pyrrolidone and dimethylaminoethyl methacrylate are available, for example, under the names Dehyquart® CC 11 and Luviquat® PQ 11 PN from BASF SE or Gafquat 440, Gafquat 734, Gafquat 755 or Gafquat 755N from Ashland Inc.
  • Polyquaternium-46 is the reaction product of vinyl caprolactam and vinyl pyrrolidone
  • Methyl vinylimidazolium methosulfate and is available, for example, from BASF SE under the name Luviquat® Hold.
  • Polyquaternium-46 is preferably used in an amount of 1 to 5% by weight, based on the total weight of the cosmetic composition. It is very particularly preferred that polyquaternium-46 is used in combination with a cationic guar compound. It is even most preferred that polyquaternium-46 be used in combination with a cationic guar compound and polyquaternium-1 1.
  • anionic film-forming polymers for example, acrylic acid polymers can be used, which can be in uncrosslinked or crosslinked form.
  • suitable anionic film-forming polymers for example, acrylic acid polymers can be used, which can be in uncrosslinked or crosslinked form.
  • Corresponding products are sold, for example, under the trade names Carbopol 980, 981, 954, 2984 and 5984 by the company Lubrizol or also under the names Synthalen M and Synthalen K by the company 3V Sigma (The Sun Chemicals, Inter Harz).
  • Suitable film-forming, hydrophilic polymers from the group of natural gums are xanthan gum, gellan gum and carob gum.
  • Suitable film-forming, hydrophilic polymers from the group of the polysaccharides are hydroxyethyl cellulose, hydroxypropyl cellulose, ethyl cellulose and carboxymethyl cellulose.
  • Suitable film-forming, hydrophilic polymers from the group of acrylamides are, for example, polymers which are prepared from monomers of (methy) acrylamido-C1-C4-alkyl-sulfonic acid or the salts thereof.
  • Corresponding polymers can be selected from the polymers of polyacrylamidomethanesulfonic acid, polyacrylamidoethanesulfonic acid, polyacrylamido propanesulfonic acid, poly2-acrylamido-2-methylpropanesulfonic acid, poly-2-methylacrylamido-2-methylpropanesulfonic acid and / or poly-2-methylacrylamido-n-butanesulfonic acid.
  • Preferred polymers of the poly (meth) arylamido-C1-C4-alkyl-sulfonic acids are crosslinked and at least 90% neutralized. These polymers can be cross-linked or non-cross-linked.
  • Crosslinked and wholly or partially neutralized polymers of the type of poly-2-acrylamido-2-methylpropanesulfonic acids are known under the INCI names "ammonium polyacrylamido-2-methyl-propane-esulphonate” or "ammonium polyacryldimethyltauramide”.
  • Another preferred polymer of this type is the crosslinked poly-2-acrylamido-2methyl-propanesulphonic acid polymer sold by Clamant under the trade name Hostacerin AMPS, which is partially neutralized with ammonia.
  • an agent according to the invention is characterized in that it contains at least one film-forming, hydrophobic polymer (c) which is selected from the group of the copolymers of acrylic acid, the copolymers of methacrylic acid, the homopolymers or copolymers of acrylic acid esters, the homopolymers or copolymers of methacrylic acid esters, the homopolymers or copolymers of acrylic acid amides, the homopolymers or copolymers of methacrylic acid amides, the copolymers of vinylpyrrolidone, the copolymers of vinyl alcohol, the copolymers of vinyl acetate, the homopolymers or copolymers of ethylene or the homopolymers Copolymers of propylene, homopolymers or copolymers of styrene, polyurethanes, polyesters and / or polyamides.
  • c film-forming, hydrophobic polymer
  • suitable film-forming hydrophobic polymers can be selected from the homopolymers or copolymers of olefins, such as, for example, cycloolefins, butadiene, isoprene or styrene, vinyl ethers, vinyl amides, the esters or amides of (meth) acrylic acid with at least one C 1 -C 12 -alkyl group, an aryl group or a C2-C10-hydroxyalkyl group.
  • olefins such as, for example, cycloolefins, butadiene, isoprene or styrene
  • vinyl ethers vinyl amides
  • the esters or amides of (meth) acrylic acid with at least one C 1 -C 12 -alkyl group, an aryl group or a C2-C10-hydroxyalkyl group such as, for example, cycloolefins, butadiene, isoprene or st
  • Further film-forming hydrophobic polymers can be selected from the homo- or
  • Further film-forming hydrophobic polymers can be selected from the homo- or
  • Preferred anionic copolymers are, for example, copolymers of acrylic acid, methacrylic acid or their C 1 -C 6 -alkyl esters, as are sold under the INCI declaration Acrylates Copolymers.
  • a suitable commercial product is, for example Aculyn ® 33 from Rohm & Haas.
  • copolymers of acrylic acid, methacrylic acid or their C1-C6 alkyl esters and the esters of an ethylenically unsaturated acid and an alkoxylated fatty alcohol are also preferred.
  • Suitable ethylenically unsaturated acids are in particular acrylic acid, methacrylic acid and itaconic acid; Suitable alkoxylated fatty alcohols are, in particular, steareth-20 or ceteth-20.
  • most preferred polymers are for example Aculyn ® 22 (Acrylates / Steareth-20 Methacrylate Copolymer), Aculyn ® 28 (Acrylates / Beheneth-25 Methacrylate Copolymer), Structure 2001 ® (Acrylates / steareth-20 itaconate Copolymer), Structure 3001 ® (Acrylates / Ceteth-20 Itaconate Copolymer), Structure Plus ® (Acrylates / Aminoacrylates C10-30 Alkyl PEG-20 Itaconate Copolymer), Carbopol® 1342, 1382, Ultrez 20, Ultrez 21 (Acrylates / C 10 -30 Alkyl Acrylate Crosspolymer), Synthalen W 2000® (
  • Suitable polymers based on vinyl monomers are the homopolymers and copolymers of N-vinylpyrrolidone, vinylcaprolactam, vinyl- (C1-C6-) alkylpyrrole, vinyloxazole and vinylthiazole, of vinyl pyrimidine, vinyl imidazole.
  • copolymers octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer are also particularly suitable.
  • copolymers octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer are commercially available from NATIONAL STARCH, for example under the trade names AMPHOMER® or LOVOCRYL® 47, or the copolymers of acrylates / octylacrylamides which are sold under the trade names DERMACRYL® LT and DERMACRYL® 79 are distributed by NATIONAL STARCH.
  • Suitable polymers based on olefins are the homo- and copolymers of ethylene, propylene, butene, isoprene and butadiene.
  • block copolymers which comprise at least one block of styrene or the derivatives of styrene can be used as the film-forming hydrophobic polymers.
  • These block copolymers can be copolymers which, in addition to a styrene block, contain one or more further blocks, such as, for example, styrene / ethylene, styrene / ethylene / butylene, styrene / butylene, styrene / isoprene, styrene / butadiene.
  • Appropriate polymers are sold commercially by BASF under the trade name "Luvitol HSB".
  • particularly good colorations can be obtained with the anionic direct dyes, even if the film-forming hydrophobic polymer carries anionic charges.
  • an agent according to the invention is characterized in that it (c) contains at least one anionic, film-forming, hydrophobic polymer.
  • An anionic polymer is understood to mean a polymer which comprises repeating units with at least one carboxylic acid group, one sulfonic acid group and / or their physiologically tolerable salts.
  • an anionic polymer is produced from monomers which have at least one carboxylic acid group, one sulfonic acid group.
  • the aforementioned hydrophobic, film-forming (co) polymers of acrylic acid and the (co) polymers of methacrylic acid are very particularly preferred.
  • the polymers of this Group are the carboxylic acid groups which contain sulfonic acid groups or their salts in an amount which ensures that the hydrophobic character of the entire polymer is retained.
  • the film-forming polymer is a polymer or copolymer based on acrylic acid and / or methacrylic acid.
  • the film-forming polymer (s) (c) are preferably used in certain quantitative ranges in the agent according to the invention.
  • the agent based on its total weight, contains one or more polymers in a total amount of 0.1 to 25.0% by weight, preferably 0.2 to 20.0% by weight, more preferably from 0.5 to 15.0% by weight and very particularly preferably from 1.0 to 7.0% by weight.
  • an agent according to the invention is therefore characterized in that, based on its total weight, it contains one or more film-forming polymers (c) in a total amount of 0.1 to 25.0% by weight, preferably 0.2 to 20.0% by weight, more preferably from 0.5 to 15.0% by weight and very particularly preferably from 1.0 to 7.0% by weight.
  • the agents according to the invention can additionally contain at least one silicone as fourth ingredient (d).
  • This silicone if present, may be pre-formulated with the organic silicon compound (a) or the coloring compound (b).
  • the silicones which are optionally used for the formulation of the organic silicon compounds (a) are preferably volatile silicones, in particular siloxanes of the formula (IV)
  • each Rio independently represents a C 1 -C 6 -alkyl group, preferably methyl or ethyl, more preferably methyl,
  • k is 0 or an integer from 1 to 30, preferably 0 to 10, more preferably 0-5, most preferably 0 or 1, i.e. Hexamethyldisiloxane and octamethyltrisiloxane.
  • Volatile silicones refers to silicones with kinematic viscosities at 25 ° C in the range 0.65 - 20.0 cSt (0.0065 - 0.2 cm 2 / s), particularly preferably silicones with 0, 65-2.0 cSt, more preferably up to 1.0 cSt. These have the property to evaporate quickly during application and do not influence the condensation reaction of the silanes.
  • the silicones which are optionally used for the formulation of the color-imparting compounds (b) are preferably PEG-modified dimethylsiloxanes of the formula (V)
  • each Rio independently represents a C 1 -C 6 -alkyl group, preferably methyl or ethyl, more preferably methyl,
  • each Rn independently represents a C 1 -C 6 -alkyl group, preferably methyl or ethyl, more preferably methyl, or a group of the formula - (CH2) i- (OCH2CH2) mOH,
  • - k represents an integer from 1 to 100, preferably 1 to 30;
  • - 1 represents an integer from 1 to 10, preferably 2 or 3;
  • n stands for an integer from 1 to 30, preferably 5 to 20, more preferably 10, 11, 12, 13 or 14; where at least one Rn, but preferably not all Rn, is a group of the formula - (CH2) I - (OCH 2 CH 2 ) mOH.
  • the agent according to the invention contains the essential ingredients (a), (b) and optionally (c) in a cosmetic carrier, preferably in an aqueous or water-containing cosmetic carrier, as already described above.
  • Agents of this type in which the ingredients mentioned are present in an aqueous or water-containing cosmetic carrier are typically the ready-to-use agents.
  • the organic silicon compound (a) which comprises one or more hydroxyl groups or hydrolyzable groups per molecule, further hydrolyzes and / or condenses in the presence of the water.
  • the resulting hydrolysis products or oligomers and / or polymers have a particularly high affinity for the surface of the keatin material.
  • the coloring compounds (b) can optionally also form a stable and resistant film together with the film-forming, hydrophilic polymer (c).
  • ingredients (a) and (b) are formulated / mixed together in an aqueous or water-containing carrier for use and the optional ingredient (c) separately formulated in an aqueous or water-containing carrier for use and in one subsequent step is used.
  • ingredient (a) in an aqueous or water-containing carrier for use and to separately formulate ingredient (b) and optionally also ingredient (c) in an aqueous or water-containing carrier for use / mix and use in a subsequent step it may also be preferred according to the invention to formulate ingredient (a) in an aqueous or water-containing carrier for use and to separately formulate ingredient (b) and optionally also ingredient (c) in an aqueous or water-containing carrier for use / mix and use in a subsequent step.
  • the agent can, based on its total weight, have a water content of 15 to 95% by weight, preferably 20 to 95% by weight, more preferably 25 to 95% by weight, still more preferably 30 up to 95% by weight and very particularly preferably from 45 to 95% by weight.
  • an agent according to the invention is characterized in that, based on its total weight, it has a water content of 15 to 95% by weight, preferably 20 to 95% by weight, more preferably 25 to 95% by weight , even more preferably from 30 to 95% by weight and very particularly preferably from 45 to 95% by weight.
  • Multi-component packaging unit (kit-of-parts)
  • the previously described agent of the first subject matter of the invention can be the ready-to-use coloring agent.
  • the organic silicon compound (s) contains a class of reactive compounds which, as described above, can undergo further hydrolysis and / or condensation in the presence of water.
  • this agent is preferably made available to the user in the form of a multi-component packaging unit (kit-of-parts). Shortly before use on the keratinous material, the user can mix the various components of this packaging unit and in this way produce the ready-to-use coloring agent.
  • kit-of-parts a multi-component packaging unit
  • a second object of the present invention is a multi-component packaging unit (kit-of-parts) for dyeing keratinous material, in particular human hair, which is made up separately from one another
  • the agent (I) contains at least one organic silicon compound (a), as defined herein, and optionally also a silicone, as defined herein,
  • the agent (II) contains water and optionally at least one coloring compound (b), as defined herein, and
  • the agent (III) contains at least one film-forming polymer (c), as defined herein, and optionally at least one coloring compound (b), as defined herein,
  • agent (II), the agent (III) or both contain at least one coloring compound (b).
  • agents (II) and (III) both contain at least one coloring compound (b) this can be the same or different.
  • the ready-to-use agent is prepared by mixing agents (I) and (II) and agent (III) is applied separately after agents (I) and (II) are applied.
  • agent (III) is applied separately after agents (I) and (II) are applied.
  • all three agents (I), (II), and (III) can be mixed into the ready-to-use agent.
  • the user can first stir or spill the agent (I) which contains the organic silicon compound (s) (a) with the water-containing agent (II).
  • This agent from (I) and (II) can then be applied directly as such to the keratin-containing material, agent (III) being applied in a subsequent step.
  • the user can optionally add the agent (III), which may contain the color-imparting compound (s) (b) and the film-forming polymer (s) (c) add to the mixture of (I) and (II) and mix all three agents together and apply the resulting mixture.
  • the agents (I), (II) and (III) are applied successively to the keratinous material, so that the agents only interact with one another on the keratinous material.
  • the user can, for example, stir or spill the agent (I) which contains the organic silicon compound (s) (a) with the water-containing agent (II).
  • the user can now apply this mixture of (I) and (II) to the keratin materials - either directly after their preparation or after a short reaction time of 10 seconds to 20 minutes.
  • the user can now apply the agent (III), which contains the film-forming polymer (c), to the keratin material.
  • the agent (II) contains coloring compounds (b).
  • agent (III) may also contain coloring compounds, but in various embodiments does not contain such compounds (b).
  • the agent (I) itself is preferably made up with little or no water.
  • a multi-component packaging unit (kit-of-parts) according to the invention is characterized in that the agent (I) - based on the total weight of the agent (I) - has a water content of less than 1% by weight, contains even more preferably less than 0.1% by weight and very particularly preferably less than 0.01% by weight.
  • a multi-component packaging unit is characterized in that the agent (I) - based on the total weight of the agent (I) - one or more organic silicon compounds (a) in a total amount of 20 contains up to 100.0% by weight, preferably from 25 to 90% by weight, more preferably from 30 to 80% by weight and very particularly preferably from 40 to 75% by weight.
  • the agent (II) contains water.
  • a multi-component packaging unit (kit-of-parts) according to the invention is characterized in that the agent (II) - based on the total weight of the agent (II) - has a water content of 15 to 100% by weight, preferably of 35 to 100% by weight, more preferably from 55 to 100% by weight, even more preferably from 65 to 100% by weight and very particularly preferably from 75 to 100% by weight.
  • the agent (III) contains at least one film-forming polymer (c), as has already been disclosed in detail in the description of the first subject of the invention.
  • agents (II) and agents (III) can independently of one another contain at least one coloring compound (b).
  • the agent (II) and / or (III) contains the abovementioned, the preferred and the particularly preferred pigments (b).
  • the agent (II) and / or (III) contains the previously mentioned, the preferred and the particularly preferred substantive dyes (b).
  • a multi-component packaging unit is characterized in that the agent (II) and / or (III) - based on the total weight of the agent (III) - one or more coloring compounds (b) in a total amount of 0 , 01 to 10.0% by weight, preferably from 0.1 to 8.0% by weight, more preferably from 0.2 to 6.0% by weight and very particularly preferably from 0.5 to 4, Contains 5% by weight.
  • the agent (III) contains the already mentioned, the preferred and the particularly preferred film-forming polymers (c).
  • a multi-component packaging unit is characterized in that the agent (III) - based on the total weight of the agent (III) - one or more film-forming polymers (b) in a total amount of 0.1 to 25.0 % By weight, preferably from 0.2 to 20.0% by weight, more preferably from 0.5 to 15.0% by weight and very particularly preferably from 1.0 to 7.0% by weight.
  • the agents (I) and (II) or the agents (I), (II) and (III) can be mixed with one another in different amounts.
  • the first container can contain 5 g to 200 g of agent (I).
  • the second container can contain 5 g to 200 g of agent (II).
  • the third container can contain 5 b to 200 g of agent (III).
  • agents (I), (II) and (III) of the kit of the second subject matter of the invention can also contain one or more optional ingredients.
  • These can comprise the silicones already described above in agents (I), (II) or (III), with the agents (I) in particular using the silicones preferred for the formulation with the organic silicon compounds (a) and agents (II ) or (III), depending on which the compounds (b) contain, the preferred silicones for the formulation with the coloring compounds (b).
  • the agents can additionally contain one or more surfactants.
  • surfactants means surface-active substances. A distinction is made between anionic surfactants consisting of a hydrophobic residue and a negatively charged hydrophilic head group, amphoteric surfactants, which carry both a negative and a compensating positive charge, cationic surfactants, which in addition to a hydrophobic residue have a positively charged hydrophilic group, and nonionic surfactants, which have no charges but strong dipole moments and are highly hydrated in aqueous solution.
  • Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one -COO () - or -S0 3 (_) - group in the molecule.
  • Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the cocoalkyl-dimethylammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammonium glycinate, for example the cocoacylaminopropyl-dimethylammonium glycinate, and 2-alkyl -3-carboxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate.
  • a preferred zwitterionic surfactant is the
  • Ampholytic surfactants are surface-active compounds which, in addition to a Cs-C24-alkyl or -acyl group, contain at least one free amino group and at least one -COOH or -SOsH group in the molecule and are capable of forming internal salts.
  • ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each with about 8 to 24 C. Atoms in the alkyl group.
  • amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, amino propionates, aminoglycinates, imidazolinium betaines and sulfobetaines.
  • ampholytic surfactants are N-coconut alkylaminopropionate, coconut acylaminoethylaminopropionate and C12-Cis-acylsarcosine.
  • the agents can also additionally contain at least one nonionic surfactant.
  • Suitable nonionic surfactants are alkyl polyglycosides and alkylene oxide adducts with fatty alcohols and fatty acids, each with 2 to 30 moles of ethylene oxide per mole of fatty alcohol or fatty acid. Preparations with good properties are also obtained if they contain, as nonionic surfactants, fatty acid esters of ethoxylated glycerol which have been reacted with at least 2 moles of ethylene oxide.
  • the nonionic surfactants are used in a total amount of 0.1 to 45% by weight, preferably 1 to 30% by weight and very particularly preferably 1 to 15% by weight, based on the total weight of the particular agent.
  • the agents can additionally contain at least one cationic surfactant.
  • Cationic surfactants are understood to mean surfactants, that is to say surface-active compounds, each having one or more positive charges. Cationic surfactants contain only positive charges. These surfactants are usually composed of a hydrophobic part and a hydrophilic head group, the hydrophobic part generally consisting of a hydrocarbon skeleton (for example consisting of one or two linear or branched alkyl chains), and the positive charge (s) are located in the hydrophilic head group. Examples of cationic surfactants are examples of cationic surfactants.
  • quaternary ammonium compounds which can carry one or two alkyl chains with a chain length of 8 to 28 carbon atoms as hydrophobic radicals,
  • the cationic charge in the form of an onium structure can also be part of a heterocyclic ring (e.g. an imidazolium ring or a pyridinium ring).
  • the cationic surfactant can also contain further uncharged functional groups, as is the case, for example, with esterquats.
  • the cationic surfactants are used in a total amount of 0.1 to 45% by weight, preferably 1 to 30% by weight and very particularly preferably 1 to 15% by weight, based on the total weight of the particular agent.
  • the agents according to the invention can also contain at least one anionic surfactant.
  • Anionic surfactants are surface-active agents with exclusively anionic charges (neutralized by a corresponding counter cation).
  • anionic surfactants are fatty acids, alkyl sulfates, alkyl ether sulfates and ether carboxylic acids with 12 to 20 carbon atoms in the alkyl group and up to 16 glycol ether groups in the molecule.
  • the anionic surfactants are used in a total amount of 0.1 to 45% by weight, preferably 1 to 30% by weight and very particularly preferably 1 to 15% by weight, based on the total weight of the particular agent.
  • the agents can also contain other active ingredients, auxiliaries and additives, such as solvents, fat components such as the Cs-C30 fatty alcohols, the Cs-C3o fatty acid triglycerides, the Cs-Cso fatty acid monoglycerides, the Cs-Cso -Fatty acid diglycerides and / or the hydrocarbons; Structurants such as glucose, maleic acid and lactic acid, hair-conditioning compounds such as phospholipids, for example lecithin and cephalins; Perfume oils, dimethyl isosorbide and cyclodextrins; active ingredients that improve fiber structure, in particular mono-, di- and oligosaccharides such as, for example, glucose, galactose, fructose, fructose
  • the additional active substances and auxiliaries are preferably used in the preparations according to the invention in amounts of in each case from 0.0001 to 25% by weight, in particular from 0.0005 to 15% by weight, based on the total weight of the particular agent.
  • agents described above - both the ready-to-use agent of the first subject matter of the invention and the agent of the multi-component packaging unit of the second subject matter of the invention - are used in processes for dyeing keratinous materials, in particular for dyeing human hair.
  • a third object of the present invention is a method for dyeing keratinous material, in particular human hair, comprising the following steps in the order given:
  • Pretreatment agent (V) in a water-containing cosmetic carrier contains at least one organic silicon compound (a) and optionally also a silicone (d), as have already been disclosed in detail in the description of the first subject of the invention,
  • a colorant (F) to the keratinous material, the colorant comprising at least one color-imparting compound (b) and at least one film-forming polymer (c), as have already been disclosed in detail in the description of the first subject of the invention or, in another embodiment,
  • a pretreatment and coloring agent (VF) on the keratinic material, the pretreatment and coloring agent (VF) containing at least one organic silicon compound (a), at least one coloring compound (b), and optionally also in a water-containing cosmetic carrier a silicone (d), as described in detail in the description of the first
  • a pretreatment and coloring agent (VF) on the keratinic material, the pretreatment and coloring agent (VF) containing at least one organic silicon compound (a), at least one coloring compound (b), and optionally also in a water-containing cosmetic carrier a silicone (d), as described in detail in the description of the first
  • the keratin materials in particular human hair, are first treated with a pretreatment agent (V) or preferably a pretreatment and coloring agent (VF). Subsequently, either the actual coloring agent (F) or a post-treatment agent (N) or a post-treatment and coloring agent (NF) - which contains the film-forming polymer and optionally the coloring compound (s) - is added to the keratin materials.
  • a pretreatment agent V
  • VF pretreatment and coloring agent
  • NF post-treatment and coloring agent
  • the pretreatment agent (V) itself contains the dyes or coloring compounds and is therefore a pretreatment and coloring agent (VF).
  • Characteristic of the pretreatment agent (V) and the pretreatment and coloring agent (VF) is its content of at least one reactive organic silicon compound (a). That or the reactive organic Silicon compounds (a) functionalize the hair surface as soon as they come into contact with it. In this way, a first, colored or uncolored film is formed.
  • a colorant (F) or a post-treatment and colorant (NF) can now be applied to the hair.
  • a film is also formed on the - now already functionalized - hair surface, with (further) coloring compounds being embedded in the film and in this way on the hair be deposited.
  • VF pre-treatment and coloring agent
  • N post-treatment agent
  • the film produced in this way "in situ", in which the coloring compound is embedded, is characterized by excellent wash fastness and a homogeneous color result.
  • the colors are shiny and the feel of the colored keratin materials is smooth and pleasant.
  • the pre-treatment agent (V) or the pre-treatment and coloring agent (VF) is the ready-to-use pre-treatment agent (V) or pre-treatment and coloring agent (VF).
  • the pretreatment agent (V) or pretreatment and coloring agent (VF) thus contains at least one organic silicon compound (a).
  • the pretreatment agent (V) or pretreatment and coloring agent (VF) contains water, the water coming from the agent (II) of the kit-of-parts according to the invention.
  • a method according to the invention is characterized in that the pretreatment agent (V) or pretreatment and coloring agent (VF) before use on the keratinous material by mixing a first agent (I) and a second agent (II) is manufactured, whereby
  • the agent (I) contains at least one organic silicon compound (a), as disclosed in detail in the description of the first and second subject matter of the invention and
  • the agent (II) contains water and optionally at least one coloring compound, as described herein.
  • the pre-treatment agent (V) or pre-treatment and coloring agent (VF) - based on the total weight of the pre-treatment agent (V) or pre-treatment and coloring agent (VF) - has a water content of 15 to 95% by weight, preferably from 20 to 95% by weight, more preferably from 25 to 95% by weight, even more preferably from 30 to 95% by weight and very particularly preferably from 45 to 95% by weight.
  • a method according to the invention is characterized in that the pretreatment agent (V) or pretreatment and coloring agent (VF) - based on the total weight of the pretreatment agent or pretreatment and coloring agent - has a water content of 15 to 95% by weight %, preferably from 20 to 95% by weight, more preferably from 25 to 95% by weight, even more preferably from 30 to 95% by weight and very particularly preferably from 45 to 95% by weight.
  • the pretreatment agent (V) preferably has a pH of from 7.0 to 11.5, preferably from 7.5 to 11, 0 and particularly preferably from 8.0 to 10.5.
  • a method according to the invention is characterized in that the pretreatment agent (V) or pretreatment and coloring agent (VF) has a pH of from 7.0 to 11.5, preferably from 7.5 to 11, 0 and particularly preferably from 8.0 to 10.5.
  • the pretreatment agent (V) or pretreatment and coloring agent (VF) preferably contains at least one alkalizing agent, which is added in an amount which ensures the setting of the optimal pH value for the particular hair treatment.
  • the pH values in the sense of the present invention are pH values which were measured at a temperature of 22 ° C.
  • the amount of alkalizing agent added can vary, usually from 0.01 to 15% by weight being necessary for this .
  • the pretreatment agent (V) or pretreatment and coloring agent (VF) can contain, for example, ammonia, alkanolamines and / or basic amino acids as the alkalizing agent.
  • alkanolamines which can be used in the agent according to the invention are preferably selected from primary amines having a C2-C6-alkyl base which carries at least one hydroxyl group.
  • Preferred alkanolamines are selected from the group consisting of 2-aminoethan-1-ol (monoethanolamine), 3-aminopropan-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-methylpropan-1-ol, 1 -Amino-2-methylpropan-2-ol, 3-aminopropan-1, 2-diol, 2-amino-2-methylpropane-1, 3-diol.
  • Alkanolamines which are particularly preferred according to the invention are selected from 2-aminoethan-1-ol and / or 2-amino-2-methylpropan-1-ol.
  • a particularly preferred embodiment is therefore characterized in that the agent according to the invention contains as alkali agent an alkanolamine selected from 2-aminoethan-1-ol and / or 2-amino-2-methylpropan-1-ol.
  • amino acid in the sense of the invention is an organic compound which contains at least one protonatable amino group and at least one -COOH or a -S03H group in its structure.
  • Preferred amino acids are aminocarboxylic acids, in particular a- (alpha) -aminocarboxylic acids and w-aminocarboxylic acids, with a-aminocarboxylic acids being particularly preferred.
  • basic amino acids are understood to mean those amino acids which have an isoelectric point p1 of greater than 7.0.
  • Basic a-aminocarboxylic acids contain at least one asymmetric carbon atom.
  • both possible enantiomers can be used equally as a specific compound or also mixtures thereof, in particular as racemates.
  • the basic amino acids are preferably selected from the group which is formed from arginine, lysine, ornithine and histidine, particularly preferably from arginine and lysine.
  • an agent according to the invention is therefore characterized in that the alkalizing agent is a basic amino acid from the group arginine, lysine, ornithine and / or histidine.
  • the agent can contain further alkalizing agents, in particular inorganic alkalizing agents.
  • inorganic alkalizing agents which can be used according to the 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.
  • Very particularly preferred alkalizing agents are ammonia, 2-aminoethan-1-ol (monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol, 1-amino-2- methylpropan-2-ol, 3-aminopropan-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.
  • a process according to the invention is characterized in that the pretreatment agent (V) or pretreatment and coloring agent (VF) contains at least one alkalizing agent, which is preferably selected from the group consisting of ammonia, 2-aminoethane-1- ol (monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2 -ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol, 1-amino-2-methylpropan-2-ol, 3-aminopropan-1, 2 - diol, 2-amino-2-methylpropane-1, 3-diol, arginine, lysine, ornithine, histidine, sodium hydroxide, potassium
  • Acidifying agents preferred according to the invention are luxury acids, such as, for example, citric acid, acetic acid, malic acid or tartaric acid, and dilute mineral acids.
  • the coloring agent (F), the after-treatment agent (N) or the after-treatment and coloring agent (NF) is applied to the keratin materials.
  • the means mentioned are in each case the ready-to-use means F, N or NF.
  • the coloring agent (F), the aftertreatment agent (N) or the aftertreatment and coloring agent (NF) contains the film-forming polymer (s) (c) and optionally the coloring compounds (c) in a cosmetic carrier, preferably in a water-containing cosmetic carrier.
  • a method according to the invention is characterized in that the colorant (F), the aftertreatment agent (N) or the aftertreatment and colorant (NF) - based on the total weight of the respective agent - has a water content of 15 to 95 % By weight, preferably from 20 to 95% by weight, more preferably from 25 to 95% by weight, even more preferably from 30 to 95% by weight and very particularly preferably from 45 to 95% by weight .
  • the coloring agent (F), the aftertreatment agent (N) or the aftertreatment and coloring agent (NF) is also alkaline and has a pH of 7. 0 to 11.5, preferably from 7.5 to 11, 0 and particularly preferably from 8.0 to 10.5.
  • a process according to the invention is characterized in that the colorant (F), the aftertreatment agent (N) or the aftertreatment and colorant (NF) preferably has a pH of from 7.0 to 11.5 from 7.5 to 11.0 and particularly preferably from 8.0 to 10.5.
  • the colorant (F), the aftertreatment agent (N) or the aftertreatment and colorant (NF) preferably also contains at least one alkalizing agent, which is added in an amount which is optimal for the particular hair treatment pH guaranteed.
  • the pH values in the sense of the present invention are pH values that were measured at a temperature of 22 ° C.
  • the colorant (F), the aftertreatment agent (N) or the aftertreatment and colorant (NF) can contain at least one alkalizing agent from the aforementioned group.
  • the colorant (F), the aftertreatment agent (N) or the aftertreatment and colorant (NF) particularly preferably contains at least one alkalizing agent which is preferably selected from the group consisting of ammonia, 2-aminoethan-1-ol (monoethanolamine) and 3-aminopropane -1-ol, 4-amino-butan-1-ol, 5-aminopentan-1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentane -3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol, 1-amino-2-methylpropan-2-ol, 3-aminopropan-1, 2-diol, 2-amino -2-methylpropane-1
  • a process according to the invention is characterized in that the colorant (F), the post-treatment agent (N) or the post-treatment and colorant (NF) contains at least one alkalizing agent, which is preferably selected from the group consisting of ammonia, 2-aminoethan-1-ol (monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol , 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol, 1-amino-2-methylpropan-2-ol, 3 -Aminopropane-1,2-diol, 2-amino-2-methylpropane-1,3-diol, arginine, lysine, ornithine,
  • alkalizing agent which is
  • the application properties of the resulting dyeing can be further improved by choosing the optimal process conditions.
  • the pretreatment agent (V) is first applied to the keratin materials, in particular human hair.
  • the pretreatment agent (V) is allowed to act on the keratin materials.
  • exposure times of 10 seconds to 10 minutes, preferably from 20 seconds to 5 minutes and very particularly preferably from 30 seconds to 2 minutes on the hair have proven to be particularly advantageous.
  • a method according to the invention is characterized by the
  • the pretreatment agent (V) can now be rinsed out of the keratin materials before the coloring agent (F) is applied to the hair in the subsequent step.
  • step (4) the colorant (F) is now applied to the keratin materials. After the application, the coloring agent (F) is now allowed to act on the hair.
  • the process according to the invention allows the dyeing agent (F) to be produced with a particularly good intensity and fastness to washing even with a short exposure time of the dye (F). Exposure times from 10 seconds to 10 minutes, preferably from 20 seconds to 5 minutes and very particularly preferably from 30 seconds to 3 minutes on the hair have proven to be particularly advantageous.
  • a method according to the invention is characterized by the
  • a conditioner can now optionally be used.
  • aftertreatment agent (N) or aftertreatment agent and colorant (NF) allowing the aftertreatment agent (N) or aftertreatment agent and colorant (NF) to act for a period of from 10 seconds to 30 minutes, preferably from 10 seconds to 10 minutes, and
  • VF pretreatment and coloring agent
  • Keratin materials especially human hair, are applied.
  • the pretreatment and coloring agent (VF) is allowed to act on the keratin materials.
  • exposure times of 30 seconds to 30 minutes, preferably from 30 seconds to 15 minutes and very particularly preferably from 30 seconds to 10 minutes have proven to be particularly advantageous.
  • a method according to the invention is characterized by the
  • the pre-treatment and coloring agent (VF) can now be rinsed out of the keratin materials before the after-treatment agent (N) or after-treatment and coloring agent (NF) is applied to the hair in the subsequent step.
  • a method comprising the following steps in the order specified is very particularly preferred
  • aftertreatment agent (N) or aftertreatment agent and colorant (NF) allowing the aftertreatment agent (N) or aftertreatment agent and colorant (NF) to act for a period of from 10 seconds to 30 minutes, preferably from 10 seconds to 10 minutes, and
  • aftertreatment agent (N) or aftertreatment agent and colorant (NF) allowing the aftertreatment agent (N) or aftertreatment agent and colorant (NF) to act for a period of from 10 seconds to 30 minutes, preferably from 10 seconds to 10 minutes, and
  • step (4) the post-treatment agent (N) or post-treatment and coloring agent (NF) is now applied to the keratin materials. After the application, the post-treatment agent (N) or post-treatment and coloring agent (NF) is then allowed to act on the hair.
  • the method according to the invention allows the production of dyeings with particularly good intensity and fastness to washing even with a short exposure time of the aftertreatment agent (N) or aftertreatment and coloring agent (NF). Exposure times to the hair from 10 seconds to 30 minutes or to 20 minutes or to 10 minutes, preferably from 20 seconds to 5 minutes and very particularly preferably from 30 seconds to 3 minutes have proven to be particularly advantageous.
  • a method according to the invention is characterized by the
  • aftertreatment agent (N) or aftertreatment and coloring agent (NF) to act on the hair for a period of from 10 seconds to 30 minutes, preferably from 20 seconds to 5 minutes and very particularly preferably from 30 seconds to 3 minutes, and
  • a conditioner can now optionally be used.
  • aftertreatment agent (N) or aftertreatment and coloring agent (NF) to act on the hair for a period of from 10 seconds to 30 minutes, preferably from 20 seconds to 5 minutes and very particularly preferably from 30 seconds to 3 minutes, and
  • the conditioner preferably contains at least one cationic and / or nonionic surfactant. Surprisingly, it has been found that the use of the conditioner - especially if it contains at least one cationic surfactant - may further improve the authenticity of the dyeings obtained and additionally intensify the color result.
  • a method according to the invention is characterized in that the conditioner contains at least one cationic and / or nonionic surfactant.
  • a method according to the invention is characterized in that the conditioner contains at least one cationic surfactant.
  • the post-treatment agent (N ) or the aftertreatment and coloring agent (NF) is a period of at most 48 hours, preferably at most 24 hours, more preferably at most 12 hours and very particularly preferably at most 6 hours.
  • a method according to the invention is characterized in that the pretreatment agent (V) or the pretreatment and coloring agent (VF) and the coloring agent (F) or post-treatment agent (N) or post-treatment and coloring agent (NF) within a period of a maximum of 48 hours, preferably a maximum of 24 hours, more preferably a maximum of 12 hours and very particularly preferably a maximum of 6 hours.
  • a fourth object of the present invention is a method for producing a cosmetic agent for use in dyeing keratinous material, in particular human hair, containing at least one organic silicon compound (a), comprising the following steps in the order given:
  • R2 independently of one another for a hydrogen atom, a Ci-C6-alkyl group, a hydroxy-Ci-C6-alkyl group, a C2-C6-alkenyl group, an amino-Ci-C6-alkyl group, an amino-Ci-C6 -alkyl- amino-Ci-C6-alkyl group or a group of formula (III),
  • R3 and R5 independently represent a Ci-C6-alkyl group, preferably a Ci-C2-alkyl group,
  • R4 and R ⁇ independently represent a Ci-C6-alkyl or a C2-C6-alkenyl group
  • - a and b each independently represent an integer from 2 to 3, preferably 3, and
  • - c is 0 or 1;
  • R7 represents a linear or branched CiC-12-alkyl group, hydroxy-Ci-Ci2-alkyl group or C2-C12 alkenyl group, preferably a linear Ci-C6-alkyl or C2-C6-alkenyl group, more preferably Ci C2 alkyl group,
  • Re represents a Ci-C6-alkyl group, preferably a Ci-C2-alkyl group,
  • R9 represents a Ci-C6-alkyl or a C2-C6-alkenyl group
  • step (1) (2) partial hydrolysis and condensation of the silanes presented in step (1) by adding a substoichiometric amount of water, preferably with removal of the liberated alcohols by means of distillation under reduced pressure.
  • the mass ratio of all compounds of the formula (I) to all compounds of the formula (II) is preferably 5: 1 to 1:20, more preferably 1: 1 to 1:10, more preferably 1: 2 to 1: 5.
  • the molar ratio of all compounds of the formula (I) to all compounds of the formula (II) is preferably 2: 1 to 1:30, more preferably 1: 1 to 1:20, more preferably 1: 2 to 1:10.
  • the water is used in a sub-stoichiometric amount, ie an amount that is less than the amount that would theoretically be required to hydrolyze all hydrolyzable groups present on the Si atoms, ie the alkoxysilane groups (hence “partial hydrolysis”).
  • the amount of water used for this is preferably at least 10% below the stoichiometric amount necessary for complete hydrolysis, preferably at least 20% below.
  • the amount of water used for the hydrolysis is particularly preferably 0.2 to 2.5 mol of water per 1 mol of Si, preferably 0.4 to 2.0 mol of water per 1 mol of Si, more preferably 0.6 to 1.2 mol Water per 1 mol Si.
  • the hydrolyzable groups on the Si Atoms hydrolyze and, since they are alkoxy groups, split off the corresponding alcohols.
  • Si-OH groups remain on the silicon, which in the next step can react with one another in a condensation reaction, ie with elimination of water.
  • the amount of water is such that the condensation is a partial condensation, whereby “partial condensation” or “partial condensation” in this context means that not all condensable groups of the silanes present react with one another, so that the organic silicon compound (a) formed each molecule has an average of at least one hydrolyzable / condensable group.
  • the average number of condensable / hydrolyzable groups per molecule of compound (a) is preferably at least 1.5, more preferably at least 2.
  • the water can be added continuously, in portions or directly as a total.
  • the addition is preferably carried out with stirring.
  • the reaction mixture can be cooled or the amount and rate of water added can be adjusted.
  • the addition and reaction can take place over a period of 2 minutes to 72 hours.
  • the addition is preferably continuous, especially on an industrial scale.
  • the temperature during the hydrolysis in step (2) does not exceed 75 ° C., preferably 60 ° C.
  • the temperature during the hydrolysis reaction and optionally also during the condensation reaction is preferably in the range from 10 to 75 ° C., preferably 20 to 60 ° C.
  • the hydrolysis reaction is carried out under a protective gas, for example nitrogen, or it is otherwise ensured that the reaction mixture does not come into contact with additional moisture, such as, for example, atmospheric moisture.
  • a protective gas for example nitrogen
  • the reaction is therefore preferably carried out in a reaction vessel which is closed with respect to the ambient atmosphere, i.e. in the absence of moisture.
  • the hydrolysis reaction is followed by a condensation reaction in which the Si-O-Si bonds are formed.
  • the condensation reaction (partial condensation) takes place under reduced pressure in order to remove the alcohols formed and, if appropriate, also water from the reaction mixture and convert them into the gas phase. This suppresses the back reaction and shifts the equilibrium of the reaction to the condensate side.
  • the reduced pressure is preferably achieved by vacuum distillation, in which the reaction mixture is subjected to reduced pressure, typically up to a maximum of 800 mbar, preferably up to a maximum of 500 mbar, for example 50-800 or 50-500 mbar, and the volatile alcohols and, if appropriate, also water condensed and collected as a liquid distillate in a template.
  • the distillation can optionally be carried out with cooling of the evaporated alcohols / water by means of a cooler.
  • the reduced pressure can be generated using conventional methods known in the art, typically using a vacuum pump.
  • methoxysilane - Or ethoxysilane groups especially di- and trimethoxy and ethoxysilanes, particularly preferably trimethoxy or triethoxysilanes.
  • production takes place in a two- or multi-stage process, in which in a first step the hydrolysis is carried out by adding substoichiometric amounts of water, either continuously, in stages or in one, under normal pressure. Only after the amount of water has been added, preferably completely, is reduced pressure applied in a subsequent step and the alcohols formed are removed by means of vacuum distillation.
  • vacuum distillation is preferably carried out after at least 50% by weight of the planned total amount of water, preferably at least 70, 80, 90, 95 or 100% by weight of the water, has been added.
  • step (2) can thus be divided into a first step (2a), in which the water is added, and a step (2b), in which the vacuum distillation takes place.
  • the vacuum distillation can also take place simultaneously with the hydrolysis.
  • the pressure is reduced before the water is added, at the start of the addition or after 5-20% by weight of the planned total amount of water has been added.
  • vacuum distillation is performed under conditions that result in a product that contains less than 5%, preferably less than 2%, more preferably less than 1% by weight of free alcohols (from the hydrolysis reaction).
  • the water content of the product after the vacuum distillation is less than 1% by weight, more preferably less than 0.1% by weight and very particularly preferably less than 0.01% by weight.
  • the condensation reaction at reduced pressure can be carried out at elevated temperature.
  • the reaction mixture can be actively heated.
  • the temperature can be adjusted such that the alcohols released in the condensation reaction can evaporate and be removed at the reduced pressure applied.
  • the temperature is not more than 75 ° C., preferably not more than 60 ° C. It may further be preferred that the reaction mixture is not actively heated and that any increase in temperature above ambient temperature is only brought about by the exothermic nature of the hydrolysis.
  • the reaction can also take place in the presence of solvents, ie in particular alcohols such as methanol or ethanol. These are then usually used in 0.1 to 5 times the amount by weight, based on the silanes used, and then removed by distillation.
  • aminopropyltri (m) ethoxysilane as component (a1) in combination with an alkyltrialkoxysilane, for example alkyltri (m) ethoxysilane, in particular Ci-3-alkyltri (m) ethoxysilane as component (a2), in order to use the organic silicon compound (a) to get.
  • the quotient of the molar ratio of Si / hydrolyzable group (in particular alkoxy group) in the molecule / oligomer produced is at least 0.3, preferably at least 0.5, more preferably at least 0.7, for example at least 1.
  • Organic silicon compounds a) according to the invention have, for example, a hydrolyzable group / alkoxy group content of, for example, 5 to 30% by weight.
  • Organic silicon compounds a) according to the invention can be chain-like or cyclic. In particular, they are mixtures of chain and / or cyclic oligomers.
  • the degree of oligomerization is typically 2 to 30, i.e. the organic silicon compounds a) according to the invention consist of 2 to 30 monomeric units which are derived from the compounds a1 and, if used, also a2, preferably 3 to 20 units.
  • the partial condensate was obtained by introducing 700.5 g of MTMS and 199.5 g of AMEO and mixing with stirring in a closed reaction vessel. Then 100.5 g of water were slowly added with stirring and the batch was stirred for a further 20 minutes. The alcohols formed were then distilled off under vacuum at 50 ° C. for 60 minutes and the remaining condensate was stabilized by adding 499.5 g of volatile silicone (Xiameter PMX 200; Dow Chemical).
  • the ready-to-use pretreatment and coloring agent (VF) was prepared by mixing 1.5 g of agent (I) and 21.5 g of agent (II). The agents (I) and (II) were shaken together for 3 minutes. The pretreatment and coloring agent (VF) was then left to stand for about 5 minutes. The pH value of the ready-to-use pre-treatment and coloring agent (VF) was approx. 10.

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Abstract

La présente demande a pour objet un agent pour colorer la matière kératinique, en particulier les cheveux humains, qui contient, dans un véhicule cosmétique (a), au moins un composé de silicium organique spécial et (b) au moins un composé colorant. L'invention concerne en outre une unité d'emballage à plusieurs composants (Kit-of-parts) pour colorer la matière kératinique, en particulier les cheveux humains, qui est confectionnée séparément en trois récipients différents les uns des autres comprenant les agents (I), (II) et (III), l'agent (I) contenant le ou les composés de silicium organiques (a) et le ou les composants colorants (b) étant contenus soit dans l'agent (II) conjointement avec de l'eau et/ou dans l'agent (III) conjointement avec au moins un polymère hydrophile filmogène (c). Pour finir, l'invention concerne également des procédés pour colorer la matière kératinique en utilisant les agents décrits ainsi que des procédés pour produire le composé de silicium organique (a).
EP19783250.4A 2018-12-19 2019-09-30 Agent pour colorer les cheveux contenant au moins un composé de silicium organique i Pending EP3897562A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102018132893.1A DE102018132893A1 (de) 2018-12-19 2018-12-19 Mittel zum Färben von Haaren enthaltend mindestens eine organische Siliciumverbindung I
PCT/EP2019/076466 WO2020126140A1 (fr) 2018-12-19 2019-09-30 Agent pour colorer les cheveux contenant au moins un composé de silicium organique i

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EP3897562A1 true EP3897562A1 (fr) 2021-10-27

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EP (1) EP3897562A1 (fr)
CN (1) CN113329731A (fr)
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WO (1) WO2020126140A1 (fr)

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DE102021202048A1 (de) * 2021-03-03 2022-09-08 Henkel Ag & Co. Kgaa Verfahren zum Färben von keratinischem Material, umfassend die Anwendung von einer siliciumorganischen Verbindung, einer farbgebenden Verbindung, eines Versiegelungsreagenz und eines Vorbehandlungsmittels
DE102021202043A1 (de) * 2021-03-03 2022-09-08 Henkel Ag & Co. Kgaa Verfahren zum Färben von keratinischem Material, umfassend die Anwendung von einer siliciumorganischen Verbindung, einer farbgebenden Verbindung, einem Versiegelungsreagenz und einem Polymer-haltigen Nachbehandlungsmittel

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FR2922760B1 (fr) * 2007-10-31 2009-11-20 Oreal Eclaircissement et/ou coloration de fibres keratiniques humaines au moyen d'une composition comprenant un compose aminosilicie particulier et composition et dispositif
EP2168633B1 (fr) 2008-09-30 2016-03-30 L'Oréal Composition cosmétique comprenant un composé organique du silicium comportant au moins une fonction basique, un polymère filmogène hydrophobe, un pigment et un solvant volatil
FR3060980B1 (fr) * 2016-12-22 2019-05-31 L'oreal Procede de coloration des fibres keratiniques mettant en oeuvre une composition comprenant au moins deux organosilanes differents l'un de l'autre
GB2561014B (en) * 2017-04-02 2020-04-22 Henkel Kgaa Compositions and methods for coloring fibers
CN108814998B (zh) * 2018-08-24 2019-12-03 福建拓烯新材料科技有限公司 一种基于石墨烯的染发剂的制备方法

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DE102018132893A1 (de) 2020-06-25

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