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
  • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
  • A61K8/0216—Solid or semisolid forms
  • A61K8/022—Powders; Compacted Powders
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
  • A61K8/11—Encapsulated compositions
• • 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
  • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
  • A61K8/25—Silicon; Compounds thereof
• • 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
  • A61K8/817—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
• • 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
  • A61K8/86—Polyethers
• • 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
  • 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
  • A61K8/894—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a polyoxyalkylene group, e.g. cetyl dimethicone copolyol
• • 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
  • A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
  • A61K8/922—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of vegetable origin
• • 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
  • A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
  • A61K8/927—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of insects, e.g. shellac
• • 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
  • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
• • 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
  • A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole

Definitions

• the present invention relates to the technical field of use of pulverulent compositions for the cosmetic treatment of keratinic fibers, in particular human hair.
• Powdered cosmetics are well known to those skilled in the art. These have long been used, for example, in the field of skin treatment. Typical examples include make-up powder or eye shadow. Furthermore, surfactant-free but solvent-containing dry shampoos which are sprayed onto the fibers by means of an aerosol device are in use for the use of the hair treatment. The starch particles contained in the dry shampoo absorb sebum and dirt after evaporation of the solvent and are brushed off after a contact time. Furthermore, the person skilled in the art knows of powdered hair colors which, however, are not applied in powder form to the fibers but are previously stirred with separately added water to form a coloring cream. The resulting cream then applies to the hair.
• Styling agents for the deformation of keratinous fibers are generally long known and are used in various embodiments for the construction, for refreshing and fixing hairstyles, which can be obtained in many hair types using only firming agents.
• Both hair treatment products which serve a permanent, as well as those that serve a temporary shaping of the hair, play an important role.
• Temporary shapes, which should give a good grip, without affecting the healthy appearance of the hair, such as their gloss, can be achieved for example by hair sprays, hair waxes, hair gels, hair drier, etc.
• Corresponding temporary shaping agents usually contain synthetic polymers as the shaping component. Preparations containing a polymer can be applied to the hair by means of propellants or by a pumping mechanism. Hair gels and hair waxes, however, are usually not applied directly to the hair, but distributed by means of a comb or hands in the hair.
• WO 2007/05151 1 A1 discloses the use of a pulverulent composition containing 50 to 95% by weight of an aqueous solvent, hydrophobicized silica powder and at least one film-forming and / or setting polymer in the aqueous solvent for the temporary deformation of keratinic fibers.
• WO 2010/054980 A1 discloses the use of a pulverulent composition with core-shell particles for the temporary deformation of keratinic fibers, wherein the shell contains the particles of at least one hydrophobized metal oxide powder and the core comprises a liquid, aqueous phase.
• These powdery core-shell particles comprise at least one film-forming and / or setting polymer in the form of particles.
• the powder compositions known from the prior art show a limited application profile.
• rinse-off cosmetic ie cosmetic is rinsed / washed from the substrate after application
• the pulverulent compositions should also be compatible and stable with the waxy esters customary in the field of hair styling.
• the powder should be able to transform into a liquid to pasty shape / consistency.
• the powdered compositions should not form fine dusts of solidifying polymers in the composition as solids.
• the setting polymer should release well from the powdered composition and be distributed evenly on the substrate.
• the powdered compositions should not form fine dusts of film-forming polymers which are solid in composition.
• the film-forming polymer should release well from the powdered composition and be evenly distributed on the substrate.
• the latter should remain stable in the presence of hydrous and powdery core-shell particles, even in the presence of at least 2% by weight of washing-active surfactants.
• These powdery compositions are predominantly provided as a rinse-off cosmetic.
• oxidation dye precursor (s) and oxidizing agent in the same powdered composition should be possible.
• oxidation dye precursor (s) and oxidizing agent in the same powdered composition should be possible.
• These powdery compositions are predominantly provided as a rinse-off cosmetic.
• a first subject of the present invention are pulverulent compositions comprising at least one particulate, amorphous metal oxide, with the proviso that in said metal oxide at least one cosmetic active ingredient is present, which is selected from waxy esters, setting polymers, film-forming polymers, oxidation dye precursors, anionic surfactants , keratin-reducing compounds or mixtures thereof.
• particles are particles which are present as grains (see DIN 66160: 1992-09) of solids.
• powders are compositions whose particles are freely free-flowing under their own weight (see DIN EN ISO 6186: 1998-08).
• An amorphous state of a solid is present when its atomic building blocks are predominantly not arranged in crystal lattices.
• a crystalline substance in which apart from a close arrangement between the building blocks (ie constant distances and angles to the nearest neighboring atoms) also a remote order (regular repetition of a motif in a crystal lattice) exists, is in the amorphous state only a more or less pronounced Nahaku vor.
• Sorption is the collective term for all processes (including absorption, adsorption) in which a substance is selectively taken up by another substance in contact with it.
• the particulate amorphous metal oxide is the sorbent and the cosmetic active ingredient is the sorbate.
• various drugs can be sorbed individually onto particles of an amorphous metal oxide.
• amorphous metal oxide For example, only one active ingredient is sorbed on the particles. These particles are then mixed (separate sorption). This results in a powdery composition having a sorbed on particulate amorphous metal oxides drug mixture, wherein on each particle of this mixture, only one of the cosmetic active ingredients is sorbed.
• the particulate, amorphous metal oxide is a precipitated silica.
• precipitated silica is in turn preferably a precipitated silica with a proportion of 0, 1 to 1, 0 wt .-% Na 2 0 based on their weight.
• the object according to the invention is achieved particularly well if the particulate, amorphous metal oxide has a DBP number of from 50 to 800 g, preferably from 100 to 500 g, particularly preferably from 200 to 400 g, most preferably from 250 to 350 g, each per 100 g of metal oxide.
• the DBP number is always given in grams of DBP (dibutyl phthalate) per 100 grams of metal oxide and determined according to the ASTM D 2414 protocol based on the dried substance.
• the release of the sorbed cosmetic active ingredient takes place particularly well when the particulate, amorphous metal oxide of the pulverulent composition according to the invention in a 5% strength by weight slurry in distilled water has a pH of the resulting mixture of 4.5 to 8.0, in particular from 5.0 to 7.5.
• This embodiment is particularly suitable for increasing the release of waxy esters and / or setting polymers and / or film-forming polymers.
• the invention works particularly well when the particulate amorphous metal oxide of the powdered composition has a BET surface area of from 50 to 1000 m 2 / g, preferably from 100 to 750 m 2 / g, particularly preferably from 150 to 500 m 2 / g (each measured according to ISO 5794-1).
• a particularly preferred powdery composition comprises at least one particulate amorphous metal oxide of embodiments (A) to (F):
• At least one cosmetic active substance is present sorbed in said metal oxide, which is selected from waxy esters, setting polymers, film-forming polymers, oxidation dye precursors, anionic surfactants, keratin-reducing compounds or mixtures thereof.
• DBP number 50 to 800 g, preferably from 100 to 500 g, more preferably from 200 to 400 g, most preferably from 250 to 350 g, each per 100 g of metal oxide, with the proviso that in said metal oxide at least one cosmetic active ingredient is present, which is selected from waxy esters, setting polymers, film-forming polymers, oxidation dye precursors, anionic surfactants, keratin-reducing compounds or mixtures thereof.
• At least one cosmetic active substance is present sorbed in said metal oxide, which is selected from waxy esters, setting polymers, film-forming polymers, oxidation dye precursors, anionic surfactants, keratin-reducing compounds or mixtures thereof.
• - causes in a 5 wt .-% - slurry in distilled water, a pH of the resulting mixture of 4.5 to 8.0, in particular from 5.0 to 7.5, with the proviso that at least one cosmetic active substance is present sorbed in said metal oxide, which is selected from waxy esters, setting polymers, film-forming polymers, oxidation dye precursors, anionic surfactants, keratin-reducing compounds or mixtures thereof.
• DBP number of 50 to 800 g, preferably from 100 to 500 g, more preferably from 200 to 400 g, most preferably from 250 to 350 g, each per 100 g of metal oxide, and
• At least one cosmetic active substance is present sorbed in said metal oxide, which is selected from waxy esters, setting polymers, film-forming polymers, oxidation dye precursors, anionic surfactants, keratin-reducing compounds or mixtures thereof.
• BET surface area of from 50 to 1000 m 2 / g, preferably from 100 to 750 m 2 / g, particularly preferably from 150 to 500 m 2 / g (measured in each case according to ISO 5794-1),
• a DBP number of from 50 to 800 g, preferably from 100 to 500 g, more preferably from 200 to 400 g, most preferably from 250 to 350 g, each per 100 g of metal oxide, and
• At least one cosmetic active substance is present sorbed in said metal oxide, which is selected from waxy esters, setting polymers, film-forming polymers, oxidation dye precursors, anionic surfactants, keratin-reducing compounds or mixtures thereof.
• At least one wax-like ester is suitable (hereinafter also: wax ester).
• Waxy esters according to the invention have a melting point in a range from 40 ° C to 95 ° C at 1013 mbar.
• the waxy esters are preferably selected from vegetable, animal and mineral waxes, preference being given to those waxes which have a melting point in the range from 40 ° C. to 90 ° C.
• the powdery composition according to the invention contains at least one waxy ester selected from at least one wax of the group beeswax (Cera Alba), carnauba wax, candelilla wax, montan wax, rice bran wax (ie wax obtainable from rice bran), hydrogenated vegetable oil and cetyl palmitate.
• the teaching according to the invention also comprises the combined use of several waxes.
• carnauba wax can be used to increase the melting and dripping point of another wax and reduce its stickiness.
• These other waxes may be different from the waxy esters.
• microcrystalline waxes in particular microcrystalline paraffin wax
• ozokerite wax are preferred. Accordingly, a number of wax mixtures, optionally in admixture with other additives, commercially available.
• the powdery compositions of the invention preferably contain the waxy esters in amounts of from 50% to 90% by weight, based on the total agent. Quantities of 75% by weight to 80% by weight, based on the total agent, are particularly preferred.
• wax-ester-containing pulverulent compositions if a particulate amorphous metal oxide is present, on the particles of which at least one wax ester and at least one emulsifier are sorbed in total.
• either the wax ester and the emulsifier may be co-sorbed on the same particle of the particulate amorphous metal oxide (co-sorption) and / or a mixture of particles of a particulate amorphous metal oxide with sorbed emulsifier with particles of a particulate amorphous metal oxide sorbed waxy ester (separate sorption).
• emulsifier preferred according to the invention, at least one nonionic oil-in-water emulsifier is suitable.
• the pulverulent compositions according to the invention contain emulsifiers - preferably nonionic oil-in-water emulsifiers - preferably in amounts of from 0.1 to 20.0% by weight, based on the total agent. Quantities of 1, 0 wt .-% to 10.0 wt .-% are particularly preferred.
• At least one nonionic oil-in-water emulsifier is at least one nonionic oil-in-water emulsifier.
• At least one nonionic oil-in-water emulsifier is at least one nonionic oil-in-water emulsifier.
• At least one nonionic oil-in-water emulsifier is at least one nonionic oil-in-water emulsifier.
• At least one nonionic oil-in-water emulsifier is at least one nonionic oil-in-water emulsifier.
• DBP number of 50 to 800 g, preferably from 100 to 500 g, more preferably from 200 to 400 g, most preferably from 250 to 350 g, each per 100 g of metal oxide, and
• At least one nonionic oil-in-water emulsifier is at least one nonionic oil-in-water emulsifier.
• BET surface area of from 50 to 1000 m 2 / g, preferably from 100 to 750 m 2 / g, particularly preferably from 150 to 500 m 2 / g (measured in each case according to ISO 5794-1),
• a DBP number of from 50 to 800 g, preferably from 100 to 500 g, more preferably from 200 to 400 g, most preferably from 250 to 350 g, each per 100 g of metal oxide, and
• At least one nonionic oil-in-water emulsifier is at least one nonionic oil-in-water emulsifier.
• Preferred cosmetic compositions according to the invention are characterized in that the emulsifiers are selected from at least one compound of the group formed from ethoxylated C 8 -C 2 alkanols with an average of from 8 to 100 moles of ethylene oxide per mole of ethoxylated C 8 -C 2 carboxylic acids having on average 8 - 100 moles of ethylene oxide per mole, with an average of 20 - 100 moles of ethylene oxide per mole of ethoxylated glycerol mono- and diesters of linear, saturated and unsaturated C 2 - C 30 carboxylic acids, which may be hydroxylated, especially those of myristic acid, palmitic acid , Stearic acid, 12-hydroxystearic acid or mixtures of these fatty acids, with an average of 20-100 moles of ethylene oxide per mole of ethoxylated sorbitan monoesters of linear saturated and unsaturated C-
• 2 -C 30 -carboxylic acids which may be
• the ethoxylated C 8 -C 2 4-alkanols have the formula R 0 (CH 2 CH 2 0) n H, where R is a linear or branched alkyl and / or alkenyl radical having 8 to 24 carbon atoms and n, the average number of ethylene oxide Units per molecule, for numbers from 8-100, preferably 8-30 moles of ethylene oxide to 1 mole of caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, tridecyl alcohol, myristyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, Arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures. Also, adducts of 8-100 moles of
• the ethoxylated C 8 -C 2 4-carboxylic acids have the formula R 0 (CH 2 CH 2 0) n H, where R 0 is a linear or branched saturated or unsaturated acyl radical having 8-24 carbon atoms and n, the average number of ethylene oxide units per molecule, for numbers from 8 to 100, preferably 10 to 30, moles of ethylene oxide to 1 mole caprylic, 2-ethylhexanoic, capric, lauric, isotridecanoic, myristic, cetylic, palmitoleic, stearic, isostearic, oleic, elaidic, petroselic, arachidic, gadoleic , Behenic acid, erucic acid and brassidic acid and their technical mixtures.
• Adducts of 10 to 100 moles of ethylene oxide with technical fatty acids containing 12 to 18 carbon atoms, such as coconut, palm, palm kernel or tallow fatty acid, are also suitable. Particularly preferred are PEG-50 monostearate, PEG-100 monostearate, PEG-50 monooleate, PEG-100 monooleate, PEG-50 monolaurate and PEG-100 monolaurate.
• C 12 -C 18 -alkanols or the C 12 -C 18 -carboxylic acids with in each case 8 to 30 units of ethylene oxide per molecule and mixtures of these substances, in particular laureth-8, laureth-10, laureth-12, laureth- 20, trideceth-8, trideceth-9, trideceth-10, tri- deceth-12, trideceth-20, ceteth-10, ceteth-12, ceteth-20, ceteth-30, steareth-10, steareth-12, steareth- 20, steareth-30, ceteareth-10, ceteareth-12, ceteareth-20, ceteareth-30, laureth-12 and beheneth-20.
• Preferred ones having on average 20-100 moles of ethylene oxide per mole of ethoxylated glycerol mono- and / or diesters of linear saturated and unsaturated d 2 -C 30 carboxylic acids which may be hydroxylated are selected from PEG-20 Hydrogenated Castor Oil, PEG-40 Hydrocarbons. genated Castor Oil and PEG-60 Hydrogenated Castor Oil.
• Preferred average of 20 - 100 moles of ethylene oxide per mole of ethoxylated sorbitan monoesters of linear saturated and unsaturated C 2 - C 30 carboxylic acids, which can be hydroxylated are selected from Polysorbate 20, Polysorbate-40, Polysorbate-60, and Polysorbate-80th
• C 8 are preferably - C 2 2-alkyl mono- and oligoglycosides employed.
• C 8 -C 2 2-alkyl mono- and oligoglycosides are known, commercially available emulsifiers. They are prepared in particular by reacting glucose or oligosaccharides with primary alcohols having 8-22 carbon atoms.
• the glycoside radical monoglycosides in which a cyclic sugar residue is glycosidically linked to the fatty alcohol and oligomeric glycosides having a degree of oligomerization of up to about 8, preferably 1-2, are suitable.
• the degree of oligomerization is a statistical mean, which is based on a homolog distribution typical for such technical products.
• Particularly preferred C 8 -C 2 2-alkyl mono- and oligoglycosides are selected from octyl glucoside, decyl glucoside, lauryl glucoside, palmityl glucoside, isostearyl glucoside, stearyl glucoside, arachidyl glucoside and behenyl glucoside and mixtures thereof.
• the glucamine-derived acylglucamides are also suitable as nonionic oil-in-water emulsifiers.
• Ethoxylated sterols in particular ethoxylated soy sterols, are also suitable oil-in-water emulsifiers according to the invention.
• the degree of ethoxylation must be greater than 5, preferably at least 10, in order to have an HLB value greater than 7.
• Suitable commercial products are, for. PEG-10 Soy Sterol, PEG-16 Soy Sterol and PEG-25 Soy Sterol.
• partial esters of polyglycerols having 2 to 10 glycerol units and having 1 to 4 saturated or unsaturated, linear or branched, optionally hydroxylated C 8 -C 30 -fatty acid radicals are preferably used if they have an HLB value of more than 7 ,
• Particularly preferred Diglycerinmonocaprylat, Diglycerinmonocaprat, Diglycerinmono- are laurate, Triglycerinmonocaprylat, Triglycerinmonocaprat, triglycerol, Tetraglycerinmono- caprylate, cerinmonocaprat Tetraglycerinmonocaprat, Tetraglycerinmonolaurat, Pentaglycerinmonocaprylat, Pentagly-, Pentaglycerinmonolaurat, Hexaglycerinmonocaprylat, Hexaglycerinmonocaprat, Hexaglycerinmonolaurat, Hexaglycerinmonomyrist
• compositions which are suitable for reshaping keratin-containing fibers, in particular human hair, and comprise as said adsorbed cosmetic active ingredient at least one active ingredient selected from waxy esters, setting polymers, film-forming polymers, mixtures thereof.
• the technical teaching of the embodiment with at least one sorbed consolidating polymer is combined in the context of a preferred embodiment with the technical teaching of sorbed waxy esters.
• the active ingredients With regard to the active ingredients, a common sorption or a separate sorption is possible.
• At least one setting polymer is suitable, in particular for providing a pulverulent composition for shaping keratin-containing fibers.
• Corresponding setting polymers are preferably selected from nonionic setting polymers, anionic setting polymers, amphoteric setting polymers, cationic setting polymers.
• Hair-setting polymers contribute to the maintenance and / or build-up of the hair volume and hair fullness of the overall hairstyle. These polymers are at the same time also film-forming polymers and therefore generally typical substances for shaping hair treatment agents such as hair fixatives, hair foams, hair waxes, hair sprays.
• the film formation can be quite selective and connect only a few fibers.
• Film-forming polymers need not be setting polymers.
• Film-forming polymers are polymers which leave a continuous film on the skin, the hair or the nails when drying.
• Such film formers can be used in a wide variety of cosmetic products, such as for example face masks, make-up, hair fixatives, hair sprays, hair gels, hair waxes, hair treatments, shampoos or nail varnishes.
• Particular preference is given to polymers which have a sufficient solubility in water or water / alcohol mixtures in order to be present in completely completely dissolved form in the pulverulent composition according to the invention.
• the film-forming polymers may be of synthetic or natural origin.
• film-forming polymers are understood as meaning polymers which, when used in 0.01 to 20% strength by weight aqueous, alcoholic or aqueous-alcoholic solution, are capable of depositing a transparent polymer film on the hair.
• the composition according to the invention contains at least one nonionic, fixing polymer sorbed in the particulate, amorphous metal oxide.
• a nonionic polymer is understood as meaning a polymer which, in standard conditions, carries no structural units with permanently cationic groups or anionic groups in a protic solvent, which units each have to be compensated by counterions while maintaining the electroneutrality.
• Quaternized ammonium groups do not include protonated amines under cationic groups.
• anionic groups include carboxyl and sulfonic acid groups.
• the nonionic, setting polymers are preferably present in the pulverulent composition according to the invention in an amount of from 0.01% by weight to 20% by weight, in particular from 0.5% by weight to 10% by weight, most preferably from 1, 0 wt .-% to 5.0 wt .-%, each based on the weight of the powdered composition.
• nonionic setting polymers are preferably selected from at least one polymer of the group that is formed
• Copolymers of N-vinylpyrrolidone with N, N-di (Ci to C 4) alkylamino (C 2 to C 4) -alkylacrylamid, according to the invention are particularly preferred.
• Suitable polyvinylpyrrolidones are, for example, commercial products such as Luviskol ® K 90 or Luviskol ® K 85 from BASF SE.
• the molar ratio of the structural units comprised of the monomer N-vinylpyrrolidone to the structural units of the polymer comprised of the monomer vinyl acetate is in the range from 20:80 to 80:20, in particular from 30 to 70 to 60 to 40, lies.
• Suitable copolymers of vinylpyrrolidone and vinyl acetate are available, for example under the trademark Luviskol ® VA 37, Luviskol ® VA 55, Luviskol ® VA 64 and Luviskol ® VA 73 from the firm BASF SE.
• At least one copolymer unit comprising at least one structural unit of the formula (M-1) and at least one structural unit of the formula (M-II) is present as nonionic fixing polymer and at least one structural unit of the formula (M-III) is used,
• these copolymers in addition to polymer units resulting from the incorporation of said structural units of the formula (Ml), (M-II) and (M-III) in the copolymer, a maximum of 5 wt .-%, preferably at most 1 Wt .-%, contain polymer units, which are due to the incorporation of other monomers.
• the copolymers are composed exclusively of structural units of the formula (M-1), (M-II) and (M-III) and can be represented by the general formula (polyl)
• Formulas (M-l), (M-II) and (M-III) are statistically distributed in the molecule.
• a particularly preferred polymer is selected from the polymers of the INCI name VP / methacrylamide / vinyl imidazole copolymer, which are obtainable, for example, under the trade name Luviset Clear from BASF SE.
• compositions which comprise, sorbed, at least one nonionic fixing polymer comprising at least one structural unit of the formula (III) and at least one structural unit of the formula (M-IV)
• R is a hydrogen atom or a methyl group
• X 1 represents an oxygen atom or a group NH
• A is a group ethane-1,2-diyl, propane-1,3-diyl or butane-1,4-diyl
• R 2 and R 3 independently of one another represent a (C 1 to C 4 ) -alkyl group.
• nonionic fixing polymer is selected from at least one polymer which satisfies for formula (ES-II) at least one or more of the following features:
• R is a methyl group
• X 1 stands for a group NH
• A is ethane-1, 2-diyl or propane-1, 3-diyl,
• R 2 and R 3 independently of one another, represent methyl or ethyl, (particularly preferably
• Vinylcaprolactam / vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer for example, INCI name: Vinyl caprolactam / PVP / di-methylaminoethyl methacrylate copolymer (Gaffix ® under the trade name VC 713 ISP)
• Vinylcaprolactam / vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer (for example as a 35-39% solids in ethanol in the form of the commercial product Advantage LC E with the INCI name: vinyl caprolactam / VP / dimethylaminoethyl methacrylate copolymer, alcohol, lauryl pyrrolidone (ISP)),
• Vinylpyrrolidone / dimethylaminopropylmethacrylamide copolymer for example, INCI name: VP / DMAPA Acrylates Copolymer under the trade name Styleze CC-10 (10% by weight of active substance) (ISP)
• ISP active substance
• compositions according to the invention contain as sorbed setting polymer at least one anionic setting polymer.
• the anionic, setting polymers are preferably present in the powdery composition according to the invention in an amount of from 0.1% by weight to 20.0% by weight, particularly preferably from 0.2% by weight to 15.0% by weight. , very particularly preferably from 0.5 wt .-% to 10.0 wt .-%, each based on the weight of the composition according to the invention.
• the anionic, fixing polymer contains at least one structural unit of the formula (S1) which is selected from at least one structural unit of the formulas (S1 -1) to (S1-3)
• At least one structural unit of the formulas (S1-1) to (S1-3) additionally contains at least one structural unit of the formula (S2), which is selected from at least one structural unit of the formulas (S2-1) to (S2-8)
• R 2 is (C 2 to C 2) for an acyl group stands (especially acetyl or neodecanoyl).
• compositions according to the invention are preferred as containing at least one polymer which contains at least one structural unit of the formula (S1-3) and at least one structural unit of the formula (S2-8) as a sorbed fixing polymer
• R 2 is a (C 2 to C 12 ) acyl group (in particular acetyl and / or neodecanoyl).
• Particularly preferred polymers of this type are selected from at least one polymer of the group formed
• Such copolymers are, for example, from the company Clariant under the trade name Aristoflex A 60 (INCI name: VA / Crotonates copolymer) in an isopropanol-water mixture (60 wt .-% of active substance), from BASF under the trade name Luviset CA 66 (Vinyl acetate / crotonic acid copolymer 90:10, INCI name VA / Crotonates Copolymer) provided by National Starch under the trade names Resyn 28-2942 and Resyn 28-2930 (INCI name: VA / Crotonates / Vinyl Neodecanoate Copolymer ) provided.
• compositions according to the invention are preferred as containing at least one polymer as sorbed anionic setting polymer, which contain at least one structural unit of the formula (S1-1) and at least one structural unit of the formula (S2-5)
• the sorbed anionic fixing polymer additionally contains at least one structural unit of the formula (S3) in addition to the above structural units of the formulas (S1-1) and (S2-5)
• R 5 represents a hydrogen atom or a methyl group
• R 6 is a (C 1 to C 4 ) -alkyl group (in particular a methyl group or an ethyl group).
• Particularly preferred polymers of this type are selected from at least one polymer of the group which is formed from copolymers of acrylic acid and ethyl acrylate and N-tert-butylacrylamide.
• Such copolymers are, for example, from BASF under the trade name Ultrahold ® strand (INCI name: Acrylates / t-butylacrylamide copolymer, white, pourable granules) or Ultrahold ® 8 (INCI name: Acrylates / t-butylacrylamide copolymer, white, pourable Granules) provided.
• anionic setting polymers in particular those mentioned as preferred
• the sorption of the anionic fixing polymer of one of the preferred particulate amorphous metal oxides in particular one of the embodiments (A) to (F)) to use (vide supra).
• compositions according to the invention preferably contain a sorbed amphoteric setting polymer.
• an amphoteric polymer is understood as meaning a polymer which, in standard conditions, carries structural units in a protic solvent with anionic groups which have to be compensated by counterions while maintaining electroneutrality and which additionally has structural units with groups which can be cationized by protonation but is free of permanently cationized groups is.
• Anionic groups include carboxyl and sulfonic acid groups.
• Permanently cationized nitrogen atoms are to be understood as meaning those nitrogen atoms which carry a positive charge and thereby form a quaternary ammonium compound.
• N-oxide containing polymers are also among the amphoteric polymers.
• amphoteric, setting polymers are preferably present in the powdery composition according to the invention in an amount of from 0.1% by weight to 20.0% by weight, particularly preferably from 0.2% by weight to 15.0% by weight. , very particularly preferably from 0.5 wt .-% to 10.0 wt .-%, each based on the weight of the composition according to the invention. It is suitable according to the invention if the amphoteric, fixing polymer contains at least one structural unit of the formula (S1) which is selected from at least one structural unit of the formulas (S1 -1) to (S1-3)
• At least one structural unit of the formulas (S1-1) to (S1-3) additionally contains at least one structural unit of the formula (S2), which is selected from at least one structural unit of the formula (S2-9) to (S2-15)
• X represents an oxygen atom or a group NH.
• amphoteric, fixing polymers in addition to at least one structural unit of the formulas (S1-1) to (S1-3) and at least one structural unit of the formulas (S2-9) to (S2-15) additionally at least one structural unit of the formulas (S2-1) to (S2-8)
• R 2 is a (C 2 to d 2 ) acyl group (especially acetyl or neodecanoyl).
• An amphoteric, consolidating polymer is preferably suitable which has at least one structural unit of the formula (S1-1), at least one structural unit of the formula (S2-3) and at least one structural unit of the formula (S2-16) (in particular selected from the group which is formed from the above formulas (S2-5) to (S2-12) with the proviso that X 3 represents an oxygen atom), (S2-3) (S2-16)
• X 3 is an oxygen atom or a group NH
• R 3 represents a hydrogen atom or a methyl group
• R 4 is an alkyl group having 4 carbon atoms (especially n-butyl, sec-butyl, iso-butyl or tert-butyl).
• amphoteric, fixing polymers in addition to the above structural units of the formulas (S1-1), (S2-3) and (S2-16) additionally contains at least one structural unit of the formula (S3)
• R 5 represents a hydrogen atom or a methyl group
• R 6 is a (C 1 to C 4 ) -alkyl group (in particular a methyl group or an ethyl group).
• Preferred polymers of this type are selected from the group consisting of copolymers of acrylic acid, (C 1 to C 4 ) -alkyl acrylate, N- (C 4 -alkyl) aminoethyl methacrylate and N- (C 8 -alkyl) acrylamide.
• fixing polymer is that available under the trade name Amphomer ® of National Starch polymer having the INCI name octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer.
• Another particularly preferred sorbed amphoteric setting polymer comprises
• At least one monomer A1 selected from acrylic acid, methacrylic acid, alkyl acrylates and methacrylic acid alkyl esters, and
• amphoteric monomer A2 selected from (meth) acryloylalkylaminoxiden of the formula A2-I
• R is H or CH 3 ,
• R 2 and R 3 are each independently of one another optionally branched Ci_i 0 alkyl and n is an integer from 1 to 20.
• amphoteric setting polymers formed from the monomers mentioned are understood to mean only those copolymers which, in addition to polymer units resulting from the incorporation of said monomers A1 and A2 into the copolymer, have a maximum of 5% by weight. %, preferably at most 1 wt .-%, contain polymer units, which are due to the incorporation of other monomers.
• the copolymers A are composed exclusively of polymer units resulting from the incorporation of said monomers A1 and A2 into the copolymer.
• Preferred monomers A1 are acrylic acid, methacrylic acid, acrylic acid Ci_ 2 o-alkyl esters and methacrylic acid-D-20-alkyl ester.
• Monomer A1 is particularly preferably selected from acrylic acid, methacrylic acid, methyl acrylate, methyl acrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl acrylate, lauryl acrylate, lauryl methacrylate, cetyl acrylate, cetyl methacrylate, stearyl acrylate and stearyl methacrylate, very particularly preferably from acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate and stearyl methacrylate.
• Preferred monomers A2 are (meth) acryloylalkylaminoxide of the formula A2-I and / or (meth) acryloylalkylbetaine of the formula A2-II, wherein R 2 and R 3 are each independently methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert. -Butyl, particularly preferably methyl.
• Preferred monomers A2 are furthermore selected from at least one monomer from the group which is formed from (meth) acryloylalkylamine oxides of the formula A2-I and / or (meth) acryloylalkylbetaines of the formula A2-II, where n is in each case an integer from 1 to 5, preferably represents an integer from 1 to 3 and particularly preferably 2.
• monomers A2 selected from at least one monomer from the group which is formed from (meth) acryloylalkylaminoxiden of formula A2-I and / or (meth) acryloylalkylbetainen of formula A2-II, wherein each R is CH 3 are preferred.
• the monomers A2 are particularly preferably selected from at least one monomer from the group which is formed from (meth) acryloylalkylamine oxides of the formula A2-I and / or (meth) acryloylalkylbetaines of the formula A2-II, where R 2 and R 3 are each independently of one another is methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl, particularly preferably methyl, n is in each case an integer from 1 to 5, preferably an integer from 1 to 3 and particularly preferably 2, and Each R is CH 3 .
• monomer A2 is selected from at least one monomer from the group formed from (meth) acryloylalkylamine oxides of the formula A2-I and / or (meth) acryloylalkylbetaines of the formula A2-II, where R, R 2 and R 3 are each stand for CH 3 and n for 2.
• the said amphoteric setting polymer is (in particular exclusively) formed from at least one monomer of the formula (A1) and at least one monomer corresponding to the respective embodiment of the formula (A2-I).
• the agent according to the invention comprises at least one amphoteric setting polymer which is formed from
• the first monomer is selected from acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate and isopropyl methacrylate
• the second monomer is selected from stearyl acrylate and stearyl methacrylate
• the agent according to the invention comprises at least one amphoteric setting polymer which is formed from
• the first monomer being selected from acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate,
• the second monomer is selected from acryloyl acrylate and methacrylic acid lauryl ester
• the third monomer is selected from stearyl acrylate and stearyl methacrylate
• Corresponding copolymers are likewise known, for example under the names Diaformer Z-61 1, Diaformer Z-612, Diaformer Z-613, Diaformer Z-631, Diaformer Z-633, Diaformer Z-651, Diaformer Z-71 1 N, Diaformer Z 712N and Diaformer Z-731 N available from the company Clariant, wherein the use of Diaformer Z-712N and Diaformer Z-651 is preferred.
• amphoteric setting polymers in particular those mentioned as preferred
• amphoteric setting polymer of one of the preferred particulate amorphous metal oxides in particular one of the embodiments (A) to (F)
• At least one film-forming polymer is suitable, in particular for providing a pulverulent composition for shaping keratin-containing fibers.
• Corresponding film-forming polymers are preferably selected from cationic film-forming polymers and / or from silicones. Among them are partially polymers, which are also fixing polymers.
• Cationic polymers are polymers which have a group in the main and / or side chain which are "permanently” cationic.
• "permanently cationic” refers to those polymers which have a cationic group, irrespective of the pH of the agent. These are usually polymers containing a quaternary nitrogen atom, for example in the form of an ammonium group.
• Preferred cationic groups are quaternary ammonium groups.
• those polymers in which the quaternary ammonium group are bonded via a CI_ 4 hydrocarbon group to a synthesized from acrylic acid, methacrylic acid or derivatives thereof, polymer backbone have been found to be particularly suitable.
• a cationic film-forming polymer which is preferably suitable according to the invention is at least one cationic film-forming polymer which contains at least one structural element of the formula (M9) and additionally at least one structural element of the formula (M10)
• R is a hydrogen atom or a methyl group
• R ', R "and R” independently of one another represent a (C 1 to C 30 ) -alkyl group
• X is an oxygen atom or a group NH
• A is an ethane-1,2-diyl group or a propane-1,3-diyl group
• n 1 or 3.
• physiologically acceptable anions such as chloride, bromide, hydrogen sulfate, methyl sulfate, ethyl sulfate, tetrafluoroborate, phosphate, hydrogen phosphate, dihydrogen phosphate or p-toluenesulfonate, triflate.
• cationic film-forming polymers which comprise at least one structural unit of the formula (M5) and at least one structural unit of the formula (V) and optionally at least one structural unit of the formula (VI)
• R and R 4 independently of one another represent a hydrogen atom or a methyl group
• a and A 2 are each independently a group of ethane-1, 2-diyl, propane-1, 3-diyl or
• R 2 , R 3 , R 5 and R 6 independently of one another represent a (C 1 to C 4 ) -alkyl group
• R 7 is a (C 8 to C 30 ) alkyl group.
• ком ⁇ онент (VI) To compensate for the positive charge of the monomer (VI) are all possible physiologically acceptable anions, such as chloride, bromide, hydrogen sulfate, methyl sulfate, Ethyl sulfate, tetrafluoroborate, phosphate, hydrogen phosphate, dihydrogen phosphate or p-toluenesulfonate, triflate.
• physiologically acceptable anions such as chloride, bromide, hydrogen sulfate, methyl sulfate, Ethyl sulfate, tetrafluoroborate, phosphate, hydrogen phosphate, dihydrogen phosphate or p-toluenesulfonate, triflate.
• Copolymers of N-vinylpyrrolidone, N- (3-dimethylaminopropyl) methacrylamide and 3- (methacryloylamino) propyl-lauryl-dimethylammonium chloride (INCI name: Polyquaternium-55), which, for example, under the trade name Styleze W 10 or Styleze W 20 (10 or 20% by weight of active substance in ethanol-water mixture) is sold by the company ISP.
• Dimethylaminopropyl) methacrylamide and 3- (methacryloylamino) propyl-lauryl dimethylammonium chloride (INCI name: Polyquaternium-69), which, for example, under the trade name AquaStyle ® 300 (28-32 wt .-% active ingredient in ethanol-water mixture) of the Company ISP is distributed.
• powdered compositions (K1) in the context of this embodiment are particularly particularly preferred, which contain at least one particulate, amorphous metal oxide in which at least one cationic film-forming polymer is sorbed, which contains at least one structural element of the formula (M9) and additionally at least contains a structural element of formula M1
• the preferred particulate, amorphous metal oxides continue to be mutatis mutandis preferred.
• the sorbed cationic film-forming polymers are particularly preferably selected from cationic, quaternized cellulose derivatives.
• Such cationic, quaternized celluloses prove to be particularly advantageous for the purposes of the invention, which carry more than one permanent cationic charge in a side chain.
• cationic celluloses such cationic celluloses with the INCI name Polyquaternium-4 in turn, are particularly suitable, which are sold for example under the names of Celquat ® H 100, Celquat L 200 ® by the company National Starch.
• such pulverulent compositions (K2) in the context of this embodiment are considered to be most particularly preferred, containing at least one particulate amorphous metal oxide in which polyquaternium-4 is sorbed as the cationic film-forming polymer.
• the preferred particulate, amorphous metal oxides are preferred.
• Cationic polymers which are particularly preferably used in the context of the invention furthermore include those cationic film-forming copolymers which contain at least one structural element of the formula M1 1)
• R is a (C 1 to C 4 ) -alkyl group, in particular a methyl group
• physiologically acceptable anions such as chloride, bromide, hydrogen sulfate, methyl sulfate, ethyl sulfate, tetrafluoroborate, phosphate, hydrogen phosphate, dihydrogen phosphate or p-toluenesulfonate, triflate.
• At least one copolymer (co1) is sorbed, which in addition to at least one structural element of the formula (M1 1) additionally comprises a structural element of the formula (M5)
• R is a (Ci to C 4 ) alkyl group, in particular a methyl group.
• R is a (Ci to C 4 ) alkyl group, in particular a methyl group.
• physiologically acceptable anions such as chloride, bromide, hydrogen sulfate, methyl sulfate, ethyl sulfate, tetrafluoroborate, phosphate, hydrogen phosphate, dihydrogen phosphate or p-toluenesulfonate, triflate.
• Very particularly preferred cationic film-forming and / or cationic fixing polymers as copolymers (co1) contain 10 to 30 mol%, preferably 15 to 25 mol% and in particular 20 mol% of structural units of the formula (M1 1) and 70 to 90 Mol .-%, preferably 75 to 85 mol .-% and in particular 80 mol .-% of structural units according to formula (M5).
• the copolymers (co1) in addition to polymer units resulting from the incorporation of said structural units of the formula (M1 1) and (M5) in the copolymer, a maximum of 5 wt .-%, preferably at most 1 wt .-% , Contain polymer units due to the incorporation of other monomers.
• polyquaternium-16 according to INCI nomenclature and are, for example, from BASF under the trade names Luviquat ® Style, Luviquat ® FC 370 , Luviquat.RTM ® FC 550, FC 905 and Luviquat.RTM ® Luviquat.RTM ® HM 552
• these N-methylvinylimidazole / vinylpyrrolidone copolymers will be referred to as Polyquaternium-44, according to INCI nomenclature and are, for example, from BASF under the trade names Luviquat ® Ultra Care available.
• Structural element of the formula (M5) comprises wherein R is a (Ci to C 4 ) alkyl group, in particular a methyl group.
• the agents according to the invention may also contain copolymers (co2) which, starting from the copolymer (co1), have structural units of the formula (M6) as additional structural units
• compositions according to the invention are thus characterized in that they comprise as cationic film-forming polymer at least one copolymer (co2) which has at least one structural unit of formula (M1 1-a) and at least one structural unit of formula (M5) and at least one structural unit according to Formula (M6) contains
• the copolymers (co2) in addition to polymer units resulting from the incorporation of the above-mentioned structural units of the formula (M1 1-a), (M5) and (M6) into the copolymer, a maximum of 5 wt .-%, preferably at most 1 wt .-%, polymer units, which go back to the incorporation of other monomers.
• the copolymers (co2) are composed exclusively of structural units of the formulas (M1 1-a), (M5) and (M6).
• physiologically acceptable anions such as chloride, bromide, hydrogen sulfate, methyl sulfate, ethyl sulfate, tetrafluoroborate, phosphate, hydrogen phosphate, dihydrogen phosphate or p-toluenesulfonate, triflate.
• N-methylvinylimidazole / vinylpyrrolidone / vinylcaprolactam copolymers are used to compensate the positive charge of the copolymer, a methosulfate designated according to INCI nomenclature as Polyquaternium-46 and are for example available under the trade name Luviquat Hold ® from BASF.
• Very particularly preferred copolymers (co2) contain 1 to 20 mol%, preferably 5 to 15 mol% and in particular 10 mol% of structural units of the formula (M1 1-a) and 30 to 50 mol%, preferably 35 to 45 mol .-% and in particular 40 mol .-% of structural units of the formula (M5) and 40 to 60 mol .-%, preferably 45 to 55 mol .-% and in particular 60 mol .-% of structural units of the formula (M6).
• the agents according to the invention may also contain copolymers (co3) as cationic film-forming polymer, which as structural units are structural units of the formulas (M1 1 -a) and (M5), as well as further structural units from the group of vinylimidazole units and further structural units from the group of the acrylamide and / or methacrylamide units.
• compositions according to the invention are characterized in that they contain at least one copolymer (co3) as sorbed cationic film-forming polymer, the at least one structural unit of formula (M1 1-a) and at least one structural unit of formula (M5) and at least one structural unit according to Formula (M10) and at least one structural unit according to formula (M12) contains
• the copolymers (co3) in addition to polymer units resulting from the incorporation of said structural units of the formula (M1 1-a), (M5), (M8) and (M12) in the copolymer, a maximum of 5 wt .-%, preferably at most 1 wt .-%, contain polymer units, which go back to the incorporation of other monomers.
• the copolymers (co3) are composed exclusively of structural units of the formula (M1 1-a), (M5), (M8) and (M12).
• physiologically acceptable anions such as chloride, bromide, hydrogen sulfate, methyl sulfate, ethyl sulfate, tetrafluoroborate, phosphate, hydrogen phosphate, dihydrogen phosphate or p-toluenesulfonate, triflate.
• a methosulfate such N-methylvinylimidazole / vinylpyrrolidone / vinylimidazole / methacrylamide copolymers are used as Polyquaternium-68, according to INCI nomenclature and are obtainable for example under the trade name Luviquat ® Supreme by BASF.
• Very particularly preferred copolymers (co3) contain 1 to 12 mol%, preferably 3 to 9 mol% and in particular 6 mol% of structural units of the formula (M1 1-a) and 45 to 65 mol%, preferably 50 to 60 mol .-% and in particular 55 mol .-% of structural units of formula (M5) and 1 to 20 mol .-%, preferably 5 to 15 mol .-% and in particular 10 mol .-% of structural units of formula (M8) and 20 to 40 mol .-%, preferably 25 to 35 mol .-% and in particular 29 mol .-% of structural units of the formula (M12).
• film-forming cationic polymers selected from the cationic polymers having at least one structural element of the above formula (M1 1-a), the following are preferred:
• Vinylpyrrolidone / 1-vinyl-3-methyl-1 H-imidazolium chloride copolymers such as for example that with the INCI name Polyquaternium-16 under the trade names Luviquat ® Style, Luviquat ® FC 370, Luviquat ® FC 550, Luviquat ® FC 905 and Luviquat ® HM 552 (BASF SE)
• Vinylpyrrolidone / 1-vinyl-3-methyl-1H-imidazolium-Cop such as for example that with the INCI name Polyquaternium-44 under the trade names Luviquat Care ® (BASF SE)
• BASF SE Luviquat Care ®
• Vinylpyrrolidone / vinyl caprolactam / 1-vinyl-3-methyl-1 H-imidazolium terpolymer (such as for example that with the INCI name Polyquaternium-46 under the trade names Luviquat ® Care or Luviquat Hold ® (BASF SE)),
• Vinylpyrrolidone / methacrylamide / vinyl imidazole / 1-vinyl-3-methyl-1 H-imidazoliummethylsulfat- copolymer for example that with the INCI name Polyquaternium-68 ® under the trade name Luviquat Supreme (BASF SE)),
• the use of at least one silicone is particularly advantageous in order to reduce or avoid particle deposition of the particulate metal oxide on the keratin-containing fiber that is visible to the naked eye.
• the silicone used is preferably at least one silicone oil and / or at least one silicone gum.
• Silicone oils or silicone gums which are suitable according to the invention are in particular dialkyl and alkylaryl siloxanes, for example dimethylpolysiloxane and methylphenylpolysiloxane, and also their alkoxylated, quaternized or else anionic derivatives. Preference is given to cyclic and linear polydialkylsiloxanes, their alkoxylated and / or aminated derivatives, dihydroxypoly-dimethylsiloxanes and polyphenylalkylsiloxanes.
• Silicone oils cause a wide variety of effects. For example, at the same time they influence the dry and wet combability, the grip of dry and wet hair and the shine.
• the term "silicone oils” is understood by the person skilled in the art as meaning several structures of silicon-organic compounds. Initially, this is understood to mean the dimethiconols.
• Examples of such products include the following commercial products: Botanisil NU-150M (Botanigenics), Dow Coming 1-1254 Fluid, Dow Corning 2-9023 Fluid, Dow Corning 2-9026 Fluid, Ultrapure Dimethiconol (Ultra Chemical), Unisil SF- R (Universal Preserve), X-21-5619 (Shin- Etsu Chemical Co.), Abil OSW 5 (Degussa Care Specialties), ACC DL-9430 Emulsion (Taylor Chemical Company), AEC Dimethiconol & Sodium Dodecylbenzenesulfonate (A & E Connock (Perfumery & Cosmetics) Ltd.), BC Dimethiconol Emulsion 95 (Basildon Chemical Company, Ltd.), Cosmetic Fluid 1401, Cosmetic Fluid 1403, Cosmetic Fluid 1501, Cosmetic Fluid 1401 DC (all aforementioned Chemsil Silicones, Inc.), Dow Corning 1401 Fluid, Dow Corning 1403 Fluid, Dow Corning 1501 Fluid, Dow Corning 1784 HVF Em
• Dimethicones form the second group of silicones which may be present according to the invention. These may be both linear and branched as well as cyclic or cyclic and branched.
• Dimethicone copolyols form another group of silicones that are suitable.
• Corresponding dimethicone copolyols are commercially available and are sold, for example, by Dow Corning under the name Dow Corning® 5330 Fluid.
• the teaching according to the invention also encompasses the fact that the dimethiconols, dimethicones and / or dimethicone copolymers can already be present as an emulsion.
• the corresponding emulsion of dimethiconols, dimethicones and / or dimethicone copolyols can be prepared both after the preparation of the corresponding dimethiconols, dimethicones and / or dimethicone copolyols from these and the conventional methods of emulsification known to the person skilled in the art.
• both cationic, anionic, nonionic or zwitterionic surfactants and emulsifiers can be used as auxiliaries for the preparation of the corresponding emulsions.
• the emulsions of dimethiconols, dimethicones and / or dimethicone copolyols can also be prepared directly by an emulsion polymerization process. Such methods are also well known to the person skilled in the art.
• the droplet size of the emulsified particles according to the invention 0.01 to 10000 ⁇ , preferably 0.01 to 100 ⁇ , more preferably 0.01 to 20 ⁇ and most preferably 0 , 01 to 10 ⁇ .
• the particle size is determined by the method of light scattering.
• branched dimethiconols, dimethicones and / or dimethicone copolyols are used, it is to be understood that the branching is greater than a random branching which caused by contamination of the respective monomers randomly.
• branched dimethiconols, dimethicones and / or dimethicone copolyols are therefore to be understood as meaning that the degree of branching is greater than 0.01%.
• a degree of branching is greater than 0.1%, and most preferably greater than 0.5%.
• the degree of branching is determined from the ratio of the unbranched monomers to the branching monomers, that is, the amount of tri- and tetrafunctional siloxanes. According to the invention, both low-branched and highly branched dimethiconols, dimethicones and / or dimethicone copolyols can be very particularly preferred.
• Particularly suitable silicones are amino-functional silicones, in particular the silicones, which are summarized under the INCI name Amodimethicone. It is therefore preferred according to the invention if the agents according to the invention additionally contain at least one amino-functional silicone. These are silicones which have at least one, optionally substituted, amino group. These silicones are referred to as amodimethicone according to the INCI nomenclature and are available for example in the form of an emulsion as a commercial product Dow Corning ® 939 or as a commercial product Dow Corning ® 949 in a mixture with a cationic and a nonionic surfactant.
• those amino-functional silicones are used which have an amine number above 0.25 meq / g, preferably above 0.3 meq / g and especially preferably above 0.4 meq / g.
• the amine number stands for the milliequivalents of amine per gram of the amino-functional silicone. It can be determined by titration and also expressed in mg KOH / g.
• quaternized aminosilicones are preferably suitable.
• a particularly preferred quaternized aminosilicone has the INCI designation quaternium-80 and is sold under the trade name Abil Quat ® from Evonik Goldschmidt.
• the agents contain the silicones preferably in amounts of from 0.01% by weight to 30.0% by weight, particularly preferably from 0.05 to 10.0% by weight, based on the total agent.
• At least one oxidation dye precursor is suitable.
• Corresponding oxidation dye precursors are preferably selected from at least one developer component and at least one coupler component.
• the person skilled in the art is familiar with so-called developer components and coupler component as oxidation dye precursors.
• the developer components form the actual dyes under the influence of oxidizing agents or of atmospheric oxygen with one another or with coupling with one or more coupler components.
• the oxidation dyes are characterized by excellent, long-lasting dyeing results.
• p-phenylenediamine derivatives of the formula (E1) it may be preferred according to the invention to use as the developer component a p-phenylenediamine derivative or one of its physiologically acceptable salts. Particular preference is given to p-phenylenediamine derivatives of the formula (E1)
• G stands for a hydrogen atom, a (C- ⁇ -C 4) alkyl, (C- ⁇ -C 4) - monohydroxyalkyl radical, a (C 2 to C 4) polyhydroxyalkyl radical, a (C- ⁇ -C 4) Alkoxy- (C 1 to C 4 ) -alkyl radical, a 4'-aminophenyl radical or a (C 1 to C 4 ) -alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical;
• G 2 represents a hydrogen atom, a (Ci to C4) alkyl, a (Ci to C 4) - monohydroxyalkyl radical, a (C 2 to C 4) polyhydroxyalkyl radical, a (Ci-C 4) alkoxy- (C to C 4 ) -alkyl radical or a (C 1 to C 4 ) -alkyl radical which is substituted by a nitrogen-containing group;
• G 3 represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or fluorine atom, a (Ci to C4) alkyl, a (Ci to C 4) monohydroxyalkyl, a (C 2 to C 4 ) - Polyhydroxyalkylrest, a (Ci to C 4 ) -hydroxyalkoxy, a (Ci to C 4 ) -alkoxy- (Ci to C 4 ) - alkyl, a (Ci to C 4 ) -Acetylaminoalkoxy, a Mesylamino- (Ci to C 4 ) alkoxy or (C 1 to C 4 ) carbamoylaminoalkoxy;
• a halogen atom such as a chlorine, bromine, iodine or fluorine atom
• a (Ci to C4) alkyl a (Ci to C 4) monohydroxyalkyl, a (C 2 to
• G 4 represents a hydrogen atom, a halogen atom, a (C 1 to C 4 ) -alkyl radical or a (C 1 to C 4 ) -alkoxy (C 1 to C 4 ) -alkyl radical, or
• G 3 and G 4 when G 3 and G 4 are ortho to each other, they may together form a bridging ⁇ , ⁇ -alkylenedioxy group such as an ethylenedioxy group.
• Particularly preferred p-phenylenediamines of formula (E1) are selected from one or more compounds of the group formed from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine , 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine , N, N-dipropyl-p-phenylenediamine, 4-amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis ( ⁇ -hydroxyethyl) -p-phenylenediamine, 4-N, N-bis ( ⁇ -hydroxyethyl) amino-2-methylaniline
• p-phenylenediamine derivatives of the formula (E1) are selected from at least one compound of the group p-phenylenediamine, p-toluenediamine, 2- (ß-hydroxyethyl) -p-phenylenediamine, 2- (a, ß-dihydroxyethyl) - p-phenylenediamine, N, N-bis- ( ⁇ -hydroxyethyl) -p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazole 1-yl) propyl] amine, as well as the physiologically acceptable salts of these compounds.
• developer component compounds which contain at least two aromatic nuclei which are substituted by amino and / or hydroxyl groups.
• binuclear developer components which can be used in the dyeing compositions according to the invention, mention may be made in particular of the compounds corresponding to the following formula (E2) and their physiologically tolerated salts:
• Z and Z 2 independently of one another represent a hydroxyl or NH 2 radical which is optionally substituted by a (C 1 to C 4 ) -alkyl radical, by a (C 1 to C 4 ) -hydroxyalkyl radical and / or by a bridging Y or which is optionally part of a bridging ring system,
• the bridge Y is an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring, which of a or a plurality of nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms may be interrupted or terminated and may be substituted by one or more hydroxyl or (C 1 to C 8 ) -alkoxy radicals, or a direct bond,
• G 5 and G 6 are each independently a hydrogen or halogen atom, a (Ci to C4) alkyl, a (Ci to C 4) monohydroxyalkyl, a (C 2 to C 4) - polyhydroxyalkyl radical, a (Ci to C 4 ) -aminoalkyl radical or a direct compound for bridging Y,
• G 7 , G 8 , G 9 , G 0 , G and G 2 independently of one another represent a hydrogen atom, a direct bond to the bridge Y or a (C 1 to C 4 ) -alkyl radical,
• Preferred binuclear developer components of the formula (E2) are in particular selected from at least one of the following compounds: N, N'-bis- ( ⁇ -hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1,3-diamino -propan-2-ol, N, N'-bis ( ⁇ -hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4'-aminophenyl) - tetramethylenediamine, N, N'-bis ( ⁇ -hydroxyethyl) -N, N'-bis (4'-aminophenyl) tetramethylenediamine, N, N'-bis (4- (methylamino) phenyl) tetramethylenediamine, N , N'-diethyl-N, N'-bis (4'-amino-3'-methylphenyl) ethylenediamine,
• Very particularly preferred binuclear developer components of the formula (E2) are selected from N, N'-bis ( ⁇ -hydroxyethyl) -N, N'-bis (4-aminophenyl) -1,3-diamino-propan-2-ol , Bis (2-hydroxy-5-aminophenyl) -methane, 1, 3-bis (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4-aminophenyl) -1, 4-diazacycloheptane, 1, 10-bis (2,5-diaminophenyl) -1, 4,7, 10-tetraoxadecane or one of the physiologically acceptable salts of these compounds.
• p-aminophenol derivatives of the formula (E3) it may be preferred according to the invention to use as the developer component a p-aminophenol derivative or one of its physiologically tolerable salts. Particular preference is given to p-aminophenol derivatives of the formula (E3)
• G 3 represents a hydrogen atom, a halogen atom, a (Ci to C4) alkyl, a (Ci to C 4) monohydroxyalkyl, a (C 2 to C 4) polyhydroxyalkyl radical, a (Ci to C 4) alkoxy (C 1 to C 4 ) -alkyl radical, a (C 1 to C 4 ) -aminoalkyl radical, a hydroxy (C 1 to C 4 ) -alkylamino radical, a (C 1 to C 4 ) -hydroxyalkoxy radical, a (C 1 to C 4 ) - Hydroxyalkyl (Ci to C 4 ) -aminoalkylrest or a (di - [(Ci to C 4 ) -alkyl] amino) - (Ci to C 4 ) -alkylrest, and
• G 4 is a hydrogen or halogen atom, a (C 1 to C 4 ) -alkyl radical, a (C 1 to C 4 ) -
• Monohydroxyalkylrest a (C 2 to C 4 ) polyhydroxyalkyl, a (C- ⁇ to C 4 ) alkoxy (Ci to
• G 5 represents hydrogen, a (Ci to C4) alkyl, a (Ci to C 4) monohydroxyalkyl, a (C 2 to C 4) polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and
• G 6 is hydrogen or a halogen atom.
• Preferred p-aminophenols of the formula (E3) are, in particular, p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4 -Amino-3-hydroxymethylphenol, 4-amino-2- ( ⁇ -hydroxyethoxy) -phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino -2-aminomethylphenol, 4-amino-2- ( ⁇ -hydroxyethyl-aminomethyl) phenol, 4-amino-2- ( ⁇ , ⁇ -dihydroxyethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2 -chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethyl-aminomethyl) -phenol and their physiological
• Very particularly preferred compounds of the formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- ( ⁇ , ⁇ -dihydroxyethyl) -phenol and 4-amino 2- (diethylaminomethyl) -phenol.
• the developer component may be selected from o-aminophenol and its derivatives such as 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.
• the developer component may be selected from heterocyclic developer components, such as pyrimidine derivatives, pyrazole derivatives, pyrazolopyrimidine derivatives or their physiologically acceptable salts.
• Preferred pyrimidine derivatives are selected according to the invention from compounds of the formula (E4) or their physiologically tolerated salts,
• G 7 , G 8 and G 9 independently of one another represent a hydrogen atom, a hydroxy group, a (C 1 to C 4 ) -alkoxy group or an amino group and
• G is a hydroxy group or a group -NG G, in which G and G independently of one another represent a hydrogen atom, a (C 1 to C 4 ) -alkyl group, a (C 1 to C 4 ) -monohydroxyalkylglyrope,
• a maximum of two of the groups of G 7 , G 8 , G 9 and G 20 denote a hydroxy group and at most two of the radicals G 7 , G 8 and G 9 represent a hydrogen atom.
• at least two groups of G 7 , G 8 , G 9 and G 20 represent a group -NG 2 G 22 and at most two groups of G 7 , G 8 , G 9 and G 20 represent a hydroxy group.
• Particularly preferred pyrimidine derivatives are in particular the compounds 2,4,5,6-tetra-aminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4 , 5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine.
• Preferred pyrazole derivatives are selected according to the invention from compounds of the formula (E5),
• G, G, G are, independently, a hydrogen atom, a (Ci to C 4) - alkyl, (Ci to C 4) monohydroxyalkyl, a (C 2 to C 4) -Polyhydroxy- alkyl group, an optionally substituted aryl group or one if necessary substituted aryl- (C 1 -C 4 ) -alkyl group, with the proviso that if G is a hydrogen atom, G 27 may additionally be a group -NH 2 in addition to the abovementioned groups,
• G 26 represents a hydrogen atom, a (Ci to C 4) alkyl group, a (Ci to C 4) - monohydroxyalkyl group or a (C 2 to C 4) polyhydroxyalkyl group and
• G 27 represents a hydrogen atom, an optionally substituted aryl group, a (C 1 to C 4 ) -alkyl group or a (C 1 to C 4 ) -monohydroxyalkyl group, in particular a hydrogen atom or a methyl group.
• the radical -NG 25 G 26 binds to the 5 position and the radical G 27 to the 3 position of the pyrazole cycle.
• Particularly preferred pyrazole derivatives are, in particular, the compounds which are selected from 4,5-diamino-1-methylpyrazole, 4,5-diamino-1- ( ⁇ -hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5- Diamino-1- (4'-chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3 phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4 5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1- ( ⁇ -hydroxyeth
• Very particularly preferred developer components are selected from at least one compound from the group formed from p-phenylenediamine, p-toluenediamine, 2- ( ⁇ -hydroxyethyl) -p-phenylenediamine, 2- ( ⁇ , ⁇ -dihydroxyethyl) -p phenylenediamine, N, N-bis ( ⁇ -hydroxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1 H -imidazol-1-yl) propyl] amine, N, N'-bis ( ⁇ -hydroxyethyl) -N, N'-bis (4-aminophenyl) -1, 3-diamino-propan-2-ol, bis (2-hydroxy-5-aminophenyl) - methane, 1,3-bis- (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4-amin
• Examples of (C 1 -C 4 ) -alkyl radicals are the groups -CH 3 , - -CH 2 CH 2 CH 3, -CH (CH 3) 2, -CH 2 CH 2 CH 2 CH 3, -CH 2 CH (CH 3) 2, -CH (CH 3) CH 2 CH 3, -C (CH 3) 3.
• Examples of (C 1 to C 4 ) -alkoxy radicals according to the invention are -OCH 3 , -OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , -OCH (CH 3 ) 2 , -OCH 2 CH 2 CH 2 CH 3 , -OCH 2 CH (CH 3 ) 2 , -OCH (CH 3 ) CH 2 CH 3 , -OC (CH 3 ) 3 , in particular a methoxy or an ethoxy group.
• a (C 1 to C 4 ) monohydroxyalkyl group -CH 2 OH, -CH 2 CH 2 OH, -CH 2 CH 2 CH 2 OH, -CHCH (OH) CH 3 , -CH 2 CH 2 CH 2 CH 2 OH, wherein the group - CH 2 CH 2 OI-l is preferred.
• a particularly preferred example of a (C 2 to C 4 ) polyhydroxyalkyl group is the 1, 2-dihydroxyethyl group.
• halogen atoms are F, CI or Br atoms, Cl atoms are very particularly preferred examples.
• nitrogen-containing groups are especially -NH 2, (Ci to C 4) - monoalkylamino, (Ci to C 4) dialkylamino, (Ci to C 4) -Trialkylammoniunri phenomenon, (Ci to C 4) -Monohydroxyalkylamino phenomenon, imidazolinium and -NH 3 + .
• Examples of (C 1 -C 4 ) -monoalkylamino groups are -NHCH 3 , -NHCH 2 CH 3 , -NHCH 2 CH 2 CH 3 , -NHCH (CH 3 ) 2 .
• Examples of (C 1 to C 4 ) -dialkylamino groups are -N (CH 3 ) 2 , -N (CH 2 CH 3 ) 2.
• Examples of (C 1 to C 4 ) trialkylammonium groups are -N + (CH 3 ) 3 , -N + (CH 3 ) 2 (CH 2 CH 3),
• Examples of (C 1 to C 4 ) -hydroxyalkylamino radicals are -NH-CH 2 CH 2 OH, -NH-CH 2 CH 2 OH, -NH-CH 2 CH 2 CH 2 OH, -NH-CH 2 CH 2 CH 2 OH.
• Examples of (C 1 -C 4 ) -alkoxy- (C 1 -C 4 ) -alkyl groups are the groups -CH 2 CH 2 -O-CH 3, -CH 2 CH 2 CH 2 -O-CH 3, -CH 2 CH 2 -O-CH 2 CH 3, -CH 2 CH 2 CH 2 -O- CH2CH3, -CH2CH2 "0-CH (CH3), -CH 2 CH 2 CH2-0-CH (CH3).
• hydroxy (C 1 -C 4 ) -alkoxy radicals are -O-CH 2 OH, -O-CH 2 CH 2 OH, -O-CH 2 CH 2 CH 2 OH, -O-CHCH (OH) CH 3 , -O-CH2CH2CH2CH2OH.
• Examples of (d to C4) are -Acetylaminoalkoxyreste -0-CH 2 NHC (0) CH 3, -0-CH 2 CH 2 NHC (0) CH 3, -0-CH 2 CH 2 CH 2 NHC (0) CH 3, -O-CH 2 CH (NHC (O) CH 3 ) CH 3 , -O-CH 2 CH 2 CH 2 CH 2 NHC (O) CH 3 .
• Examples of (C 1 to C 4 ) -carbamoylaminoalkoxy radicals are -O-CH 2 Cl-1 2 -NI-1 C (0) -NI-12, -O-CH 2 CH 2 CH 2 -NH-C (O) -NH 2, CH 2 CH 2 CH 2 0-CH2-NH-C (0) -NH2.
• Examples of (C 1 to C 4 ) aminoalkyl radicals are -CH 2 NH 2 , -CH 2 CH 2 NH 2 , -CH 2 CH 2 CH 2 NH 2 , -CH 2 CH (NH 2 ) CH 3 , -CH 2 CH 2 CH 2 CH 2 NH 2 .
• Examples of (C 1 to C 4 ) -cyanoalkyl radicals are -CH 2 CN, -CH 2 CH 2 CN, -CH 2 CH 2 CH 2 CN.
• Examples of (C 1 to C 4 ) -hydroxyalkylamino (C 1 to C 4 ) -alkyl radicals are -CH 2 CH 2 NH-CH 2 CH 2 OH, -CH 2 CH 2 CH 2 NH-CH 2 CH 2 OH, -CH 2 CH 2 NH-CH 2 CH 2 CH 2 OH, -CH 2 CH 2 CH 2 NH-CH 2 CH 2 CH 2 OH.
• Examples of di [(C 1 to C 4 ) hydroxyalkyl] amino (C 1 to C 4 ) alkyl radicals are -CH 2 CH 2 N (CH 2 CH 2 OH) 2, -CH 2 CH 2 CH 2 N (CH 2 CH 2 OH) 2, -CH 2 CH 2 N (CH 2 CH 2 CH 2 OH) 2, -CH 2 CH 2 CH 2 N (CH 2 CH 2 CH 2 OH) 2.
• An example of aryl groups is the phenyl group.
• Coupler components do not form a significant color within the framework of the oxidative dyeing alone, but always require the presence of developer components. Therefore, it is preferred according to the invention that at least one coupler component is additionally used when using at least one developer component.
• Coupler components according to the invention allow at least one substitution of a chemical residue of the coupler by the oxidized form of the developer component. This forms a covalent bond between the coupler and the developer component.
• Couplers are preferably cyclic compounds which carry on cycle at least two groups selected from (i) optionally substituted amino groups and / or (ii) hydroxy groups. When the cyclic compound is a six-membered ring (preferably aromatic), said groups are preferably in ortho position or meta position to each other.
• Coupler components according to the invention are preferably selected as at least one compound from one of the following classes:
• o-aminophenol derivatives such as o-aminophenol
• Naphthalene derivatives having at least one hydroxy group having at least one hydroxy group
• Pyrazolone derivatives such as 1-phenyl-3-methylpyrazol-5-one,
• Morpholine derivatives such as, for example, 6-hydroxybenzomorpholine or 6-aminobenzomorpholine,
• m-aminophenols or derivatives thereof which can be used according to the invention are preferably selected from at least one compound of the formula (K1) and / or from at least one physiologically tolerated salt of a compound of the formula (K1),
• G and G z independently of one another represent a hydrogen atom, a (C 1 to C 4 ) -alkyl group, a (C 3 to C 6 ) -cycloalkyl group, a (C 2 to C 4 ) -alkenyl group, a (C 1 to C 4 ) Monohydroxyalkyl group, a (C 2 to C 4 ) polyhydroxyalkyl group, a (C 2 to C 4 ) perfluoroacyl group, an aryl (C 1 to C 6 ) alkyl group, an amino (C 1 to C 6 ) alkyl group, a (Ci to C 6 ) -Dialkylamino- (Ci to C 6 ) -alkyl distr or a (Ci to C 6 ) -alkoxy- (Ci to C 6 ) -alkyl distr, whereby G and G 2 together with the nitrogen atom a five-membered, six-membered or form a seven-membered
• G J and G are independently a hydrogen atom, a halogen atom, a (Ci to C 4) alkyl group, a (Ci to C4) alkoxy group, a hydroxy group, a (Ci to C 4) monohydroxyalkyl, a (C 2 to C 4 ) polyhydroxyalkyl, a hydroxy (Ci to C 4 ) -alkoxy, a (Ci to C 6 ) -alkoxy (C 2 to C 6 ) -alkoxy distr, an aryl group or a heteroaryl group.
• Particularly preferred m-aminophenol coupler components are selected from at least one compound selected from the group consisting of m-aminophenol, 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6 -methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4 -methoxy-2-methylphenol, 5- (2'-hydroxyethyl) amino-2-methylphenol, 3- (diethylamino) -phenol, N-cyclopentyl-3-aminophenol, 1, 3-dihydroxy-5- (methylamino) - benzene, 3-ethylamino-4-methylphenol, 2,4-dichloro-3-aminophenol and the physiologically acceptable salts of all the abovementioned compounds.
• m-diaminobenzenes or derivatives thereof which can be used according to the invention are preferably selected from at least one compound of the formula (K2) and / or from at least one physiologically tolerated salt of a compound of the formula (K2),
• G 5 , G 6 , G 7 and G independently represent a hydrogen atom, a (Ci to C 4) - alkyl group, a (C 3 -C 6) cycloalkyl group, a (C 2 -C 4) -alkenyl, (C- ⁇ -C 4) monohydroxyalkyl , a (C 2 to C 4 ) polyhydroxyalkyl group, a (C 1 to C 4 ) alkoxy (C 1 to C 4 ) alkyl group, an aryl (C 1 to C 4 ) alkyl group, a heteroaryl (C 1 to C 4 ) alkyl group, a (C 2 to C 4 ) perfluoroacyl group, or together with the nitrogen atom form a five-membered or six-membered heterocycle
• G a and G 'independently of one another represent a hydrogen atom, a halogen atom, a (C 1 to C 4 ) -alkyl group, a u (2,4-diaminophenyl) - (C 1 to C 4 ) -alkyl group, a (jj- (2 , 4-Diaminophenyloxy) - (Ci to C 4) alkoxy, (Ci to C 4) alkoxy group, a hydroxy group, a (C- ⁇ -C 4) alkoxy (C 2 to C 4) - alkoxy group, alkoxy monohydroxyalkyl, a (C 2 to C 4) -polyhydroxyalkyl group, a hydroxy (Ci to C 4) - an aryl group, a heteroaryl group, a (Ci to C4).
• Particularly preferred m-diaminobenzene coupler components are selected from at least one compound from the group formed from m-phenylenediamine, 2- (2,4-diaminophenoxy) ethanol, 1, 3-bis (2,4-diaminophenoxy) propane, 1-Methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 1, 3-bis (2,4-diaminophenyl) propane, 2,6-bis (2'-hydroxyethylamino) -1-methylbenzene, 2- ( ⁇ 3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl ⁇ amino) ethanol, 2 - ( ⁇ 3 - [(2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl ⁇ amino) ethanol, 2 - ( ⁇ 3 - [(2-hydroxyethyl) amino] -4,5-dimethylphenyl ⁇ amino) ethanol, 2- [3-morpholin-4
• o-diaminobenzenes or their derivatives which can be used according to the invention are preferably selected from at least one compound of the formula (K3) and / or from at least one physiologically tolerated salt of a compound of the formula (K3),
• G, G 2, G 3 and G 4 independently represent a hydrogen atom, a (C- ⁇ -C 4) - alkyl group, a (C 3 -C 6) cycloalkyl group, a (C 2 to C 4) - alkenyl , a (Ci to C 4) monohydroxyalkyl, a (C 2 to C 4) - polyhydroxyalkyl group, a (Ci to C 4) alkoxy alkyl (Ci to C 4), aryl (Ci to C 4) alkyl group, a heteroaryl (Ci to C 4 ) alkyl group, a (C 2 to C 4 ) perfluoroacyl group, or together with the nitrogen atom form a five-membered or six-membered heterocycle
• G 5 and G 6 are independently a hydrogen atom, a halogen atom, a carboxyl group, a (C- ⁇ -C 4) alkyl group, a (C- ⁇ -C 4) - alkoxy group, a hydroxy group, a (Ci to C 4) - monohydroxyalkyl, a (C 2 to C 4) -polyhydroxyalkyl group, a hydroxy (Ci to C4) alkoxy group.
• Particularly preferred o-diaminobenzene coupler components are selected from at least one compound selected from the group consisting of 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene and the physiologically acceptable salts of all of the aforementioned compounds.
• Preferred di- or trihydroxybenzenes and their derivatives are selected from at least one compound of the group formed from resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1 , 2,4-trihydroxybenzene.
• the pyridine derivatives which can be used according to the invention are preferably selected from at least one compound of the formula (K4) and / or from at least one physiologically tolerable salt of a compound of the formula (K4),
• G and G independently represent a hydroxy group or a group
• G 2 and G 22 independently of one another represent a hydrogen atom, a (C 1 to C 4 ) -alkyl group, a (C 3 to C 6 ) -cycloalkyl group, a (C 2 to C 4 ) -alkenyl group, an aryl group, a ( Ci to C 4) monohydroxyalkyl, a (C 2 to C 4) -polyhydroxyalkyl group, a (C -C 4) alkoxy (Ci -C 4) - alkyl group, an aryl (Ci alkyl to C4), a heteroaryl (C 1 to C 4 ) alkyl group,
• G 9 and G independently of one another represent a hydrogen atom, a halogen atom, a (C 1 to C 4 ) -alkyl group or a (C 1 to C 4 ) -alkoxy group.
• radicals G 7 and G 8 are in the ortho position or in the meta position relative to one another.
• Particularly preferred pyridine derivatives are selected from at least one compound of the group formed from 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino 6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine, 3,5-diamino-2, 6-dimethoxypyridine, 3,4-diaminopyridine, 2- (2-methoxyethyl) amino-3-amino-6-methoxypyridine, 2- (4'-methoxyphenyl) amino-3-aminopyridine, and the physiologically acceptable salts of the aforementioned compounds.
• Preferred naphthalene derivatives having at least one hydroxy group are selected from at least one compound of the group formed from 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1, 3 Dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene.
• the indole derivatives which can be used according to the invention are preferably selected from at least one compound of the formula (K5) and / or from at least one physiologically tolerable salt of a compound of the formula (K5),
• G is a hydrogen atom, a (C 1 -C 4 ) -alkyl group, a (C 3 -C 6 ) -cycloalkyl group, a (C 2 -C 4 ) -alkenyl group, a (C 1 -C 4 ) -monohydroxyalkyl group, a (C 2 to C 4) -polyhydroxyalkyl group, an aryl (Ci to C 4) alkyl group,
• G 24 represents a hydroxy group or a group -NG 26 G 27 , wherein G 26 and G 27 independently of one another represent a hydrogen atom, a (C 1 to C 4 ) -alkyl group, a (C 3 to C 6 ) -cycloalkyl group, a (C 2 -C 4) -alkenyl, (Ci to C 4) monohydroxyalkyl, a (C 2 to C 4) polyhydroxyalkyl group,
• G 25 is a hydrogen atom, a halogen atom or a (C 1 -C 4 ) -alkyl group,
• Particularly preferred indole derivatives are selected from at least one compound of the group which is formed from 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole and the physiologically acceptable salts of the abovementioned compounds.
• the indoline derivatives which can be used according to the invention are preferably selected from at least one compound of the formula (K6) and / or from at least one physiologically tolerable salt of a compound of the formula (K6),
• G stands for a hydrogen atom, a (Ci to C 4) alkyl group, a (C 3 -C 6) - cycloalkyl group, a (C 2 to C 4) alkenyl group, a (Ci to C 4) monohydroxyalkyl, a ( C 2 to C 4 alkyl) -polyhydroxyalkyl group, an aryl (Ci to C 4),
• G 29 represents a hydroxy group or a group -NG 3 G 32 , in which G 3 and G 32 independently of one another represent a hydrogen atom, a (C 1 to C 4 ) -alkyl group, a (C 3 to C 6 ) -cycloalkyl group, a (C 2 -C 4) -alkenyl, (Ci to C 4) monohydroxyalkyl, a (C 2 to C 4) polyhydroxyalkyl group,
• G 30 is a hydrogen atom, a halogen atom or a (C 1 to C 4 ) -alkyl group,
• Particularly preferred indoline derivatives are selected from at least one compound of the group formed from 4-hydroxyindoline, 6-hydroxyindoline and 7-hydroxyindoline and the physiologically acceptable salts of the aforementioned compounds.
• Preferred pyrimidine derivatives are selected from at least one compound of the group formed from 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2 -Amino-4-methylpyrimidine, 2-amino-4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine and the physiologically acceptable salts of the aforementioned compounds.
• coupler components according to the invention are selected from m-aminophenol, 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 5-amino-4-chloro-2-methylphenol , 5- (2'-hydroxyethyl) amino-2-methylphenol, 2,4-dichloro-3-aminophenol, o-aminophenol, m-phenylenediamine, 2- (2,4-diaminophenoxy) ethanol, 1,3-bis (2,4-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 1, 3-bis (2,4-diaminophenyl) propane, 2,6-bis (2'-bis) hydroxyethylamino) -1-methylbenzene, 2 - ( ⁇ 3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl ⁇
• the coupler components are preferably used in an amount of from 0.005 to 20% by weight, preferably from 0.1 to 5% by weight, based in each case on the corresponding pulverulent oxidation dye.
• developer components and coupler components are generally used in approximately molar amounts to each other.
• a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer components and coupler components in a molar ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1: 2 , can stand.
• Examples of (C 3 to C 6 ) cycloalkyl groups according to the invention are cyclopropyl, cyclopentyl and cyclohexyl.
• Examples of (C 1 to C 4 ) -alkoxy radicals according to the invention are -OCH 3 , -OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , -OCH (CH 3 ) 2 , -OCH 2 CH 2 CH 2 CH 3 , -OCH 2 CH (CH 3 ) 2 , -OCH (CH 3 ) CH 2 CH 3 , -OC (CH 3 ) 3 , in particular a methoxy or an ethoxy group.
• a particularly preferred example of a (C 2 to C 4 ) polyhydroxyalkyl group is the 1, 2-dihydroxyethyl group.
• halogen atoms are F, CI or Br atoms, Cl atoms are very particularly preferred examples.
• nitrogen-containing groups are especially -NH 2, (Ci to C 4) - monoalkylamino, (Ci to C 4) dialkylamino, (Ci to C 4) -Trialkylammonium phenomenon, (Ci to C 4) -Monohydroxyalkylamino phenomenon, imidazolinium and -NH 3 + .
• Examples of (C 1 -C 4 ) -monoalkylamino groups are -NHCH 3 , -NHCH 2 CH 3 , -NHCH 2 CH 2 CH 3 , -NHCH (CH 3 ) 2 .
• Examples of (C 1 to C 4 ) -dialkylamino groups are -N (CH 3 ) 2 , -N (CH 2 CH 3 ) 2 .
• Examples of (C 1 to C 4 ) -alkoxy (C 1 to C 4 ) -alkyl groups are the groups -CH 2 CH 2 -O-CH 3 , -CH 2 CH 2 CH 2 -O-CH 3 , -CH 2 CH 2 -O-CH 2 CH 3 , -CH 2 CH 2 CH 2 -O-CH 2 CH 3 , -CH 2 CH 2 -O-CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 -O-CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 -O-CH (CH 3 ) 2 .
• Examples of (C 1 to C 4 ) -alkoxy (C 1 to C 4 ) -alkoxy groups are the groups -O-CH 2 CH 2 -O-CH 3 , -O-CH 2 CH 2 CH 2 -O-CH 3 , -O-CH 2 CH 2 -O-CH 2 CH 3 , -O-CH 2 CH 2 CH 2 -O-CH 2 CH 3 , -O-CH 2 CH 2 -O-CH (CH 3 ) 2 ,
• hydroxy (C 1 -C 4 ) alkoxy radicals are -O-CH 2 OH, -O-CH 2 CH 2 OH, -O-CH 2 CH 2 CH 2 OH, -O-CH 2 CH (OH) CH 3 , -O-CH 2 CH 2 CH 2 CH 2 OH.
• Examples of (C 1 to C 4 ) aminoalkyl radicals are -CH 2 NH 2 , -CH 2 CH 2 NH 2 , -CH 2 CH 2 CH 2 NH 2 , -CH 2 CH (NH 2 ) CH 3 , -CH 2 CH 2 CH 2 CH 2 NH 2 .
• aryl groups is the phenyl group, which may also be substituted.
• aryl (C 1 to C 4 ) alkyl groups are the benzyl group and the 2-phenylethyl group.
• oxidation dye precursors in particular those mentioned as preferred
• amorphous metal oxides in particular one of embodiments (A) to (F)
• at least one anionic surfactant is suitable, in particular for providing a pulverulent composition for purifying keratin-containing fibers.
• the pulverulent compositions according to the invention preferably contain anionic surfactants in amounts of from 0.5% by weight to 30.0% by weight, based on the total agent. Amounts of from 5.0% to 15.0% by weight are particularly preferred.
• Suitable anionic surfactants in inventive compositions are the following preferred anionic surfactants:
• Sulfobernsteinklamono- and dialkyl esters having 8 to 24 carbon atoms in the alkyl group and sulfosuccinic monoalkylpolyoxyethylester having 8 to 24 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups.
• Alpha-sulfofatty acid methyl esters of fatty acids having 8 to 30 carbon atoms are alpha-sulfofatty acids having 8 to 30 carbon atoms.
• Alkyl sulfates and alkyl polyglycol ether sulfates of the formula R-O (CH 2 -CH 2 O) x -OSO 3 H, in which R is a preferably linear alkyl group having 8 to 30 C atoms and x 0 or 1 to 12,
• Hydroxysulfonates corresponding to at least one of the following two formulas or mixtures thereof and salts thereof,
• R 2 is hydrogen, a radical (CH 2 CH 2 0) nR 2 or X, n is from 1 to 10 and X is hydrogen, an alkali or alkaline earth metal or NR 3 R 4 R 5 R 6 , where R 3 to R 6 independently of one another represent hydrogen or a C 1 to C 4 hydrocarbon radical,
• RCO-- for a linear or branched, aliphatic, saturated and / or unsaturated acyl radical having 6 to 22 C atoms
• Alk for CH 2 CH 2 , CHCH 3 CH 2 and / or CH 2 CHCH 3
• n for numbers of 0 , 5 to 5 and M is a metal such as alkali metal, in particular sodium, potassium, lithium, alkaline earth metal, in particular magnesium, calcium, zinc, or ammonium ion, such as + NR 3 R 4 R 5 R 6 , with R 3 to R 6 independently of one another represent hydrogen or a C1 to C4 hydrocarbon radical
• R 8 CO is a linear or branched acyl radical having 6 to 22 carbon atoms
• x, y and z are in total 0 or numbers of 1 to 30, preferably 2 to 10
• X is an alkali or alkaline earth metal.
• monoglyceride ether sulfates suitable for the purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride and their ethylene oxide adducts with sulfur trioxide or chlorosulfonic acid in the form of their sodium salts.
• monoglyceride sulfates are used, in which R 8 CO is a linear acyl radical having 8 to 18 carbon atoms,
• Amide ether carboxylic acids R-CO-NR 2 -CH 2 CH 2 -0- (CH 2 CH 2 0) n CH 2 COOM, with R as a straight-chain or branched alkyl or alkenyl radical with a number of carbon atoms in the chain 2-30 , n is an integer from 1 to 20 and R 2 is hydrogen, a methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl or iso-butyl radical and M is hydrogen or a metal such as alkali metal, especially sodium, potassium, lithium, Alkaline earth metal, in particular magnesium, calcium, zinc, or an ammonium ion, such as + NR 3 R 4 R 5 R 6 , with R 3 to R 6 independently of one another represent hydrogen or a C 1 to C 4 hydrocarbon radical.
• Such products are obtainable, for example, by the company Chem Y under the product name Akypo ®.
• Condensation products of a water-soluble salt of a water-soluble protein hydrolyzate with a C8-C30 fatty acid are available under the trademark Lamepon® ®, Maypon ®, Gluadin® ®, Hostapon® ® KCG or Amisoft ® long been commercially.
• the anionic surfactants used comprise polyglycol ether chains, it is very particularly preferred that they have a narrow homolog distribution. Further, in the case of mild anionic surfactants having polyglycol ether units, it is preferable that the number of glycol ether groups is 1 to 20, preferably 2 to 15, more preferably 2 to 12. Particularly mild anionic surfactants having polyglycol ether groups with no restricted homolog distribution can be obtained, for example on the one hand the number of polyglycol ether groups is 4 to 12 and Zn or Mg ions are selected as the counterion. One example is the commercial product Texapon.RTM ® ASV.
• anionic surfactants in particular those mentioned as preferred
• one of the preferred particulate, amorphous metal oxides in particular one of the embodiments (A) to (F)) (vide supra)
• the preferred amounts or proportions in particular in the preferred amounts or proportions.
• At least one keratin-reducing compound is suitable.
• the permanent deformation of keratin fibers is usually carried out by treating the fibers with a keratin-reducing compound preparation and shaping them by mechanical deformation aids. Thereafter, rinsing after an exposure time with water or an aqueous solution. In a second step, the fiber is then treated with a preparation of an oxidizing agent. After a contact time is also rinsed this and freed the fiber from the mechanical deformation aids (winder, papillote).
• the keratin-reducing compound cleaves a portion of the disulfide bonds of the keratin to -SH groups, thus causing a loosening of the peptide cross-linking and, due to the stress of the fiber due to the mechanical deformation, reorientation of the keratin layer. Under the influence of the oxidizing agent again disulfide bonds are knotted, and in this way the Keratingechege is reflowed in the given deformation.
• One such such method is the permanent wave treatment of human hair. This can be used both to create curls and waves in straight hair and to smooth ruffled hair.
• the keratin-reducing compounds contained in the powdered composition in sorbed form are preferably selected from compounds having at least one thiol group and their derivatives, sulfites, hydrogen sulfites, disulfites.
• Compounds having at least one thiol group and derivatives thereof are, for example, thioglycolic acid, thiolactic acid, thiomalic acid, phenylthioglycolic acid, mercaptoethanesulphonic acid and its salts and esters (such as isooctylthioglycolate and isopropylthioglycolate), cysteamine, cysteine, Bunte salts and salts of sulphurous acid.
• thioglycolic acid thiolactic acid, thiomalic acid, phenylthioglycolic acid, mercaptoethanesulphonic acid and its salts and esters (such as isooctylthioglycolate and isopropylthioglycolate), cysteamine, cysteine, Bunte salts and salts of sulphurous acid.
• thioglycolic acid thiolactic acid
• Examples of keratin-reducing compounds of the disulfites, which may be contained in the powdered composition sorbiert are alkali metal disulfites, such as sodium disulfite (Na 2 S 2 0 5 ) and potassium disulfite (K 2 S 2 0 5 ), and magnesium disulfite and ammonium disulfite ((NH 4 ) 2 S 2 0 5 ). Ammonium disulfite may be preferred according to the invention.
• Examples of keratin-reducing compounds of hydrogen sulfites which may be contained in the powdered composition sorbed, are hydrogen sulfites as alkali metal, magnesium, ammonium or alkanolammonium salt based on a C 2 -C 4 mono-, di- or trialkanolamine.
• Ammonium hydrogen sulfite may be a particularly preferred hydrogen sulfite.
• Examples of keratin-reducing compounds of the sulfites, which may be contained sorbed in the powdered composition are sulfites as alkali, ammonium or alkanolammonium salt based on a C 2 -C 4 mono-, di- or trialkanolamine. Ammonium sulfite is preferred.
• Preferred sulfur-containing, keratin-reducing compounds are cysteamine, cysteine, Bunte salts and salts of sulfurous acid, thioglycolic acid, thiolactic acid, thiomalic acid, mercaptoethanesulfonic acid and the salts and esters of the aforementioned thioacids.
• the keratin-reducing compound is preferably used in an amount of 5 to 20 wt .-%, based on the total powdered composition.
• the core-shell particles of the powdery composition according to the above preferred embodiment of the present invention comprise a core comprising an aqueous liquid phase.
• the core is thus in liquid form.
• This core is surrounded by a shell based on separable individual particles of at least one hydrophobized metal oxide powder.
• hydrophobized metal oxide is not limited in principle, as long as it is ensured that upon intensive mixing with the liquid, aqueous phase, a corresponding core-shell particle is formed.
• hydrophobed are to be understood as meaning those metal oxides which have been modified at least on the surface of the particles in such a way that the modified particle is wetted less by water than the unmodified particle.
• silanized, hydrophobized metal oxides are preferred.
• at least one member of the group which is formed is preferably selected from silanes, halosilanes, alkoxysilanes and silazanes.
• Preferred hydrophobized metal oxides of the hydrophobized metal oxide powder are selected according to the invention from at least one member of the group formed from hydrophobized silicates, hydrophobicized aluminum silicates, hydrophobized titanium dioxide and hydrophobized silica.
• Aluminum silicates also called aluminosilicates
• aluminosilicates are selected from phyllosilicates, tectosilicates or mixtures thereof.
• Preferred phyllosilicates are selected from kaolins (here in particular kaolinite, dickite, halloysite and nacrite), serpentine, talc, pyrophyllite, montmorillonite, quartz, bentonite, mica (in particular below IIIit, muscovite, paragonite, phlogopite, biotite, lepidolite, margarite , Smectite (here in particular montmorillonite, saponite, nontronite, hectorite)).
• kaolins here in particular kaolinite, dickite, halloysite and nacrite
• serpentine talc
• pyrophyllite montmorillonite
• quartz in particular below IIIit, muscovite, paragonite, phlogopite
• biotite lepidolite
• margarite margarite
• Smectite here in particular montmorillonite,
• Preferred tectosilicates are selected from feldspar minerals (especially albite, orthoclase, anorthite, leucite, sodalite, hauyne, labradorite, lasurite, nosean, nepheline), zeolites.
• the core-shell particles of the powdered compositions preferred according to the invention preferably contain the hydrophobized metal oxide powder in an amount of from 0.5 to 30% by weight, based on the weight of the core-shell particles contained in the pulverulent composition according to the invention.
• the hydrophobized metal oxides have a particle diameter of less than 5 ⁇ m, preferably less than 1 ⁇ m, particularly preferably between 20 and 100 nm.
• the pulverulent composition according to the invention particularly preferably contains as hydrophobized metal oxide powder of the core-shell particles at least one hydrophobized silicon dioxide, in particular at least one silanized, hydrophobicized silicon dioxide.
• At least one member of the group which is formed from silanes, halosilanes, alkoxysilanes and silazanes is preferably suitable according to the invention.
• Preferred representatives of the group of silanes are hexa (CiC 2 o) alkyldisilanes, in particular hexamethyldisilane.
• halosilane when a halosilane is used as the silylating agent, as the preferred halosilane, at least one compound selected from the group consisting of the compounds is selected
• X represents a chlorine, bromine or iodine atom
• z ' is a number 1, 2 or 3
• y ' is a number 0, 1 or 2
• n is an integer from 1 to 20 and
• alkoxysilane As the silylating agent, as the preferred alkoxysilane, at least one compound selected from the group consisting of the compounds is selected
• n is an integer from 1 to 20 and
• z is a number 1, 2, or 3
• silazane is at least one compound from the class of disilazanes, in particular at least one compound of disilazanes of the formula
• R ' is a (Ci-C 2 o) alkyl group
• R represents a (C 1 -C 20 ) alkyl group or a vinyl group, a particularly preferred silazane being hexamethyldisilazane.
• alkyl groups may be both cyclic and linear or branched.
• alkyl groups which can be used according to the invention are methyl, ethyl, n-propyl, isopropyl, n-butyl, cyclopentyl, cyclohexyl, n-decyl, lauryl, myristyl, cetyl, stearyl, isostearyl and behenyl.
• An example of an aryl group according to the invention is the phenyl group.
• Examples of a (Ci-C6) perfluoroalkyl group according to the invention are trifluoromethyl, perfluoroethyl, perfluoropropyl and perfluorohexyl.
• Silanized hydrophobized silicas are particularly preferably selected from at least one compound of the group formed from trimethylsilylate-coated silica, dimethylsilylate-coated silica, octylsilylate-coated silica. It is again preferred to select the hydrophobized metal oxide powder of the core-shell particles of silica silylates. These are hydrophobized silicas that comply with the INCI name Silica Silylate.
• hydrophobicized silicon dioxides which have a BET specific surface area between 10 and 400 m 2 / g, preferably between 80 and 300 m 2 / g.
• hydrophobized silicon dioides are preferably suitable silanized, in particular silica silylate.
• hydrophobized silicas are commercially available. Examples include Aerosil ® R104 V, Aerosil ® R106, Aerosil ® R202, Aerosil ® R805, Aerosil ® R812, Aerosil ® R812S, Aerosil ® R972 and Aerosil ® R8200, all Degussa, and HDK ® H2000, HDK ® H2050 and HDK ® H3004 , all Wacker, called.
• the hydrophobic silicas are used which are available under the names Aerosil ® R202, Aerosil ® R812S or Aerosil ® R972.
• the silicon dioxide comes with the INCI name silica Silylate used, which is sold by Degussa under the name Aerosil ® R812S.
• the core-shell particles of the powdered compositions preferred according to the present invention preferably contain the hydrophobized silica powder in an amount of 0.5 to 30% by weight based on the weight of the core-shell particles contained in the powdery composition of the present invention.
• the optimum amount depends primarily on the hydrophobicity of the silica powder used. The more hydrophobic the silica powder is, the less of it is needed to obtain a stable, powdered product.
• the pulverulent composition according to the invention preferably contains as hydrophobized metal oxide at least one hydrophobicized phyllosilicate, in particular at least one hydrophobicized mica and / or at least one hydrophobicized talc.
• at least one silanized, hydrophobized phyllosilicate or at least one silanized hydrophobized mica and / or at least one hydrophobized talc is preferably used.
• reagent for silanizing the phyllosilicate or the mica at least one member of the group which is formed, from silanes, halosilanes, alkoxysilanes and silazanes, is preferably suitable.
• Silanized, hydrophobized mica are particularly preferably selected from at least one compound of the group formed from trimethylsilylate-coated mica, dimethylsilylate-coated mica, octylsilylate-coated mica.
• Silanized, hydrophobicized talc is particularly preferably selected from at least one compound of the group formed from trimethylsilylate-coated talc, dimethylsilylate-coated talc, octylsilylate-coated talc.
• hydrophobically modified phyllosilicate which can be used according to the invention include, for example, silanized, hydrophobized talc silanized with triethoxycaprylsilane, hydrophobized mica with triethoxycaprylsilane, for example from LCW.
• the core-shell particles of the powdered compositions preferred according to the invention contain on the surface fluorine-containing, organic-group-coated metal oxide particles as hydrophobized metal oxide powder (in particular on the surface with fluorine-containing, organic group-coated mica, on the surface with fluorine-containing organic groups coated titanium dioxide, on the surface with fluorine-containing, organic groups coated silica).
• on the surface with fluorine-containing, organic groups coated metal oxide particles are those which have been coated on the surface with perfluorinated organic compounds, in particular with Perfluoralkylresten.
• metal oxides are preferred, which have been hydrophobicized with at least one radical selected from perfluoroalkylsilyl, polyperfluoro (C 2 to C 6 ) alkylene oxide, polysiloxane having perfluoroalkyl groups, perfluoroalkyl, Polyfluoralkylphosphatether.
• at least one radical selected from perfluoroalkylsilyl, polyperfluoro (C 2 to C 6 ) alkylene oxide, polysiloxane having perfluoroalkyl groups, perfluoroalkyl, Polyfluoralkylphosphatether preference is given to using those metal oxide particles coated on the surface with fluorine-containing, organic groups which carry polyperfluoro (C 2 to C 6 ) -alkylene oxide radicals on the surface.
• These are preferably selected from polyperfluoro- (C 2 to C 6 ) -alkylene oxide-coated mica and / or polyperfluoro- (C 2 to C 6 ) -alkylene oxide-coated titanium dioxide and / or with polyperfluoro- (C 2 to C 6 ) - alkylene oxide-coated silica and / or with polyperfluoro (C 2 to C 6 ) alkylene oxide-coated talc.
• Metal oxide particles coated with reagents of formula (I) are covalently surface-bonded polyperfluoro- (C 2 to C 6 ) -alkylene oxide moieties.
• the metal oxide particles coated on the surface with fluorine-containing, organic groups to be coated by at least one compound of the formula (Ia)
• n + m stands for an integer of 20 to 80.
• These compounds have the INCI name Polyperfluoromethylisopropyl Ether. Particular preference is given to compounds of the formula (Ia) which have a molecular weight of from 1500 to 4000 g / mol.
• the commercial product PW F-MS (with polyperfluoromethyl isopropyl ether (CAS No .: 69991-67-9, EINECS 274-225-4) and triethoxycaprylylsilan coated, nanofine titanium dioxide (INCI name: Cl 77891, Polyperfluoromethylisopropyl ether, Triethoxycaprylylsilane) from Sensient / LCW.
• a liquid, aqueous phase is understood as meaning a liquid which contains at least 40% by weight, in particular at least 65% by weight, of water, based on the weight of the liquid, aqueous phase in the core.
• the liquid, aqueous phase of the core-shell particles of the preferred embodiment of the pulverulent composition preferably contains an aqueous solvent selected from water or a mixture of water and a C 1 -C 4 -alcohol, in particular ethanol.
• an aqueous solvent selected from water or a mixture of water and a C 1 -C 4 -alcohol, in particular ethanol.
• the core-shell particles in the liquid, aqueous phase based on the weight of the core-shell particles of the powdered composition contain from 70 wt .-% to 90 wt .-%, particularly preferably 80 to 90 wt .-%, one aqueous solvent.
• water or a mixture of water and a maximum of 60% by weight of C 1 -C 4 -alcohol, based on the solvent mixture is therefore used as the aqueous solvent.
• Particularly preferred aqueous solvents are water or a mixture of water and a maximum of 30 wt .-% Ci-C4-alcohol, based on the solvent mixture. Very particular preference is given to using water as the aqueous solvent.
• the core-shell particles of the preferred embodiment of the powdered composition are suitable for releasing the liquid, aqueous phase of the core from the core-shell particle by mechanical loading of the core-shell particles, in particular by friction and / or pressure to form a liquid from the powdered composition.
• the pulverulent composition according to the invention comprises said core-shell particles and is configured as an oxidative hair dye comprising at least one oxidation dye precursor
• the liquid, aqueous phase of the core-shell particles preferably comprises at least one oxidizing agent, in particular hydrogen peroxide.
• the pulverulent composition according to the invention comprises said core-shell particles and is designed as a permanent hair-shaping composition comprising at least one keratin-reducing compound
• the liquid, aqueous phase of the core-shell particles preferably contains at least one alkalizing agent.
• alkalizing agents according to the invention are ammonia, alkali metal and ammonium carbonates and bicarbonates or organic amines such as monoethanolamine, and mixtures thereof.
• the pulverulent compositions can be formulated in virtually any containers. If the composition according to the invention contains core-shell particles, it merely has to be ensured that the mechanical loading of the powder during the removal of the composition is not so high that the powder is converted into liquid form already on removal. Suitable, for example, crucibles, bottles or tetra packs, the container can be configured for example with a bulk and metering device.
• the particulate amorphous metal oxides containing at least one sorbed active ingredient according to the invention are prepared, for example, as follows:
• the said cosmetic active ingredient is obtained in liquid form (obtained either by dissolving in a solvent or by melting) with the particulate amorphous metal oxide in a mixer ( Eg propeller mixer) first slurried and then stirred until the particulate, amorphous metal oxide has taken up said cosmetic active ingredient and a powdered composition results.
• Another manufacturing method is the intimate one Mixing a solid sorbate with the said amorphous metal oxide as a sorbent, for example in a mortar or grinder.
• the core-shell particles as an additive within the scope of the preferred embodiment of the pulverulent composition according to the invention can be prepared simply. It has proven useful when using different metal oxide particles coated according to the invention to first mix all of the metal oxide particles coated according to the invention. Then, in a separate mixer, all ingredients except for said inventively coated metal oxide particles are incorporated into the aqueous phase with stirring. Finally, the coated metal oxide particles are added to the aqueous phase with vigorous stirring.
• the mixing time required depends on the mixing energy introduced and the composition of the mixture, but is usually between 15 seconds and 5 minutes. If mixed too briefly, no stable powder forms and an oily phase is formed. If the mixing time is too long, the initially resulting powder is converted into a creamy or creamy consistency, whereby this process is not reversible. It is therefore advisable to determine the optimum mixing time for the respective system through a few preliminary tests.
• a powdered composition comprising core-shell particles which is preferred according to the invention is provided, for example, by carefully mixing the core-shell particles with the said sorbate-containing, pulverulent, amorphous metal oxide.
• a second object of the invention is the use of a powdery composition of the first subject of the invention for the cosmetic treatment of keratinous fibers, in particular human hair.
• keratin-containing fibers for the temporary deformation of keratin-containing fibers, in particular human hair, or / and
• keratin-containing fibers for conditioning keratin-containing fibers, in particular human hair and / or
• pulverulent compositions according to the invention for the temporary deformation of keratin-containing fibers, in particular human hair.
• keratin-containing fibers are understood to mean furs, wool, feathers and in particular human hair.
• a fourth subject of the invention is a process for the cosmetic treatment of keratin-containing
• this powdered composition is subjected to mechanical stress during or after application to the keratin-containing fibers, the powdered composition comprising said core shell Transforms particles into a liquid,
• the applied composition acts on the keratin-containing fibers and optionally rinsed out.
• Preferred is a method for shaping keratin-containing fibers, in particular human hair, in the
• the keratin-containing fibers are moistened
• this powdered composition is subjected to mechanical stress during or after application to the keratin-containing fibers, the powdered composition comprising said core shell Transforms particles into a liquid,
• the form of the keratin-containing fibers is temporarily fixed by said powdered composition.
• the desired amount of pulverulent composition is preferably first removed from the container.
• the composition can be applied directly to the keratin fiber to be treated or, for example, to the hand.
• the composition according to the invention is preferably applied to wet to wet hair.
• application to dry fiber is also possible.
• the powdered composition can be applied directly from the container to the fibers, but of course also with an aid, such as the hand, a brush, a sponge, a cloth, a brush or a comb.
• the adjuvants can also be used to distribute the applied composition on the fiber.
• the applied powder can be exposed directly to the keratinic fiber to a mechanical load, for example by means of the hands or tools (vide supra), whereby the liquid, aqueous phase contained in the powdered composition core Sheath particles are released directly onto the fiber and the effect of the sorbed drug is unfolded.
• the pulverulent composition comprising core-shell particles is first given to the hand, it can first be distributed carefully in the hair and then again subjected to greater mechanical stress, for example by massaging the powder into the hair. As a result, the liquid, aqueous phase of the core shell particles is released directly on the fiber and unfolds the effect of the sorbed active ingredient. This makes it very possible to achieve an excellent cosmetic effect.
• Kahlwax 6240 Vegetable Wax 10.0 10.0 5.0 5.0 5.0 5.0 10.0 10.0 5.0 5.0
• the powdered styling agents E1 to E19 according to the invention were prepared as described below.
• 19 hair strands were treated with one of the above-mentioned styling agents.
• the strand of hair was moistened and applied to the wet strand of the composition of the invention and massaged.
• the treated strand of hair was fixed stretched on a board and allowed to dry.
• compositions E1 to E20 according to the invention an excellent hold was obtained.
• the hair had much more structure and texture.
• the particulate precipitated silica used no visible matting of the hair was observed.
• the hair retained its natural shine.
• Amphomer white powder INCI name: Octylacrylamide / Acrylates / inoethyl methacrylate copolymer (Akzo Nobel)
• Aerosil ® R 812 S modified fumed silica INCI name: Silica
• DOW Corning® 193 C fluid silicone glycol copolymer (INCI name: PEG-12
• Kahlwax ® 6240 Vegetable Wax self-emulsifying wax ester (solid) (Kahl GmbH & Co.) Verityl ® AB 1000 Liquid 1, 4-Dihydroxymethylcyclohexane

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