DE102012223838A1 - Process for the gentle heat-assisted transformation of keratin-containing fibers - Google Patents

Abstract

An active ingredient combination of (a) at least one nonionic polymer (a) with at least one structural unit of the formula (M1) and at least one structural unit of the formula (M2) in which R 'denotes a (C1 to C30) acyl group, in particular an acetyl group, and (b) at least one cationic polymer (b) with at least one structural unit of the formula (M1) and at least one structural unit of the formula (M3) and at least one structural unit of the formula (M4) wherein R ″ represents a (C1 to C4) -alkyl group , in particular a methyl group, is suitable for the heat protection of keratin-containing fibers, heat from a temperature of 80 ° C to 350 ° C (preferably 80 ° C to 280 ° C, particularly preferably 100 ° C to 250 ° C, more preferred 140 ° C to 220 ° C). The effect unfolds especially during the heat treatment. The active ingredient combination is preferably suitable for use in straightening irons. The active ingredient combination according to the invention is located on the keratin-containing fibers during the application of heat.

Description

The invention relates to the technical field of shaping keratinhaltige fibers. As keratin-containing fibers, in principle all animal hair, e.g. Wool, horsehair, angora hair, furs, feathers and products made therefrom or textiles. However, the invention is preferably used in the context of heat-assisted hair shaping, in particular the smoothing of curly human hair and wigs made therefrom.

Deformation of keratin-containing fibers is usually carried out by mechanically deforming the fiber and defining the deformation by suitable means. Before and / or after this deformation, the fiber is treated with at least one cosmetic preparation in order to fix the newly impressed form to the fiber collective.

As part of a perm, for example, keratin-containing chamfers are treated with keratin-reducing compounds. After a rinsing operation, the fiber is then treated with an oxidizing agent preparation in the so-called fixing step, rinsed and freed from the forming aids (e.g., winders, papillots) after or during the fusing step. When, as a keratin reducing component, a mercaptan, e.g. Ammonium thioglycolate is used, this part of the disulfide bridges of the keratin molecule cleaves to -SH groups, so that there is a softening of keratin fibers. In the later oxidative fixation again disulfide bridges are knotted in the hair keratin, so that the Keratingefüge is fixed in the predetermined deformation.

As part of a temporary shaping, the newly imprinted form of the fiber collective is fixed by the application of so-called hair fixatives. Such hair fixatives are, for example, waxes or setting polymers.

Often, when using water-based cosmetics, the moist keratin fibers are reshaped, the mold is first mechanically fixed, then by applying heat to remove the water and additionally by restaging the hydrogen bonds within and between the keratin protein strands to accomplish a fixation of the new form.

To smooth keratin-containing fibers, the curled hair is wound in a corresponding process either on winder with a large diameter of usually more than 15 mm or the hair smoothed under the action, for example a keratin-reducing composition. Instead of the winder, it is also possible to smooth the fiber on a smoothing board. Smoothing boards are usually rectangular panels e.g. made of plastic. Preferably, the fiber is wetted with a liquid. Supporting the mechanically fixed in the new form fibers are subjected to a heat treatment, for example by a hot blower or contact with hot surfaces.

One way of hair straightening is to straighten with a hot iron. However, the structure of the keratin-containing fiber changes during the heat treatment of the hair during the smoothing (see McMullen, R. et al., J. Cosmet. Sci., 1998, 49, 223-244 ). This change in fiber structure should be countered by appropriate measures or repaired afterwards.

In general, the known forming methods, especially in the case of smoothing, have the disadvantage that the keratin-containing fiber is charged electrostatically. In addition, the deformation result of the known methods in terms of the degree of deformation and the uniformity of the deformation is in need of improvement. When an improvement in the degree of deformation is achieved, this is usually accompanied by an increased damage to the keratin-containing fiber.

The object of the invention is therefore to provide a heat-assisted forming process for keratin-containing fibers, in particular for human hair, which provides a very good shape fixation, maintains the fiber and protects the structure of the fiber from heat (heat protection).

Surprisingly, it has been found that the object is ensured by a shaping process for keratin-containing fibers, in particular human hair, which provides for the presence of a special active substance combination during heat application.

• (a) mindestens einem nichtionischen Polymer (a) mit mindestens einer Struktureinheit der Formel (M1) und mindestens einer Struktureinheit der Formel (M2)
  
  worin R’ eine (C₁- bis C₃₀)-Acylgruppe bedeutet, insbesondere eine Acetylgruppe, und
• (b) mindestens einem kationischen Polymer (b) mit mindestens einer Struktureinheit der Formel (M1) und mindestens einer Struktureinheit der Formel (M3) und mindestens einer Struktureinheit der Formel (M4)
  
  worin R’’ für eine (C₁ bis C₄)-Alkylgruppe, insbesondere für eine Methylgruppe, steht, zum Hitzeschutz keratinhaltiger Fasern, die Wärme von einer Temperatur von 80°C bis 350°C (vorzugsweise 80°C bis 280°C, besonders bevorzugt 100°C bis 250°C, weiter bevorzugt 140°C bis 220°C) ausgesetzt werden. Als Wärmequelle dient bevorzugt ein Heißluftgebläse (beispielsweise in der Ausführungsform als Föhn, Haube oder Lockenstab), ein Glätteisen oder ein Welleisen. Glätteisen oder Welleisen sind besonders bevorzugte Wärmequellen.

A first subject of the invention is therefore the use of an active ingredient combination

• (a) at least one nonionic polymer (a) having at least one structural unit of the formula (M1) and at least one structural unit of the formula (M2)
  
  wherein R 'is a (C ₁ - to C ₃₀ ) acyl group, in particular an acetyl group, and
• (b) at least one cationic polymer (b) having at least one structural unit of the formula (M1) and at least one structural unit of the formula (M3) and at least one structural unit of the formula (M4)
  
  wherein R "is a (C ₁ to C ₄ ) alkyl group, in particular a methyl group, for the heat protection keratinhaltiger fibers, the heat of a temperature of 80 ° C to 350 ° C (preferably 80 ° C to 280 ° C. , more preferably 100 ° C to 250 ° C, more preferably 140 ° C to 220 ° C) are exposed. As a heat source is preferably a hot air blower (for example, in the embodiment as a hair dryer, hood or curling iron), a flat iron or a corrugated iron. Straighteners or corrugated iron are particularly preferred heat sources.

Very particular preference is given to said active ingredient combination in the context of restructuring keratinhaltiger fibers, especially human hair, previously a heat-assisted smoothing at a temperature of 80 ° C to 350 ° C (preferably 80 ° C to 280 ° C, particularly preferably 100 ° C to 250 ° C, more preferably 140 ° C to 220 ° C) were used.

The active ingredient combination used according to the invention contains the polymers (a) and (b) in a weight ratio range of 10: 1 to 1: 10, in particular 5: 1 to 1: 5, more preferably 3: 1 to 1: 3 preferably from 1.5 to 1 to 1 to 1.5.

Particularly suitable nonionic polymers (a) are in particular copolymers of N-vinylpyrrolidone and vinyl acetate. In this case, it is again preferred if 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 in the range from 30:70 to 60:40 , lies; for example, sold under the trademark Luviskol ^® VA 37, Luviskol ^® VA 55, Luviskol ^® VA 64 and Luviskol ^® VA 73 from the firm BASF SE.

It is particularly preferred according to the invention in the active ingredient combination to use those cationic polymers (b) in which R '' is a methyl group according to formula (M4).

It is particularly preferred if the cationic polymers (b) in addition to polymer units resulting from the incorporation of said structural units of formula (M1), (M3) and (M4) 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. Preferably, the polymers (b) are composed exclusively of structural units of the formulas (M1), (M3) and (M4).

Very particularly preferred cationic polymers (b) contain 1 to 20 mol%, preferably 5 to 15 mol% and in particular 10 mol% of structural units of the formula (M4) (in particular with R "= methyl) and 30 to 50 Mol .-%, preferably 35 to 45 mol .-% and in particular 40 mol .-% of structural units according to formula (M1) and 40 to 60 mol .-%, preferably 45 to 55 mol .-% and in particular 60 mol .-% Structural units according to formula (M3).

To compensate for the positive polymer charge of the polymer (b) 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.

If a methosulfate is used to compensate for the positive charge of the copolymer, it is a most preferred cationic polymer (b) N-methylvinylimidazole / vinylpyrrolidone / vinylcaprolactam copolymer, referred to as Poly Quaternium-46 by INCI nomenclature. This polymer is available, for example, by BASF under the trade name Luviquat.RTM ^® Hold.

In the context of the use according to the invention, it has proved to be advantageous and therefore preferred according to the invention to incorporate said active substance combination into a cosmetic carrier and to use the resulting cosmetic product as part of a heat-assisted shaping.

The agents used according to the invention preferably contain the polymers (a) in a total amount of from 0.01 to 9.99% by weight, more preferably from 0.25 to 7.75% by weight, very particularly from 0.5 to 4, 5% by weight, most preferably from 1.0 to 4.0% by weight, based in each case on the weight of the ready-to-use agent.

The agents used according to the invention preferably contain the polymers (b) in a total amount of from 0.01 to 9.99% by weight, more preferably from 0.25 to 7.75% by weight, very particularly from 0.5 to 4, 5% by weight, most preferably from 1.0 to 4.0% by weight, based in each case on the weight of the ready-to-use agent.

The agents used according to the invention preferably contain the active ingredient combination of the polymers (a) and (b) in a total amount of from 0.1 to 10.0% by weight, particularly preferably from 0.5 to 8.0% by weight, completely especially 1.0 to 5.0% by weight, most preferably 2.0 to 5.0% by weight, based in each case on the weight of the ready-to-use agent.

The agents used according to the invention contain the polymers (a) and (b) in a weight ratio range of 10: 1 to 1: 10, more preferably 5: 1 to 1: 5, more preferably 3: 1 to 1: 3 preferably from 1.5 to 1 to 1 to 1.5.

• – die Wirkstoffkombination aus den Polymeren (a) und (b) in einer Gesamtmenge von 0,1 bis 10,0 Gew.-%, besonders bevorzugt von 0,5 bis 8,0 Gew.-%, ganz besonders 1,0 bis 5,0 Gew.%, am bevorzugtesten 2,0 bis 5,0 Gew.%, jeweils bezogen auf das Gewicht des anwendungsbereiten Mittels, und
• – die Polymere (a) und (b) in einem Gewichtsverhältnisbereich von 10 zu 1 bis 1 zu 10, insbesondere von 5 zu 1 bis 1 zu 5, besonders bevorzugt von 3 zu 1 bis 1 zu 3, ganz besonders bevorzugt von 1.5 zu 1 bis 1 zu 1.5

enthalten. It is particularly preferred according to the invention if the agents used according to the invention

• - The active ingredient combination of the polymers (a) and (b) in a total amount of 0.1 to 10.0 wt .-%, particularly preferably from 0.5 to 8.0 wt .-%, especially 1.0 to 5.0% by weight, most preferably 2.0 to 5.0% by weight, based in each case on the weight of the ready-to-use agent, and
• - The polymers (a) and (b) in a weight ratio range of 10 to 1 to 1 to 10, in particular from 5 to 1 to 1 to 5, more preferably from 3 to 1 to 1 to 3, most preferably from 1.5 to 1 to 1 to 1.5

contain.

It has proved to be preferred if the agents according to the invention additionally contain at least one cationic surfactant. Again, cationic surfactants selected from quaternary ammonium compounds, esterquats and amidoamines or mixtures thereof are preferred. Preferred quaternary ammonium compounds are ammonium halides, especially chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. For example, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, and the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.

Esterquats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element. Preferred ester quats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines.

The alkylamidoamines are usually prepared by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. An inventively particularly suitable compound from this group of substances under the name Tegoamid ^® S 18 commercial stearamidopropyl dimethylamine is.

The cationic surfactants are contained in the agents according to the invention preferably in amounts of 0.05 to 10 wt .-%, based on the total agent. Amounts of 0.1 to 5 wt .-% are particularly preferred.

• – Anlagerungsprodukte von 2 bis 100 Mol Ethylenoxid und/oder 1 bis 5 Mol Propylenoxid an lineare und verzweigte Fettalkohole mit 8 bis 30 C-Atomen, an Fettsäuren mit 8 bis 30 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe,
• – mit einem Methyl- oder (C₂ bis C₆)-Alkylrest endgruppenverschlossene Anlagerungsprodukte von 2 bis 50 Mol Ethylenoxid und/oder 1 bis 5 Mol Propylenoxid an lineare und verzweigte Fettalkohole mit 8 bis 30 C-Atomen, an Fettsäuren mit 8 bis 30 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe,
• – C₁₂-C₃₀-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 Mol Ethylenoxid an Glycerin,
• – Anlagerungsprodukte von 5 bis 60 Mol Ethylenoxid an Rizinusöl und gehärtetes Rizinusöl,
• – Polyolfettsäureester,
• – alkoxilierte Triglyceride,
• – alkoxilierte Fettsäurealkylester der Formel (E4-I) R¹CO-(OCH₂CHR²)_wOR³ (E4-I) in der R¹CO für einen linearen oder verzweigten, gesättigten und/oder ungesättigten Acylrest mit 6 bis 22 Kohlenstoffatomen, R² für Wasserstoff oder Methyl, R³ für lineare oder verzweigte Alkylreste mit 1 bis 4 Kohlenstoffatomen und w für Zahlen von 1 bis 20 steht,
• – Aminoxide,
• – Sorbitanfettsäureester und Anlagerungeprodukte von Ethylenoxid an Sorbitanfettsäureester wie beispielsweise die Polysorbate,
• – Zuckerfettsäureester und Anlagerungsprodukte von Ethylenoxid an Zuckerfettsäureester,
• – Anlagerungsprodukte von Ethylenoxid an Fettsäurealkanolamide und Fettamine,
• – Zuckertenside vom Typ der Alkyl- und Alkenyloligoglykoside gemäß Formel (E4-II), R₄O-[G]p (E4-II) in der R⁴ für einen Alkyl- oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen, G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen und p für Zahlen von 1 bis 10 steht. Sie können nach den einschlägigen Verfahren der präparativen organischen Chemie erhalten werden.

It has proved to be particularly preferred if the agents according to the invention additionally comprise at least one nonionic surfactant. Nonionic surfactants contain, for example, a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether group as the hydrophilic group. Such compounds are, for example

• - Addition products of 2 to 100 moles of ethylene oxide and / or 1 to 5 moles of propylene oxide to linear and branched fatty alcohols having 8 to 30 carbon atoms, to fatty acids having 8 to 30 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group,
• - With a methyl or (C ₂ to C ₆ ) -alkyl radical endgruppenverschlossene addition products of 2 to 50 moles of ethylene oxide and / or 1 to 5 moles of propylene oxide to linear and branched fatty alcohols having 8 to 30 carbon atoms, to fatty acids having 8 to 30 C atoms and alkylphenols having 8 to 15 C atoms in the alkyl group,
• C ₁₂ -C ₃₀ -fatty acid mono- and diesters of addition products of 1 to 30 mol of ethylene oxide with glycerol,
• Adducts of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil,
• - polyol fatty acid ester,
• - alkoxylated triglycerides,
• Alkoxylated fatty acid alkyl esters of the formula (E4-I) R ¹ CO- (OCH ₂ CHR ² ) _w OR ³ (E4-I) in the R ¹ CO is a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen or methyl, R ^{3 is a} linear or branched alkyl radical having 1 to 4 carbon atoms and w is a number from 1 to 20 stands,
• - amine oxides,
• Sorbitan fatty acid esters and adducts of ethylene oxide with sorbitan fatty acid esters such as the polysorbates,
• Sugar fatty acid esters and addition products of ethylene oxide with sugar fatty acid esters,
• Adducts of ethylene oxide with fatty acid alkanolamides and fatty amines,
• Sugar surfactants of the alkyl and alkenyl oligoglycoside type of formula (E4-II), R ₄ O- [G] p (E4-II) in which R ^{4 is} an alkyl or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry.

As very particularly preferred nonionic surfactants, the alkylene oxide addition products of saturated linear fatty alcohols and fatty acids having in each case 2 to 100 moles of ethylene oxide per mole of fatty alcohol or fatty acid have been found. Preparations with excellent properties are also obtained when they contain as nonionic surfactants C ₁₂ -C ₃₀ fatty acid mono- and diesters of addition products of 1 to 30 moles of ethylene oxide with glycerol and / or addition products of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil , The agents according to the invention as surfactant very particularly preferably contain at least one addition product of from 15 to 100 mol of ethylene oxide, in particular from 15 to 50 mol of ethylene oxide, to a linear or branched (in particular linear) fatty alcohol having from 8 to 22 carbon atoms. These are very particularly preferably ceteareth-15, ceteareth-25 or ceteareth-50, which are marketed as Eumulgin ^® CS 15 (Cognis), Cremophor A25 (BASF SE) or Eumulgin ^® CS 50 (Cognis).

The compositions used according to the invention may further comprise the auxiliaries and additives which are usually added to conventional styling agents.

As suitable auxiliaries and additives in particular additional care substances are mentioned.

As a care material, for example, a silicone oil and / or a silicone gum can be used. 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, dihydroxypolydimethylsiloxanes and polyphenylalkylsiloxanes. Dimethicones form the second group of silicones which may be present according to the invention. These can be both linear as well also branched as well as cyclic or cyclic and branched. Dimethicone copolyols form another group of silicones that are suitable. Particularly suitable silicones are amino-functional silicones, in particular the silicones, which are summarized under the INCI name Amodimethicone. The agents contain the silicones preferably in amounts of from 0.01% by weight to 15% by weight, particularly preferably from 0.05 to 2% by weight, based on the total agent.

As a care substance of another class of compounds, the agent particularly preferably contains at least one protein hydrolyzate and / or one of its derivatives. The protein hydrolysates are present in the agents according to the invention, for example, in concentrations of from 0.01% by weight to 20% by weight, preferably from 0.05% by weight to 15% by weight and very particularly preferably in amounts of 0 , 05 wt .-% up to 5 wt .-%, each based on the total application preparation included. As a care substance, the agent according to the invention may further comprise at least one vitamin, a provitamin, a vitamin precursor and / or one of their derivatives. Very particular preference is given to using D-panthenol as care substance, if appropriate in combination with at least one of the abovementioned silicone derivatives. As a conditioner, the compositions according to the invention can furthermore contain at least one plant extract. Mono- or oligosaccharides can also be used as a care substance in the compositions according to the invention. The mono- or oligosaccharides are preferably present in the compositions according to the invention in an amount of from 0.1 to 8% by weight, particularly preferably from 1 to 5% by weight, based on the total application preparation. The agent may further contain at least one lipid as a care substance. The agents according to the invention preferably contain the lipids in amounts of from 0.01 to 10% by weight, in particular from 0.1 to 5% by weight, based on the total application preparation.

Furthermore, oil bodies are suitable as a care substance.

• – pflanzliche Öle.
• – flüssige Paraffinöle, Isoparaffinöle und synthetische Kohlenwasserstoffe sowie Di-n-alkylether mit insgesamt zwischen 12 bis 36 C-Atomen, insbesondere 12 bis 24 C-Atomen, wie beispielsweise Di-n-octylether, Di-n-decylether, Di-n-nonylether, Di-n-undecylether, Di-n-dodecylether, n-Hexyl-n-octylether, n-Octyl-n-decylether, n-Decyl-n-undecylether, n-Undecyl-n-dodecylether und n-Hexyl-n-Undecylether sowie Di-tert-butylether, Di-iso-pentylether, Di-3-ethyldecylether, tert.-Butyl-n-octylether, iso-Pentyl-n-octylether und 2-Methyl-pentyl-n-octylether.
• – Esteröle. Unter Esterölen sind zu verstehen die Ester von C₆-C₃₀-Fettsäuren mit C₂-C₃₀-Fettalkoholen.
• – Dicarbonsäureester wie Di-n-butyladipat, Di-(2-ethylhexyl)-adipat, Di-(2-ethylhexyl)-succinat und Di-isotridecylacelaat sowie Diolester wie Ethylenglykol-dioleat, Ethylenglykol-di-isotridecanoat, Propylenglykol-di(2-ethylhexanoat), Propylenglykol-di-isostearat, Propylenglykol-di-pelargonat, Butandiol-di-isostearat, Neopentylglykoldicaprylat,
• – symmetrische, unsymmetrische oder cyclische Ester der Kohlensäure mit Fettalkoholen, beispielsweise beschrieben in der DE-OS 197 56 454 , Glycerincarbonat oder Dicaprylylcarbonat (Cetiol^® CC),
• – Trifettsäureester von gesättigten und/oder ungesättigten linearen und/oder verzweigten Fettsäuren mit Glycerin,
• – Fettsäurepartialglyceride, worunter Monoglyceride, Diglyceride und deren technische Gemische zu verstehen sind. Bei der Verwendung technischer Produkte können herstellungsbedingt noch geringe Mengen Triglyceride enthalten sein. Die Partialglyceride folgen vorzugsweise der Formel (D4-I),
  
  in der R¹, R² und R³ unabhängig voneinander für Wasserstoff oder für einen linearen oder verzweigten, gesättigten und/oder ungesättigten Acylrest mit 6 bis 22, vorzugsweise 12 bis 18, Kohlenstoffatomen stehen mit der Maßgabe, dass mindestens eine dieser Gruppen für einen Acylrest und mindestens eine dieser Gruppen für Wasserstoff steht. Die Summe (m + n + q) steht für 0 oder Zahlen von 1 bis 100, vorzugsweise für 0 oder 5 bis 25. Bevorzugt steht R¹ für einen Acylrest und R² und R³ für Wasserstoff und die Summe (m + n + q) ist 0. Typische Beispiele sind Mono- und/oder Diglyceride auf Basis von Capronsäure, Caprylsäure, 2-Ethyl¬hexansäure, Caprinsäure, Laurinsäure, Isotridecansäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Elaeostearinsäure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure sowie deren technische Mischungen. Vorzugsweise werden Ölsäuremonoglyceride eingesetzt.

The natural and synthetic cosmetic oil bodies include, for example:

• - vegetable oils.
• Liquid paraffin oils, isoparaffin oils and synthetic hydrocarbons and di-n-alkyl ethers having a total of from 12 to 36 carbon atoms, in particular 12 to 24 carbon atoms, such as, for example, di-n-octyl ether, di-n-decyl ether, di-n- nonyl ether, di-n-undecyl ether, di-n-dodecyl ether, n-hexyl n-octyl ether, n-octyl n-decyl ether, n-decyl n-undecyl ether, n-undecyl n-dodecyl ether and n-hexyl n-undecyl ether and di-tert-butyl ether, di-iso-pentyl ether, di-3-ethyldecyl ether, tert-butyl n-octyl ether, iso-pentyl n-octyl ether and 2-methyl-pentyl-n-octyl ether.
• - Ester oils. Ester oils are understood as meaning the esters of C ₆ -C ₃₀ -fatty acids with C ₂ -C ₃₀ -fatty alcohols.
• Dicarboxylic acid esters such as di-n-butyl adipate, di (2-ethylhexyl) adipate, di- (2-ethylhexyl) succinate and di-isotridecyl acelate, and diol esters such as ethylene glycol dioleate, ethylene glycol diisotridecanoate, propylene glycol di (2 ethylhexanoate), propylene glycol diisostearate, propylene glycol di-pelargonate, butanediol diisostearate, neopentyl glycol dicaprylate,
• Symmetrical, unsymmetrical or cyclic esters of carbonic acid with fatty alcohols, for example described in US Pat DE-OS 197 56 454 , Glycerol carbonate or dicaprylyl carbonate (Cetiol ^® CC),
• Triflic acid esters of saturated and / or unsaturated linear and / or branched fatty acids with glycerol,
• - fatty acid partial glycerides, which are understood to mean monoglycerides, diglycerides and their technical mixtures. With the use of technical products production reasons may still contain small amounts of triglycerides. The partial glycerides preferably follow the formula (D4-I),
  
  in which R ¹ , R ² and R ³ independently of one another represent hydrogen or a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22, preferably 12 to 18, carbon atoms, with the proviso that at least one of these groups represents a Acyl radical and at least one of these groups is hydrogen. The sum (m + n + q) is 0 or numbers from 1 to 100, preferably 0 or 5 to 25. Preferably, R ^{1 is} an acyl radical and R ² and R ^{3 are} hydrogen and the sum (m + n + q) is 0. Typical examples are mono- and / or diglycerides based on caproic acid, Caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid, and technical mixtures thereof. Preferably, oleic acid monoglycerides are used.

The amount used of the natural and synthetic cosmetic oil bodies in the compositions according to the invention is usually 0.1-30% by weight, based on the total application preparation, preferably 0.1-20% by weight, and in particular 0.1-15% by weight. %.

Although each of the aforementioned care substances alone already gives a satisfactory result, in the context of the present invention, all embodiments are also included, in which the agent contains a plurality of care substances also from different groups.

By adding a UV filter, both the agents themselves and the treated fibers can be protected from the harmful effects of UV radiation. The UV filters are usually contained in quantities of 0.01-5% by weight, based on the total application preparation. Amounts of 0.1-2.5 wt .-% are preferred.

In a particular embodiment, the composition according to the invention also contains one or more substantive dyes. This allows the treated keratin fiber not only to be temporarily patterned when the agent is applied, but also dyed at the same time. This may be particularly desirable if only a temporary dyeing is desired, for example, with eye-catching fashion colors, which can be removed again by simple washing from the keratinic fiber.

• (a) kationische Triphenylmethanfarbstoffe, wie beispielsweise Basic Blue 7, Basic Blue 26, Basic Violet 2 und Basic Violet 14,
• (b) aromatischen Systeme, die mit einer quaternären Stickstoffgruppe substituiert sind, wie beispielsweise Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 und Basic Brown 17, sowie
• (c) direktziehende Farbstoffe, die einen Heterocyclus enthalten, der mindestens ein quaternäres Stickstoffatom aufweist, wie sie beispielsweise in der EP-A2-998 908 , auf die an dieser Stelle explizit Bezug genommen wird, in den Ansprüchen 6 bis 11 genannt werden.

Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyes are those having the international designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 known compounds as well as 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) -aminophenol, 2- (2'-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2'-hydroxyethyl) - amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-carbo acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene. Preference is given to using cationic substantive dyes. Particularly preferred are

• (a) cationic triphenylmethane dyes such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,
• (b) aromatic systems substituted with a quaternary nitrogen group, such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well as
• (C) direct dyes containing a heterocycle having at least one quaternary nitrogen atom, as described for example in the EP-A2-998 908 to which reference is made at this point, are called in the claims 6 to 11.

The dyes which are also known by the names Basic Yellow 87, Basic Orange 31 and Basic Red 51 are very particularly preferred cationic substantive dyes of group (c). The cationic substantive dyes sold under the trademark Arianor® are also very particularly preferred cationic substantive dyes according to the invention. The agents according to the invention according to this embodiment preferably contain the substantive dyes in an amount of 0.001 to 20 wt .-%, based on the total agent.

It is preferred according to the invention that the agents according to the invention are free of oxidation dye precursors. Oxidation dye precursors are classified into so-called developer components and coupler components. 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 formulation of the compositions according to the invention can be carried out in all forms customary for styling agents, for example in the form of solutions which can be applied to the hair as hair lotions or pump or aerosol spray, in the form of creams, emulsions, waxes, gels or surfactant-containing foaming solutions or other preparations suitable for use on the hair.

• (i) ein kosmetisches Mittel, enthaltend in einem kosmetisch akzeptablen Träger die Wirkstoffkombination des ersten Erfindungsgegenstandes (vide supra), aufgetragen wird,
• (ii) die Fasern nach einer Einwirkzeit – nicht gespült werden und – gegebenenfalls getrocknet werden,
• (iii) die Fasern einer Wärmebehandlung unterzogen werden,
• (iv) die Fasern gegebenenfalls gespült werden.

A second subject of the invention is a method for reshaping, in particular for smoothing, keratin-containing fibers, in particular human hair, in which

• (i) a cosmetic composition comprising, in a cosmetically acceptable carrier, the active ingredient combination of the first subject of the invention (vide supra),
• (ii) the fibers are not rinsed after a contact time and are optionally dried,
• (iii) the fibers are subjected to a heat treatment,
• (iv) optionally rinsing the fibers.

It is preferred in accordance with the invention to apply the agent in step (i) as a spray, i. to spray the agent in step (i) on the keratin-containing fibers. It is a pump spray or aerosol spray.

• – nach, vor oder während Schritt (i) verformt, und/oder
• – während Schritt (iii) verformt. Verformungshilfsmittel im Sinne des erfindungsgemäßen Verfahrens können
• – z.B. Lockenwickler oder Papilloten im Falle einer Dauerwelle,
• – oder Hilfsmittel für eine mechanische Glättung, wie ein Kamm oder eine Bürste, ein Glättungsboard oder ein beheizbares Glätteisen im Falle einer Haarglättung sein.

In a method which is preferred according to the invention, the fibers are formed with the aid of deformation aids

• - deformed after, before or during step (i), and / or
• - deformed during step (iii). Deformation aids in the sense of the method according to the invention can
• - for example curlers or papillots in the case of a perm,
• - or auxiliary for a mechanical smoothing, such as a comb or a brush, a smoothing board or a heated flat iron in case of hair straightening.

Mechanical smoothing is understood according to the invention to mean stretching of the curly fiber along its longest spatial extent.

It is preferred, in the context of a hair straightening, to smooth the fibers mechanically during the contact time from step (ii), in particular by combing or with the aid of a smoothing board.

If the shaping aids, for example winder, are attached to the fiber by means of a corrugated process for a longer period of time, it is expedient to remove these deformation aids after step (iv).

In a preferred embodiment of the invention, the keratin-containing fibers are moistened prior to step (i). This can be done by spraying the fibers with a liquid, preferably water. Preferably, prior to step (i), the fibers are shampooed with a conventional shampoo, rinsed and then toweled with a towel. After completion of the terry step remains a noticeable residual moisture in the hair back.

The reaction time of step (ii) is preferably 1-150 minutes, more preferably 1-60 minutes.

It is preferred according to the invention to dry the fibers in step (ii) before the heat treatment of step (iii). A dry keratin-containing fiber according to step (ii) of the method according to the invention is present when the water residues adhering to the hair have evaporated to such an extent that the hairs fall individually. Preferably, in dry keratin fiber, either the moisture content of the fiber is substantially in equilibrium with the humidity of the air, or the fiber absorbs moisture from the ambient air. Such a dry fiber is preferably obtained by drying the wet fiber with hot air using a hair dryer. The drying in step (ii) is preferably carried out if after step (ii) a heat treatment takes place in the context of a forming process in which the surface of the keratin-containing fibers is directly treated with a tempered surface of a forming aid (eg flat iron or corrugated iron) during a forming step ,

In a preferred embodiment, in step (iii), the fibers are subjected to a heat treatment with simultaneous deformation of the fiber at a temperature of 50 ° C to 350 ° C (preferably 80 ° C to 280 ° C, more preferably 100 ° C to 250 ° C). more preferably 140 ° C to 220 ° C). Simultaneous deformation means that during the heat treatment the fiber is transformed into a mold, e.g. by mechanical smoothing or fixing the shape by winder or papillotene, brought or held.

In a specific embodiment, as part of a hair straightening the fibers in step (iii) a heat treatment with mechanical smoothing of the fiber at a temperature of 50 ° C to 350 ° C (preferably 80 ° C to 280 ° C, particularly preferably 100 ° C to 250 ° C, more preferably 140 ° C to 220 ° C). The heat treatment can be done with hot air. In this case, the fiber is heated during the combing exactly at the point where the mechanical smoothing takes place. Moreover, it is particularly preferred that the heat treatment in the manner of smoothing with the aid of a so-called smoothing iron with appropriately tempered plates, in particular metal or ceramic plates, takes place in which the plate is pressed onto the fiber to be smoothed and pressed onto the fiber plate is moved along the fiber. The plates may optionally be coated with heat resistant materials. Particularly preferably, the keratin-containing fiber to be smoothed is pressed between two appropriately tempered plates and both plates are simultaneously moved along the longest spatial extent of the fiber. It is again preferred that both plates are connected to each other, so that both plates can be moved uniformly along the fiber. When the heat treatment is performed on living hair, the fiber is attached to one end (hair root). The plates in this case are preferably moved evenly away from the hair root along the entire fiber. This movement causes a mechanical smoothing of the fiber. A suitable device for heat treatment, for example, the device "Ceramic Flat-Master" (sold by: Efalock, Germany) or Schwarzkopf Professional: Model No: IP30A.

In a further embodiment, as part of a corrugation, the fibers are heat-treated under mechanical curling of the fiber in a step (iii) following step (ii) at a temperature of 50 ° C to 350 ° C (preferably 80 ° C to 280 ° C , more preferably 100 ° C to 250 ° C, more preferably 140 ° C to 220 ° C). The heat treatment can be done with a hot air blower. In this case, either the fiber is wound around a corresponding hot air curling iron and heated precisely at the point where the Krausung occurs. Or the fibers are wound on curlers as a deformation aid and heated with a hair dryer. Another possibility of heat-assisted corrugation takes place in which the fibers are wound around a rod with a correspondingly heated surface without the use of a hot-air blower and heated precisely at the point at which the curling takes place. A suitable device for heat treatment, for example, the device from Schwarzkopf Professional, Model No: CPL Type F37.

Furthermore, the fibers can be treated as part of a post-treatment at the end of the process according to the invention with a commercial conditioner.

• 1. Verwendung einer Wirkstoffkombination aus (a) mindestens einem nichtionischen Polymer (a) mit mindestens einer Struktureinheit der Formel (M1) und mindestens einer Struktureinheit der Formel (M2)
  
  worin R’ eine (C₁- bis C₃₀)-Acylgruppe bedeutet, insbesondere eine Acetylgruppe, und (b) mindestens einem kationischen Polymer (b) mit mindestens einer Struktureinheit der Formel (M1) und mindestens einer Struktureinheit der Formel (M3) und mindestens einer Struktureinheit der Formel (M4)
  
  worin R’’ für eine (C₁ bis C₄)-Alkylgruppe, insbesondere für eine Methylgruppe, steht, zum Hitzeschutz keratinhaltiger Fasern, die Wärme von einer Temperatur von 80°C bis 350°C (vorzugsweise 80°C bis 280°C, besonders bevorzugt 100°C bis 250°C, weiter bevorzugt 140°C bis 220°C) ausgesetzt werden.
• 2. Verwendung gemäß Punkt 1, dadurch gekennzeichnet, dass die Wärmequelle ein Glätteisen oder Welleisen ist.
• 3. Verwendung nach einem der Punkte 1 oder 2, dadurch gekennzeichnet, dass das nichtionische Polymer (a) ein Polymer aus N-Vinylpyrrolidon und Vinylacetat ist.
• 4. Verwendung nach einem der Punkt 3, dadurch gekennzeichnet, dass das Molverhältnis der aus dem Monomer N-Vinylpyrrolidon enthaltenen Struktureinheiten zu den aus dem Monomer Vinylacetat enthaltenen Struktureinheiten des nichtionischen Polymers (a) im Bereich von 20 zu 80 bis 80 zu 20, insbesondere im Bereich von 30 zu 70 bis 60 zu 40, liegt.
• 5. Verwendung nach einem der Punkte 1 bis 4, dadurch gekennzeichnet, dass R’’ in Formel (M4) für eine Methylgruppe steht.
• 6. Verwendung nach einem der Punkte 1 bis 5, dadurch gekennzeichnet, dass das kationische Polymer (b) 1 bis 20 Mol-%, vorzugsweise 5 bis 15 Mol.-% und insbesondere 10 Mol.-% Struktureinheiten gemäß Formel (M4) (insbesondere mit R’’ = Methyl) und 30 bis 50 Mol.-%, vorzugsweise 35 bis 45 Mol.-% und insbesondere 40 Mol.-% Struktureinheiten gemäß Formel (M1) und 40 bis 60 Mol.-%, vorzugsweise 45 bis 55 Mol.-% und insbesondere 60 Mol.-% Struktureinheiten gemäß Formel (M3) enthält.
• 7. Verwendung nach einem der Punkte 1 bis 6, dadurch gekennzeichnet, dass das kationische Polymer (b) das Polymer mit der INCI-Nomenklatur Polyquarternium-46 ist.
• 8. Verwendung nach einem der Punkte 1 bis 7, dadurch gekennzeichnet, dass die Wirkstoffkombination die Polymere (a) und (b) in einem Gewichtsverhältnisbereich von 10 zu 1 bis 1 zu 10, insbesondere von 5 zu 1 bis 1 zu 5, besonders bevorzugt von 3 zu 1 bis 1 zu 3, ganz besonders bevorzugt von 1.5 zu 1 bis 1 zu 1.5, enthält.
• 9. Verfahren zur Umformung, insbesondere zur Glättung, keratinhaltiger Fasern, insbesondere menschlicher Haare, in welchem (i) ein kosmetisches Mittel, enthaltend in einem kosmetisch akzeptablen Träger die Wirkstoffkombination wie sie in einem der Punkte 1 bis 8 definiert wird, aufgetragen wird, (ii) die Fasern nach einer Einwirkzeit – nicht gespült werden und – gegebenenfalls getrocknet werden, (iii) die Fasern einer Wärmebehandlung unterzogen werden, (iv) die Fasern gegebenenfalls gespült werden.
• 10. Verfahren nach Punkt 9, dadurch gekennzeichnet, dass in Schritt (iii) einer Wärmebehandlung unter gleichzeitiger Verformung der Faser bei einer Temperatur von 50°C bis 350°C (vorzugsweise 80°C bis 280°C, besonders bevorzugt 100°C bis 250°C, weiter bevorzugt 140°C bis 220°C) unterworfen werden.
• 11. Verfahren nach einem der Punkte 9 oder 10, dadurch gekennzeichnet, dass im Rahmen einer Haarglättung die Fasern in Schritt (iii) einer Wärmebehandlung unter mechanischer Glättung der Faser bei einer Temperatur von 50°C bis 350°C (vorzugsweise 80°C bis 280°C, besonders bevorzugt 100°C bis 250°C, weiter bevorzugt 140°C bis 220°C) unterworfen, wobei die Wärmebehandlung nach Manier des Glättens mit Hilfe eines sogenannten Glätteisens mit entsprechend temperierter Platten, insbesondere Metall- oder Keramikplatten, erfolgt, in dem die Platte auf die zu glättende Faser gedrückt wird und die an die Faser gedrückte Platte entlang der Faser bewegt wird.
• 12. Verfahren nach einem der Punkte 9 bis 11, dadurch gekennzeichnet, dass die Wirkstoffkombination aus den Polymeren (a) und (b) bevorzugt in einer Gesamtmenge von 0,1 bis 10,0 Gew.-%, bevorzugt von 0,5 bis 8,0 Gew.-%, besonders bevorzugt 1,0 bis 5,0 Gew.%, am bevorzugtesten 2,0 bis 5,0 Gew.%, jeweils bezogen auf das Gewicht des anwendungsbereiten Mittels, in dem kosmetischen Mittel des Schritts (i) enthalten ist.
• 13. Verfahren nach einem der Ansprüche 9 bis 12, dadurch gekennzeichnet, dass das Mittel in Schritt (i) auf die keratinhaltigen Fasern gesprüht wird.

The following points describe a preferred embodiment of the invention:

• 1. Use of an active substance combination of (a) at least one nonionic polymer (a) having at least one structural unit of the formula (M1) and at least one structural unit of the formula (M2)
  
  wherein R 'is a (C ₁ to C ₃₀ ) acyl group, in particular an acetyl group, and (b) at least one cationic polymer (b) having at least one structural unit of the formula (M1) and at least one structural unit of the formula (M3) and at least one structural unit of the formula (M4)
  
  wherein R "is a (C ₁ to C ₄ ) alkyl group, in particular a methyl group, for the heat protection keratinhaltiger fibers, the heat of a temperature of 80 ° C to 350 ° C (preferably 80 ° C to 280 ° C. , more preferably 100 ° C to 250 ° C, more preferably 140 ° C to 220 ° C) are exposed.
• 2. Use according to item 1, characterized in that the heat source is a flat iron or corrugated iron.
• 3. Use according to one of the items 1 or 2, characterized in that the nonionic polymer (a) is a polymer of N-vinylpyrrolidone and vinyl acetate.
• 4. Use according to one of the items 3, characterized in that the molar ratio of the structural units comprised of the monomer N-vinylpyrrolidone to the structural units of the nonionic polymer (a) contained in the monomer vinyl acetate is in the range from 20 to 80 to 80 to 20, in particular in the range of 30 to 70 to 60 to 40, lies.
• 5. Use according to one of the items 1 to 4, characterized in that R '' in formula (M4) is a methyl group.
• 6. Use according to one of the items 1 to 5, characterized in that the cationic polymer (b) 1 to 20 mol%, preferably 5 to 15 mol% and in particular 10 mol% of structural units of the formula (M4) ( in particular with R "= methyl) and 30 to 50 mol%, preferably 35 to 45 mol% and in particular 40 mol% of structural units of the formula (M1) and 40 to 60 mol%, preferably 45 to 55 mol .-% and in particular 60 mol .-% of structural units according to formula (M3).
• 7. Use according to one of the items 1 to 6, characterized in that the cationic polymer (b) is the polymer with the INCI nomenclature Polyquarternium-46.
• 8. Use according to one of items 1 to 7, characterized in that the combination of active substances, the polymers (a) and (b) in a weight ratio range of 10 to 1 to 1 to 10, in particular from 5 to 1 to 1 to 5, particularly preferred from 3 to 1 to 1 to 3, most preferably from 1.5 to 1 to 1 to 1.5.
• 9. A process for reshaping, in particular for smoothing, keratin-containing fibers, in particular human hair, in which (i) a cosmetic composition containing, in a cosmetically acceptable carrier, the active ingredient combination as defined in any one of items 1 to 8, ii) the fibers are not rinsed after a contact time and are optionally dried, (iii) the fibers are subjected to a heat treatment, (iv) the fibers are optionally rinsed.
• 10. The method according to item 9, characterized in that in step (iii) a heat treatment with simultaneous deformation of the fiber at a temperature of 50 ° C to 350 ° C (preferably 80 ° C to 280 ° C, more preferably 100 ° C to 250 ° C, more preferably 140 ° C to 220 ° C).
• 11. The method according to any one of items 9 or 10, characterized in that in the context of a Haarglättung the fibers in step (iii) a heat treatment with mechanical smoothing of the fiber at a temperature of 50 ° C to 350 ° C (preferably 80 ° C to 280 ° C, more preferably 100 ° C to 250 ° C, more preferably 140 ° C to 220 ° C), wherein the heat treatment in the manner of smoothing by means of a so-called smoothing iron with appropriately tempered plates, in particular metal or ceramic plates takes place in that the plate is pressed onto the fiber to be smoothed and the plate pressed against the fiber is moved along the fiber.
• 12. The method according to any one of items 9 to 11, characterized in that the active substance combination of the polymers (a) and (b) preferably in a total amount of 0.1 to 10.0 wt .-%, preferably from 0.5 to 8.0% by weight, particularly preferably 1.0 to 5.0% by weight, most preferably 2.0 to 5.0% by weight, in each case based on the weight of the ready-to-use agent, in the cosmetic product of step ( i) is included.
• 13. The method according to any one of claims 9 to 12, characterized in that the agent in step (i) is sprayed onto the keratin-containing fibers.

Examples

1.0 Proof of effect

The following cosmetic agent was prepared by mixing the components. Table 1: Test compositions raw material V1 [% by weight] V2 [% by weight] V3 [% by weight] E1 [% by weight] Luviskol VA 64 W ¹ - 5.00 - 2.50 Polyquaternium-46 2.50 - - 1.25 water ad 100 ad 100 100 ad 100 ¹ Copolymer of vinylpyrrolidone and vinyl acetate (60:40) (50% active substance in water, INCI name: VP / VA copolymer) (BASF)

The composition marked E is according to the invention, the compositions marked V are not according to the invention.

1.1 Test Method HP-DSC (High Pressure Differential Scanning Calorimetry)

Thermoanalytical studies are particularly suitable for the characterization of two-phase systems, which include the human hair as fiber keratin with their crystalline α-helix content and amorphous matrix portion also belong. On the one hand, glass transition and aging behavior of the amorphous matrix can be investigated; on the other hand, the melting behavior of the crystalline, helical phase provides important insights. Thermoanalytical investigations are first described in 1899, first differential thermoanalysis (DTA) on protein fibers was carried out in the late fifties. In the following years, various thermoanalytical measuring methods, such as DTA, HP-DTA (High Pressure, High Pressure DTA) and DSC (Differential Scanning Calorimetry), have been applied to keratin fibers, e.g. to investigate the phenomenon of supercontraction, α-β phase transitions of helices or denaturation processes. The HP-DSC method was used to study keratin fibers, which eliminates the problems of pyrolytic effects found in conventional DSC and problems with data acquisition and interpretation inherent in DTA. DSC measurements are carried out on keratins enclosed with water in commercially available, pressure-tight measuring capsules. In the keratin-water system, when heated above 100 ° C in the encapsulated steel crucibles, a high water vapor pressure develops, from which the HP-DSC analysis is derived. The major difference between the HP-DSC thermograms of human hair compared to normal DSC thermograms is that the endothermic peaks representing the point of transformation and enthalpy of transformation are shifted by about 90 ° C to lower temperatures. This is due to the fact that the water, after diffusion into the hair fiber by weakening and cleavage of hydrogen bonds and salt bonds reduces the protein stability and thus reduces the "gluing temperature" of the keratins. If only hydrogen bonds and salt bridges are dissolved by the supercontracting agent, such as water, the thermal effect is reversible (supercontraction). However, the process becomes irreversible, as soon as covalent bonds such. B. disulfide bridges are cleaved. This occurs when heated human hair fibers in pressure-resistant capsules with water to above 150 ° C. The irreversible transformation, interpreted as transition of the α-helical regions in the proteins to a disordered state, results in endothermic peaks, the peak representing the transformation or denaturation point and the peak area representing the conversion or denaturation enthalpy.

Thus, using differential scanning calorimetry (DSC), structural as well as chemical conditions and changes in fiber keratins and especially in human hair can be detected. Under well-defined experimental conditions can record in human hair, the calorimetric detectable processes using thermograms and with respect to the Peaklagen, structures and surfaces as an indicator for the influence of order-disorder transitions by changes in internal and / or external parameters, cause z. B. by cosmetic treatment of the hair use. Ie. From the endothermic peaks recorded in the thermogram of human hair, statements about firmness or damage to the human hair fiber can be made on the basis of peak position (transformation point) and peak area (transformation enthalpy).

Extensive studies on the influence of cystine content on the denaturation of α-helices in keratins have, for. For example, it has been shown that the denaturation temperature (transition temperature) of the keratin increases linearly with the cystine content. The increased stability of the matrix region due to the higher degree of crosslinking of the increased proportion of disulfide bridges in the matrix makes the conversion of the helices embedded in this matrix more difficult and thus results in an increase in the denaturation temperature. Conversely, a denaturation temperature and above all denaturation enthalpy reduction in human hair treated by perming or bleaching or dyeing can generally be observed ( H. Deutz, doctoral thesis, RWTH Aachen 1993 ).

1.2 Implementation

Human hair tresses (Kerling International (Backnang, Germany) "European natural hair 7/0") were each treated with 0.7 g of tress with 0.7 g of one of the test compositions listed in Table 1 and dried in the air without rinsing.

A flat iron (brand: Schwarzkopf Professional, Model No: IP30A) was heated at the highest level (210 ° C) for at least 10 minutes. The temperature between the heating plates measured with a contact thermometer (brand: Qtemp 300) was 180 ° C after 10 minutes.

Now the dried strand of hair was smoothed with the preheated flat iron. Care was taken to guide the smoothing along the hair fiber: 4 times short (1 second per strand of hair), 2 times long (5 seconds per strand of hair). The temperatures reached fluctuate between 146 and 181 ° C.

The hair strand was cooled in the air to room temperature, rinsed with water for about 1 minute (water temperature about 35 to 39 ° C), excess water removed with a finger and dabbed dry with a towel, hung up and left to rest and allowed to dry.

This treatment was repeated 40 times for each strand.

By thermoanalytical investigations (DSC apparatus: Perkin Elmer DSC 7, 60 μl stainless steel crucible with O-ring (24 atm)) was then tested for structural stabilization by the test compositions after repeated heat application. Each strand was divided into parts of approx. 1 mm each. Twelve of these aliquots of the same tress were placed in a DSC measuring crucible and 50 μl bidistilled water added. The measuring crucibles were closed and the sample measured in a temperature range of 100 ° C to 170 ° C (heating rate: 10 Kelvin per minute).

The untreated starting hair is also subjected to a DSC measurement.

For each test composition, 5 strands were tested. The keratin melting points calculated by arithmetic mean from the individual measurements are listed in Table 2. Table 2: Heat protection of the structure by the active ingredient combination according to the invention composition Keratinous melting point [° C] V1 145.6 V2 145.0 V3 144.0 E1 147.5 untreated home hair 153.4

The keratin melting point of the E1 treated strands is significantly higher than the fibers treated with the non-inventive test compositions. By using the combination of active substances according to the invention consequently the hair structure is protected from the action of heat.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• DE 19756454 A [0037]
• EP 2998908 A2 [0042]

Cited non-patent literature

• McMullen, R. et al., J. Cosmet. Sci., 1998, 49, 223-244 [0007]
• H. Deutz, Doctoral Thesis, RWTH Aachen 1993 [0064]

Claims (11)

Use of an active substance combination of (a) at least one nonionic polymer (a) having at least one structural unit of the formula (M1) and at least one structural unit of the formula (M2)

wherein R 'is a (C ₁ to C ₃₀ ) acyl group, in particular an acetyl group, and (b) at least one cationic polymer (b) having at least one structural unit of the formula (M1) and at least one structural unit of the formula (M3) and at least one structural unit of the formula (M4)

wherein R "is a (C ₁ to C ₄ ) alkyl group, in particular a methyl group, for the heat protection keratinhaltiger fibers, the heat of a temperature of 80 ° C to 350 ° C (preferably 80 ° C to 280 ° C. , more preferably 100 ° C to 250 ° C, more preferably 140 ° C to 220 ° C) are exposed. Use according to claim 1, characterized in that the heat source is a flat iron or corrugated iron. Use according to one of claims 1 or 2, characterized in that the nonionic polymer (a) is a polymer of N-vinylpyrrolidone and vinyl acetate. Use according to one of Claims 3, characterized in that the molar ratio of the structural units comprised of the monomer N-vinylpyrrolidone to the structural units of the nonionic polymer (a) contained in the monomer vinyl acetate is in the range from 20 to 80 to 80 to 20, in particular in the range from 30 to 70 to 60 to 40, lies. Use according to one of claims 1 to 4, characterized in that R "in formula (M4) represents a methyl group. Use according to one of claims 1 to 6, characterized in that the cationic polymer (b) is the polymer with the INCI nomenclature Polyquarternium-46. Use according to one of claims 1 to 7, characterized in that the combination of active substances, the polymers (a) and (b) in a weight ratio range of 10 to 1 to 1 to 10, in particular from 5 to 1 to 1 to 5, particularly preferably from 3 to 1 to 1 to 3, most preferably from 1.5 to 1 to 1 to 1.5 contains. Process for reshaping, in particular for smoothing, keratin-containing fibers, in particular human hair, in which (i) a cosmetic composition containing, in a cosmetically acceptable carrier, the active ingredient combination as defined in any one of claims 1 to 8, (ii) the fibers after an exposure time - not be rinsed and - optionally dried, (iii) the fibers are subjected to a heat treatment, (iv) optionally rinsing the fibers. A method according to claim 8, characterized in that in step (iii) a heat treatment with simultaneous deformation of the fiber at a temperature of 50 ° C to 350 ° C (preferably 80 ° C to 280 ° C, more preferably 100 ° C to 250 ° C, more preferably 140 ° C to 220 ° C) are subjected. Method according to one of claims 8 or 9, characterized in that in the context of a Haarglättung the fibers in step (iii) a heat treatment with mechanical smoothing of the fiber at a temperature of 50 ° C to 350 ° C (preferably 80 ° C to 280 ° C, more preferably 100 ° C to 250 ° C, more preferably 140 ° C to 220 ° C), wherein the heat treatment in the manner of smoothing with the aid of a so-called smoothing iron with appropriately tempered plates, in particular metal or ceramic plates takes place, in the plate is pressed onto the fiber to be smoothed and the pressed onto the fiber plate is moved along the fiber. Method according to one of claims 8 to 10, characterized in that the active ingredient combination of the polymers (a) and (b) preferably in a total amount of 0.1 to 10.0 wt .-%, preferably from 0.5 to 8, 0 wt .-%, particularly preferably 1.0 to 5.0 wt.%, Most preferably 2.0 to 5.0 wt.%, Each based on the weight of the ready-to-use agent, in the cosmetic agent of step (i) is included.