DE102004045253A1 - New cationic diagonally cross linked copolymer useful for improving physical characteristics of keratinic fibers (preferably human hair) and for styling and conditioning hairs - Google Patents

Abstract

Cationic diagonally cross linked copolymer (I) (obtained by copolymerisation of (A) at least one monomer A, monomer B, at least doubly unsaturated monomer C, which is copolymerisable with monomers A and B, where in the copolymer, the quantity of B and C is 35-99 wt.% and 0.5-10 wt.%, respectively related to total weight amounts of A and B) is new. Cationic diagonally cross linked copolymer (I) (obtained by copolymerisation of (A) at least one monomer A of formula (H2C=C(R1>)-C(=O)-X-R3>), monomer B of formula (H2C=C(R1>)-C(=O)-X-(CH2)n-N+>(R4>)(R6>)-(R5>) (Y->) and at least doubly unsaturated monomer C, which is copolymerisable with monomers A and B, where in the copolymer, the quantity of B and C is 35-99 wt.% and 0.5-10 wt.%, respectively related to total weight amounts of A and B) is new. R1>H or CH3; X : O or NR2>; R2>H or 1-6C alkyl; and R3>1-12C alkyl; n : 1-8; R4>-R6>1-8C alkyl, each carry one hydroxy- or amino group; and X : halo or mono alkyl sulfate. Independent claims are also included for: (1) the preparation of (I); (2) agent for the treatment of keratinic fibers comprising at least (I); and (3) a method for improving the physical characteristics of keratinic fibers, comprising applying a agent in an effective quantity on the fibers.

Description

The The present invention relates to cationic crosslinked copolymers, the use of these copolymers to improve the physical Properties of keratinic fibers and agents containing these copolymers contain.

Human Hair is becoming more diverse today Treated with hair cosmetic preparations. These include about Cleaning hair with shampoos, care and regeneration with rinses and cures, as well as bleaching, dyeing and shaping the hair with waving, toning and styling preparations.

Either the use of shampoos as well as the decorative design of the Hairstyle for example by dyeing or perms are interventions that are as well as environmental influences the natural Structure and properties of hair affect. So can subsequently such treatment or by environmental influences such as the action of intensive Solar radiation, for example wet and dry combability, the stop, the fullness, the softness and the grip of the hair will be unsatisfactory or the hair is raised Have split or "flying" due to electrostatic charge.

It has therefore been common for a long time to subject the hair to a special aftertreatment. It will, usually in the form of a conditioner or hair conditioner, the hair with special active ingredients, for example quaternary Ammonium salts or special polymers treated. Through this Depending on the wording, treatment will be combability, hold and fullness Hair improves and the split rate reduced.

by virtue of from current fashion trends Again and again, hairstyles are considered chic, affecting many hair types only build up using certain firming agents or for a longer one Period of time.

to Shaping and styling of hair it is common to use hairstyle setters like hair fixatives or hair sprays. Become a hair fixer distributed to hair styling in wet hair while hair sprays be sprayed on the finished hairstyle for fixation.

Around to achieve a sufficient hair firming effect, come in general means of application which remain on the hair. However, this is the risk of unwanted stress on the hair connected.

The strengthening agents, which are usually polymeric Compounds are usually in the form of hair fixatives or hair sprays applied. However, it is also possible to use them in conventional hair-cleaning or conditioner to incorporate.

That's how it describes DE 19839261 hair-fixing agents containing a mixture of at least two different polymers. One of the polymers is an amphoteric or zwitterionic silicone polymer, the other a silicone-free amphoteric or zwitterionic polymer. The latter may contain cationic or cationic substituted acrylic acid derivatives as one type of monomer, but it necessarily also contains a monomer having a neutralized or unneutralized acidic group.

the One skilled in the art is aware of a number of firming agents, as well also a number of nourishing and conditioning agents. If both hair setting and conditioning effects are desired, is usually to resort to combination preparations.

From the EP 0661965 are hair conditioning shampoos with styling effects, especially hair stiffening effects, known. The shampoos contain as compelling components at least one cationic polymer, a long-chain non-aromatic anionic surfactant and another, sulfate or sulfonate-containing anionic surfactant. The cationic polymers must have a certain minimum charge density and may be selected, for example, from polymers and copolymers of dialkyldiallylammonium salts or certain copolymers of vinylimidazole and vinylpyrrolidone.

The However, active ingredients known from the prior art can not all be Wishes fulfill.

So show the known hair-setting agents at high ambient humidity often no longer sufficient effects. You can also strain the hair or its handle, its volume or its shine in unwanted Change way.

Further is the applicability of the known hair cosmetic agents through their solubilities or Dispersibilities in the corresponding hair treatment agents limited as well as through their compatibility with the rest contained in recipe ingredients. This is how it can be with the combination the widely used as hair-fixing agents cationic Polymers with anionic recipe ingredients to undesirable precipitations come.

Of the The present invention was based on the object, new active ingredients for the preparation of hair treatment compositions which are suitable for strengthening keratinic fibers and opposite to the have known in the prior art agents have advantages. In a further aspect, it was an object of the invention that these Active ingredients simultaneously have conditioning properties should.

It was now surprisingly found that certain cationic crosslinked copolymers contain these Meet requirements in an excellent way.

• (a) mindestens einem Monomer A der Formel (I)
  
  worin R¹ = H oder Methyl, X = O oder NR², R² = Wasserstoff oder einen linearen oder verzweigten Alkylrest mit 1 bis 6 Kohlenstoffatomen und R³ einen linearen oder verzweigten Alkylrest mit 1 bis 12 Kohlenstoffatomen bedeuten,
• (b) mindestens einem Monomer B der Formel (II)
  
  worin R¹ = H oder Methyl, X = O oder NR², R² = Wasserstoff oder einen linearen oder verzweigten Alkylrest mit 1 bis 6 Kohlenstoffatomen, n eine ganze Zahl von 1 bis 8, R⁴, R⁵, R⁶ gleich oder verschieden sind und jeweils einen Alkylrest mit 1 bis 8 Kohlenstoffatomen bedeuten, der jeweils eine Hydroxy- oder eine Aminogruppe tragen kann, und Y ein Halogen oder ein Monoalkylsulfat bedeutet, und
• (c) mindestens einem wenigstens zweifach ungesättigten Monomer C, welches mit den Monomeren A und B copolymerisierbar ist,

wobei im Copolymer der Mengenanteil des/der Monomeren B zwischen 35 und 99 Gew.-% und der Mengenanteil des/der Monomeren C zwischen 0,5 und 10 Gew.-% beträgt, jeweils bezogen auf das Gesamtgewicht der Monomeren A und B.A first subject of the invention is therefore a cationic crosslinked copolymer obtainable by copolymerization of

• (a) at least one monomer A of the formula (I)
  
  wherein R ^{1 is} H or methyl, X is O or NR ² , R ^{2 is} hydrogen or a linear or branched alkyl radical having 1 to 6 carbon atoms and R ^{3 is} a linear or branched alkyl radical having 1 to 12 carbon atoms,
• (b) at least one monomer B of the formula (II)
  
  wherein R ¹ = H or methyl, X = O or NR ² , R ² = hydrogen or a linear or branched alkyl radical having 1 to 6 carbon atoms, n is an integer from 1 to 8, R ⁴ , R ⁵ , R ^{6 is the} same or are each different and each represents an alkyl radical having 1 to 8 carbon atoms, which may each carry a hydroxy or an amino group, and Y is a halogen or a monoalkyl sulfate, and
• (c) at least one at least diunsaturated monomer C which is copolymerizable with the monomers A and B,

wherein in the copolymer, the proportion of / of the monomer B between 35 and 99 wt .-% and the proportion of the / the monomer C is between 0.5 and 10 wt .-%, each based on the total weight of the monomers A and B.

When Monomers A are the esters and amides of acrylic acid and of methacrylic acid, which are based on alcohols or amines containing up to 12 carbon atoms contain. Suitable alcohols are, for example, methanol, ethanol, n- and iso-propyl alcohol, n-butyl alcohol, tert-butyl alcohol, sec-butyl alcohol, n-pentyl alcohol, 2-methylbutyl alcohol, 3-methylbutyl alcohol, 2,2-dimethylpropyl alcohol, 1,2-dimethylpropyl alcohol, 1,1-dimethylpropyl alcohol, sec-pentyl alcohol and n-hexyl alcohol, as well as cyclic alcohols such as e.g. Cyclohexyl.

When Alcohols are preferably isopropyl alcohol, tert-butyl alcohol, sec-butyl alcohol, 2-methylbutyl alcohol, 3-methylbutyl alcohol, 2,2-dimethylpropyl alcohol, 1,2-Dimethylpropylalkohol and 1,1-dimethylpropyl alcohol.

suitable Amines are, for example, methylamine, dimethylamine, ethylamine, ethylmethylamine, Diethylamine, n- and iso-propylamine, n-butylamine, tert-butylamine, sec-butylamine, n-pentylamine, 2-methylbuytlamine, 3-methylbutylamine, 2,2-dimethylpropylamine, 1,2-dimethylpropylamine, 1,1-dimethylpropylamine, sec-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, N-undecylamine, n-dodecylamine, as well as cyclic amines such as e.g. Cyclohexylamine.

When Amines are preferred are isopropylamine, tert-butylamine, sec-butylamine, 2-Methylbuytlamin, 3-methylbutylamine, 2,2-dimethylpropylamine, 1,2-dimethylpropylamine and 1,1-dimethylpropylamine.

When Monomer A suitable esters are, for example, methyl acrylate, ethyl acrylate, n- and iso-propyl acrylate, n-butyl acrylate, tert-butyl acrylate, sec-butyl acrylate, n-pentyl acrylate, 2-methylbutyl acrylate, 3-methylbutyl acrylate, 2,2-dimethylpropyl acrylate, 1,2-dimethylpropyl acrylate, 1,1-dimethylpropyl acrylate, sec-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate n-nonyl acrylate, n-decyl acrylate, N-undecyl acrylate, n-dodecyl acrylate, as well as cyclic variants e.g. cyclohexyl, Furthermore, methyl (meth) acrylate, ethyl (meth) acrylate, n- and iso-propyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, sec-butyl (meth) acrylate, n-pentyl (meth) acrylate, 2-methylbutyl (meth) acrylate, 3-methylbutyl (meth) acrylate, 2,2-dimethylpropyl (meth) acrylate, 1,2-dimethylpropyl (meth) acrylate, 1,1-dimethylpropyl (meth) acrylate, sec-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, N-undecyl (meth) acrylate and n-dodecyl (meth) acrylate, as well as cyclic variants e.g. Cyclohexyl (meth) acrylate. Preferred esters are isopropyl acrylate, tert-butyl acrylate, sec-butyl acrylate, 2-methylbutyl acrylate, 3-methylbutyl acrylate, 2,2-dimethylpropyl acrylate, 1,2-dimethylpropyl acrylate, 1,1-dimethylpropyl acrylate, iso-propyl (meth) acrylate, tert-butyl (meth) acrylate, sec-butyl (meth) acrylate, 2-methylbutyl (meth) acrylate, 3-methylbutyl (meth) acrylate, 2,2-dimethylpropyl (meth) acrylate, 1,2-dimethylpropyl (meth) acrylate and 1,1-dimethylpropyl (meth) acrylate.

When Monomer A suitable amides are, for example, N-methylacrylamide, N-Ethylacrylsäureamid, N-n- and iso-propylacrylic acid amide, N-n-Butylacrylsäureamid, N-tert-Butylacrylsäureamid, N-sec-Butylacrylsäureamid, N-n-Pentylacrylsäureamid, N-2-Methylbuytlacrylsäureamid, N-3-methylbutylacrylamide, N-2,2-dimethylpropylacrylamide, N-1,2-Dimethylpropylacrylsäureamid, N-1,1-Dimethylpropylacrylsäureamid, N-sec-Pentylacrylsäureamid, N-n-Hexylacrylsäureamid, N-n-Heptylacrylsäureamid, N-n-Octylacrylsäureamid, N-n-Nonylacrylsäureamid, N-n-Decylacrylsäureamid, N-Undecylacrylsäureamid, N-n-Dodecylacrylsäureamid, and cyclic amides, e.g. N-Cyclohexylacrylsäureamid, Furthermore, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-n and iso-propyl (meth) acrylamide, N-n-butyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-sec-butyl (meth) acrylamide, N-n-pentyl (meth) acrylamide, N-2-methylbutyl (meth) acrylamide, N-3-methylbutyl (meth) acrylamide, N-2,2-dimethylpropyl (meth) acrylamide, N-1,2-dimethylpropyl (meth) acrylamide, N-1,1-dimethylpropyl (meth) acrylamide, N-sec-pentyl (meth) acrylamide, N-n-hexyl (meth) acrylamide, N-n-heptyl (meth) acrylamide, N-n-octyl (meth) acrylamide, N-n-nonyl (meth) acrylic acid amide, N-n-decyl (meth) acrylic acid amide, N-undecyl (meth) acrylic acid amide and N-n-dodecyl (meth) acrylamide, and cyclic amides, e.g. N-cyclohexyl (meth) acrylamide. Preferred amides are N-isopropyl-propylacrylamide, N-tert-butylacrylamide, N-sec-butylacrylamide, N-2-Methylbuytlacrylsäureamid, N-3-Methylbutylacrylsäureamid, N-2,2-Dimethylpropylacrylsäureamid, N-1,2-Dimethylpropylacrylsäureamid, N-1,1-Dimethylpropylacrylsäureamid, N-iso-propyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-sec-butyl (meth) acrylamide, N-2-Methylbuytl (meth) acrylamide, N-3-methylbutyl (meth) acrylamide, N-2,2-dimethylpropyl (meth) acrylamide, N-1,2-dimethylpropyl (meth) acrylamide and N-1,1-dimethylpropyl (meth) acrylamide.

in the As the invention is particularly preferred as the monomer A is N-Isopropylacrylsäureamid.

Suitable monomers B are the esters and amides of acrylic acid and the formula (I) Methacrylic acid, which carry a quaternary ammonium group in the molecule. Examples of suitable monomers B are acrylic acid (methyltrimethylammonium salt) ester, 2-acrylic acid (ethyltrimethylammonium salt) ester, 2-acrylic acid (propyltrimethylammonium salt) ester, 3-acrylic acid (propyltrimethylammonium salt) ester, 4-acrylic acid (butyltrimethylammonium salt ) esters, 5-acrylic acid (pentyltrimethylammonium) esters, 6-acrylic acid (hexyltrimethylammonium) esters, 4-acrylic acid (hexyltrimethylammonium) esters, methacrylic acid (methyltrimethylammonium) esters, 2-methacrylic acid (ethyltrimethylammonium) esters , 2-Methacrylic acid (propyltrimethylammonium salt) ester, 3-methacrylic acid (propyltrimethylammonium salt) ester, 4-methacrylic acid (butyltrimethylammonium salt) ester, 5-methacrylic acid (pentyltrimethylammonium salt) ester, 6-methacrylic acid (hexyltrimethylammonium salt) ester , 4-methacrylic acid (hexyltrimethylammonium salt) esters, acrylamidomethyltrimethylammonium salts, 2-acrylamidoethyltrimethylammonium salts, 2-acrylamidopropyltrimethylammonium salts, 3-acrylamido propyltrimethylammonium salts, 4-acrylamidobutyltrimethylammonium salts, 5-acrylamidopentyltrimethylammonium salts, 6-acrylamidohexyltrimethylammonium salts, 4-acrylamidohexyltrimethylammonium salts, methacrylamidomethyltrimethylammonium salts, 2-methacrylamidoethyltrimethylammonium salts, 2-methacrylamidopropyltrimethylammonium salts, 3-methacrylamidopropyltrimethylammonium salts, 4-Methacrylamidobutyl-trimethylammonium salts, 5-Methacrylamidopentyl-trimethylammonium salts, 6-Methacrylamidohexyl-trimethylammonium salts and 4-Methacrylamidohexyl-trimethylammonium salts, wherein the counterion of the ammonium salt is selected from the group of halides, chalcogenides, sulfates, monoalkyl sulfates, carbonates or phosphates.

preferred Monomers B are 2-acrylic acid (ethyltrimethylammonium salt) ester, 2-acrylic acid (propyl-trimethylammonium salt) ester, 3-acrylic acid (propyl-trimethylammonium salt) ester, 4-acrylic acid (butyl-trimethylammonium salt) ester, 2-methacrylic acid (propyl-trimethylammonium salt) ester, 3-methacrylic acid (propyl-trimethylammonium salt) ester, 4-methacrylic acid (butyl-trimethylammonium salt) ester, 2-acrylamidoethyltrimethylammonium salts, 2-acrylamidopropyltrimethylammonium salts, 3-acrylamidopropyl-trimethylammonium salts, 4-acrylamidobutyltrimethylammonium salts, 2-methacrylamidoethyltrimethylammonium salts, 2-methacrylamidopropyl trimethylammonium salts, 3-methacrylamidopropyltrimethylammonium salts and 4-methacrylamidobutyltrimethylammonium salts.

As counterions Y ^{- of} the ammonium salts, halides, alkyl sulfates such as methosulfate, and sulfate are preferred.

in the According to the invention, monomer B is particularly preferably 3-acrylamidopropyltrimethylammonium salts, in particular (3-acrylamidopropyl) trimethylammonium chloride.

All particularly preferred are copolymers which, as monomers, are N-isopropylacrylamide and a 3-acrylamidopropyltrimethylammonium salt, especially (3-acrylamidopropyl) trimethylammonium chloride.

Especially good effects could be observed with copolymers according to the invention in which the proportion of the / the monomer B between 45 and 90 and in particular between 50 and 80 wt .-%, based on the total weight of monomers A and B.

The Copolymers of the invention are cross-linked, which by the copolymer contained at least diunsaturated Monomers C is achieved. Suitable monomers C are, for example, N, N-methylenebisacrylamide, Ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate and divinylbenzene, as well as mixtures of these substances. The cross-linking with N, N'-methylene is preferred for the purposes of the invention.

Of the Amount of the / the monomer C is preferably between 1 and 7, and more preferably between 2 and 4 wt .-%, based on the total weight of monomers A and B in the copolymer.

The Copolymers of the invention are cationic. For the purposes of the invention is to be understood as meaning that the polymer skeleton, d. H. without consideration present counterions Y, a total of positive charge. It is not excluded that anionic or anionizable in the polymer backbone Groups such as e.g. Carboxylate or carboxyl groups are present, as long as the polymer backbone overall is positively charged. According to the invention, however, preference is given to copolymers, in the polymer backbone do not carry any anionic or anionizable groups. Particularly according to the invention preferred are copolymers of the above-described formula (I), which exclusively consist of the monomers A, B and C.

The Preparation of the Copolymers of the Invention is carried out by methods which are known per se to those skilled in the art.

Preferably are the copolymers of the invention available, by mixing the monomers on which the copolymer is based in one solvent or emulsion polymerization polymerized together. It will the crosslinking expediently caused by that one the monomers to be polymerized, a suitable amount of a polyfunctional Monomers C added.

When Emulsifiers for the preparation of the copolymers according to the invention by a Emulsion polymerization are, for example, anionic surfactants such as sodium dodecyl sulfate or alkylaryl polyglycol ether sulfate sodium salt.

The Emulsion polymerization is preferably carried out in water as a dispersing agent carried out.

When Each polymerization initiator is for such an emulsion polymerization suitable initiator, but preferably water-soluble initiators such as potassium peroxodisulfate used.

The Reaction mixture obtained in the emulsion polymerization can be further purified in a conventional manner. That's the way it works be freed, for example by dialysis of residual monomers, and by centrifugation, filtration, freeze drying or spray drying the water content can be reduced to a desired extent or the copolymers are obtained in the anhydrous state.

in the Under the present invention, it has been found that the previously described copolymers of the invention outstanding to improve the physical properties of keratin Fibers are suitable.

The Copolymers of the invention show hair-stabilizing, hair-firming properties when applied to hair as well as hair styling properties without causing negative influences the grip, the shine and the volume of the hair comes. In addition are the copolymers with conventional Hair detergent formulations generally well tolerated, even if they contain anionic surfactants.

Thereby the copolymers of the invention are suitable especially for the formulation of hair treatment products, in addition to a hair cleansing at the same time a conditioning and a consolidation effect the hair, so that three effects in a single formulation unite.

One Another object of the invention is thus the use of the foregoing copolymers of the invention described to improve the physical properties of keratin Fibers.

Under Keratin fibers are according to the invention furs, skins, wool, feathers, Hair and especially human hair to understand.

Under an improvement in the physical properties keratinischer Fibers is in the context of the invention, in particular a styling and / or to understand a conditioning of hair. Hair styling means the in-molding of hair. In the sense of the invention it means in particular, an improvement in strengthening after blowing, the Hairstyle case, neck volume, volume, modeling ability during the Drying and / or improved fit of the hairstyle.

Under Conditioning is in the context of the invention in particular an increase in Wet and dry combing, an improvement of the grip of dry and wet hair and to understand the shine of keratinous fibers.

Also The invention relates to an agent for the treatment of keratinischer Fibers, the at least one of the cationic crosslinked invention Contains copolymers.

Preferably it is a cosmetic hair treatment product, the one physiologically compatible carrier includes.

The type of hair treatment compositions according to the invention is not subject to any fundamental restrictions. It may, for example, to cleansing agents such as shampoos, conditioning agents such as conditioners, hair treatments and hair conditioners, strengthening agents such as hair setting, hair sprays and hair drier, permanent Deformation agents such as perming and fixing agents, color-modifying agents such as bleaching, oxidation colorants and toning agents based on direct dyes, hair lotions and hair tip fluids act. Accordingly, the formulations may be formulated as solutions, emulsions, gels, creams, aerosols or lotions. Furthermore, the hair treatment compositions according to the invention can be both rinse-off and leave-on products. The use of the copolymers according to the invention in rinse-off products is preferred. These are agents in which rinsing out of the active ingredients after the desired exposure time with water or at least predominantly water-containing agent is provided. The contact time with the hair is usually short, but may be up to 20 minutes beispilesweise.

According to the invention preferred Hair treatment agents are conditioning hair treatment agents, in particular conditioning hair rinses, and firming hair treatment preparations, in particular firming Hair shampoos, hair conditioners, hair tonics and hair foams.

The agents according to the invention contain at least one copolymer according to the invention from 0.01 to 10, but especially 0.1 to 5 wt .-%, based on the total weight of the agent.

In a further preferred embodiment contain the agents of the invention 0.01 to 30, but especially 0.01 to 20 wt .-%, based on the Total weight of the agent, at least one surfactant, particularly preferred an anionic surfactant.

Under the term surfactants is understood to mean surface-active substances, which carry an anionic or cationic charge in the molecule. Likewise, in the molecule both an anionic and a cationic charge may be present. These zwitterionic or amphoteric surface-active substances can also be used according to the invention be used. Furthermore you can the surface active Substances also be non-ionic.

• – lineare und verzweigte Fettsäuren mit 8 bis 30 C-Atomen (Seifen),
• – Ethercarbonsäuren der Formel R-O-(CH₂-CH₂O)_x-CH₂-COOH, in der R eine lineare Alkylgruppe mit 8 bis 30 C-Atomen und x = 0 oder 1 bis 16 ist,
• – Acylsarcoside mit 8 bis 24 C-Atomen in der Acylgruppe,
• – Acyltauride mit 8 bis 24 C-Atomen in der Acylgruppe,
• – Acylisethionate mit 8 bis 24 C-Atomen in der Acylgruppe,
• – Sulfobernsteinsäuremono- und -dialkylester mit 8 bis 24 C-Atomen in der Alkylgruppe und Sulfobernsteinsäuremono-alkylpolyoxyethylester mit 8 bis 24 C-Atomen in der Alkylgruppe und 1 bis 6 Oxyethylgruppen,
• – lineare Alkansulfonate mit 8 bis 24 C-Atomen,
• – lineare Alpha-Olefinsulfonate mit 8 bis 24 C-Atomen,
• – Alpha-Sulfofettsäuremethylester von Fettsäuren mit 8 bis 30 C-Atomen,
• – Alkylsulfate und Alkylpolyglykolethersulfate der Formel R-O(CH₂-CH₂O)_x-OSO₃H, in der R eine bevorzugt lineare Alkylgruppe mit 8 bis 30 C-Atomen und x = 0 oder 1 bis 12 ist,
• – Gemische oberflächenaktiver Hydroxysulfonate gemäß DE-A-37 25 030,
• – sulfatierte Hydroxyalkylpolyethylen- und/oder Hydroxyalkylenpropylenglykolether gemäß DE-A-37 23 354,
• – Sulfonate ungesättigter Fettsäuren mit 8 bis 24 C-Atomen und 1 bis 6 Doppelbindungen gemäß DE-A-39 26 344,
• – Ester der Weinsäure und Zitronensäure mit Alkoholen, die Anlagerungsprodukte von etwa 2-15 Molekülen Ethylenoxid und/oder Propylenoxid an Fettalkohole mit 8 bis 22 C-Atomen darstellen,
• – Alkyl- und/oder Alkenyletherphosphate der Formel (I)
  
  in der R bevorzugt für einen aliphatischen Kohlenwasserstoffrest mit 8 bis 30 Kohlenstoffatomen, R² für Wasserstoff, einen Rest (CH₂CH₂O)_nR¹ oder X, n für Zahlen von 1 bis 10 und X für Wasserstoff, ein Alkali- oder Erdalkalimetall oder NR³R⁴R⁵R⁶, mit R³ bis R⁶ unabhängig voneinander stehend für einen C₁ bis C₄- Kohlenwasserstoffrest, steht,
• – sulfatierte Fettsäurealkylenglykolester der Formel (II) R⁷CO(AlkO)_nSO₃M (II)in der R⁷CO- für einen linearen oder verzweigten, aliphatischen, gesättigten und/oder ungesättigten Acylrest mit 6 bis 22 C-Atomen, Alk für CH₂CH₂, CHCH₃CH₂ und/oder CH₂CHCH₃, n für Zahlen von 0,5 bis 5 und M für ein Kation steht, wie sie in der DE-OS 197 36 906.5 beschrieben sind,
• – Monoglyceridsulfate und Monoglyceridethersulfate der Formel (III),
  
  in der R⁸CO für einen linearen oder verzweigten Acylrest mit 6 bis 22 Kohlenstoffatomen, x, y und z in Summe für 0 oder für Zahlen von 1 bis 30, vorzugsweise 2 bis 10, und X für ein Alkali- oder Erdalkalimetall steht. Typische Beispiele für im Sinne der Erfindung geeignete Monoglycerid(ether)sulfate sind die Umsetzungsprodukte von Laurinsäuremonoglycerid, Kokosfettsäuremonoglycerid, Palmitinsäuremonoglycerid, Stearinsäuremonoglycerid, Ölsäuremonoglycerid und Talgfettsäuremonoglycerid sowie deren Ethylenoxidaddukte mit Schwefeltrioxid oder Chlorsulfonsäure in Form ihrer Natriumsalze. Vorzugsweise werden Monoglyceridsulfate der Formel (III) eingesetzt, in der R⁸CO für einen linearen Acylrest mit 8 bis 18 Kohlenstoffatomen steht. Monoglyceridsulfate und Monoglyceridethersulfate werden beispielsweise in der EP-B1 0 561 825, der EP-B1 0 561 999, der DE-A1 42 04 700 oder von A.K.Biswas et al. in J.Am.Oil.Chem.Soc. 37, 171 (1960) und F.U.Ahmed in J.Am.Oil.Chem.Soc. 67, 8 (1990) beschrieben.

Suitable anionic surfactants in compositions according to the invention are all anionic surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. As a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 8 to 30 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts having 2 to 4 C atoms in the alkanol group,

• - linear and branched fatty acids with 8 to 30 carbon atoms (soaps),
• Ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group having 8 to 30 C atoms and x = 0 or 1 to 16,
• Acylsarcosides having 8 to 24 C atoms in the acyl group,
• Acyltaurides having 8 to 24 carbon atoms in the acyl group,
• Acyl isethionates having 8 to 24 C atoms in the acyl group,
• Sulfosuccinic acid mono- and dialkyl esters having 8 to 24 C atoms in the alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl esters having 8 to 24 C atoms in the alkyl group and 1 to 6 oxyethyl groups,
• - linear alkanesulfonates having 8 to 24 carbon atoms,
• - linear alpha-olefin sulfonates having 8 to 24 carbon atoms,
• Alpha-sulfofatty acid methyl esters of fatty acids having 8 to 30 C atoms,
• Alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (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,
• Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030,
• Sulfated hydroxyalkylpolyethylene and / or hydroxyalkylene-propylene glycol ethers according to DE-A-37 23 354,
• Sulfonates of unsaturated fatty acids having 8 to 24 C atoms and 1 to 6 double bonds according to DE-A-39 26 344,
• Esters of tartaric acid and citric acid with alcohols which are adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols containing 8 to 22 carbon atoms,
• Alkyl and / or alkenyl ether phosphates of the formula (I)
  
  in the R preferred for an aliphatic hydrocarbon radical having 8 to 30 carbon atoms, R ^{2 is} hydrogen, a radical (CH ₂ CH ₂ O) _n R ¹ 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 are each independently a C ₁ to C ₄ hydrocarbon radical,
• Sulfated fatty acid alkylene glycol esters of the formula (II) R ⁷ CO (AlkO) _n SO ₃ M (II) in the R ⁷ CO- for a linear or branched, aliphatic, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, Alk for CH ₂ CH ₂ , CHCH ₃ CH ₂ and / or CH ₂ CHCH ₃ , n for numbers from 0.5 to 5 and M is a cation, as described in DE-OS 197 36 906.5,
• Monoglyceride sulphates and monoglyceride ether sulphates of the formula (III),
  
  in which 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, and X is an alkali or alkaline earth metal. Typical examples of 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. Preferably, monoglyceride sulfates of the formula (III) are used, in which R ⁸ CO is a linear acyl radical having 8 to 18 carbon atoms. Monoglyceride sulfates and monoglyceride ether sulfates are described for example in EP-B1 0 561 825, EP-B1 0 561 999, DE-A1 42 04 700 or AKBiswas et al. in J.Am.Oil. Chem. Soc. 37, 171 (1960) and FUAhmed in J.Am.Oil.Chem.Soc. 67, 8 (1990).

preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 C atoms in the alkyl group and up to 12 glycol ether groups in the molecule and sulfosuccinic acid mono- and -dialkylester having 8 to 18 C-atoms in the alkyl group and sulfosuccinic monoalkylpolyoxyethylester with 8 to 18 C atoms in the alkyl group and 1 to 6 oxyethyl groups.

Zwitterionic surfactants are those surface-active compounds which carry in the molecule at least one quaternary ammonium group and at least one -COO ^(-) or -SO ₃ ^(-) group. Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyl dimethylammonium glycinate, N-acylaminopropyl N, N-dimethylammonium glycinates, for example cocoacylaminopropyl-dimethylammonium glycinate, and 2-alkyl 3-carboxymethyl-3-hydroxyethyl-imidazolines having in each case 8 to 18 carbon atoms in the alkyl or acyl group and the Kokosacylaminoethylhydroxyethylcarboxymethylglycinat. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.

Ampholytic surfactants are understood as meaning those surface-active compounds which, in addition to a C ₈ -C ₂₄ -alkyl or -acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO ₃ H group and are capable of forming internal salts , Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 24 C Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C ₁₂ -C ₁₈ acylsarcosine.

• – Anlagerungsprodukte von 2 bis 50 Mol Ethylenoxid und/oder 0 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-C₆-Alkylrest endgruppenverschlossene Anlagerungsprodukte von 2 bis 50 Mol Ethylenoxid und/oder 0 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, wie beispielsweise die unter den Verkaufsbezeichnungen Dehydol^® LS, Dehydol^® LT (Cognis) erhältlichen Typen,
• – 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, wie beispielsweise das Handelsprodukt Hydagen^® HSP (Cognis) oder Sovermol – Typen (Cognis),
• – alkoxilierte Triglyceride,
• – alkoxilierte Fettsäurealkylester der Formel R⁹CO-(OCH₂CHR¹⁰)_wOR¹¹, in der R⁹CO für einen linearen oder verzweigten, gesättigten und/oder ungesättigten Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹⁰ für Wasserstoff oder Methyl, R¹¹ für lineare oder verzweigte Alkylreste mit 1 bis 4 Kohlenstoffatomen und w für Zahlen von 1 bis 20 steht,
• – Aminoxide,
• – Hydroxymischether, wie sie beipielsweise in der DE-OS 19738866 beschrieben sind,
• – 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,
• – Fettsäure-N-alkylglucamide,
• – Alkylpolygykoside entsprechend der allgemeinen Formel RO-(Z)_x wobei R für Alkyl, Z für Zucker sowie x für die Anzahl der Zuckereinheiten steht. Die erfindungsgemäß verwendbaren Alkylpolyglykoside können lediglich einen bestimmten Alkylrest R enthalten. Üblicherweise werden diese Verbindungen aber ausgehend von natürlichen Fetten und ölen oder Mineralölen hergestellt. In diesem Fall liegen als Alkylreste R Mischungen entsprechend den Ausgangsverbindungen bzw. entsprechend der jeweiligen Aufarbeitung dieser Verbindungen vor.

Nonionic surfactants contain as hydrophilic group z. A polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups. Such compounds are, for example

• - Addition products of 2 to 50 moles of ethylene oxide and / or 0 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 -C ₆ -alkyl radical endgruppenverschlossene addition products of 2 to 50 mol Ethylene oxide and / or 0 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, such as those sales names Dehydrol® ^® LS, Dehydrol® ^® LT (Cognis) types,
• 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, such as the commercially available product ^® Hydagen HSP (Cognis) or Sovermol - types (Cognis),
• - alkoxylated triglycerides,
• Alkoxylated fatty acid alkyl esters of the formula R ⁹ CO- (OCH ₂ CHR ¹⁰ ) _w OR ¹¹ in which R ^{9 is} CO for a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R ^{10 is} hydrogen or methyl, R ^{11 is a} linear or branched alkyl radical having 1 to 4 carbon atoms and w is a number from 1 to 20,
• - amine oxides,
• Hydroxymix ethers, as described for example in DE-OS 19738866,
• 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,
• Fatty acid N-alkylglucamides,
• - Alkylpolygykoside according to the general formula RO- (Z) _x wherein R is alkyl, Z is sugar and x is the number of sugar units. The alkyl polyglycosides which can be used according to the invention can only contain one particular alkyl radical R. Usually, however, these compounds are prepared starting from natural fats and oils or mineral oils. In this case, the alkyl radicals R are mixtures corresponding to the starting compounds or corresponding to the particular work-up of these compounds.

• – im wesentlichen aus C₈- und C₁₀-Alkylgruppen,
• – im wesentlichen aus C₁₂- und C₁₄-Alkylgruppen,
• – im wesentlichen aus C₈- bis C₁₆-Alkylgruppen oder
• – im wesentlichen aus C₁₂- bis C₁₆-Alkylgruppen oder
• – im wesentlichen aus C₁₆ bis C₁₈-Alkylgruppen besteht.

Particularly preferred are those alkyl polyglycosides in which R

• Consisting essentially of C ₈ and C ₁₀ -alkyl groups,
• Essentially of C ₁₂ and C ₁₄ alkyl groups,
• - Essentially from C ₈ - to C ₁₆ alkyl groups or
• - Essentially from C ₁₂ - to C ₁₆ alkyl groups or
• - Consists essentially of C ₁₆ to C ₁₈ alkyl groups.

When Sugar component Z can any mono- or oligosaccharides are used. Usually Sugar with 5 or 6 carbon atoms and the corresponding oligosaccharides used. Such sugars are, for example, glucose, fructose, Galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, Gulose, idose, talose and sucrose. Preferred sugar building blocks are Glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.

The usable according to the invention Alkyl polyglycosides contain on average from 1.1 to 5 sugar units. Alkyl polyglycosides having x values of 1.1 to 2.0 are preferred. Very particular preference is given to alkyl glycosides in which x 1.1 to 1.8.

Also The alkoxylated homologs of said alkyl polyglycosides can be used according to the invention become. These homologs can an average of up to 10 ethylene oxide and / or propylene oxide units per alkyl glycoside unit.

When preferred nonionic surfactants are the alkylene oxide addition products to saturated linear Fatty alcohols and fatty acids with in each case 2 to 30 moles of ethylene oxide per mole of fatty alcohol or fatty acid. Preparations with excellent properties will also be obtained when they are fatty acid esters as nonionic surfactants of ethoxylated glycerol.

These Connections are identified by the following parameters. The alkyl radical R contains 6 to 22 carbon atoms and can be both linear and branched be. Preference is given to primary linear and methyl-branched in the 2-position aliphatic radicals. Such Examples of alkyl radicals are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. Particularly preferred are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl. When using so-called "oxo-alcohols" as starting materials, compounds predominate an odd number of carbon atoms in the alkyl chain.

at it may be the compounds with alkyl groups used as surfactant each are uniform substances. It is, however, in usually preferred in the preparation of these substances by native vegetable or animal raw materials, so that you substance mixtures obtained with different, depending on the raw material alkyl chain lengths.

at the surfactants, the adducts of ethylene and / or propylene oxide represent fatty alcohols or derivatives of these addition products, can both products with a "normal" homolog distribution as well as those with a narrow homolog distribution become. Under "normal" homolog distribution are understood to mean mixtures of homologs which are used in the Reaction of fatty alcohol and alkylene oxide using alkali metals, Alkali metal hydroxides or alkali metal alcoholates as catalysts receives. Narrowed homolog distributions are obtained when, for example Hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with narrow homolog distribution may be preferred.

In a preferred embodiment can nonionic, zwitterionic and / or amphoteric surfactants as well their mixtures are preferred.

Usable according to the invention are also cationic surfactants of the quaternary ammonium type, the esterquats and the amidoamines. Preferred quaternary ammonium compounds are ammonium halides, especially chlorides and bromides, such as Alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltri methylammonium chloride, Stearyltrimethylammonium chloride, distearyldimethylammonium chloride, Lauryldimethylammonium chloride, Lauryldimethylbenzylammoniumchlorid and Tricetylmethylammoniumchlorid, as well as those under the INCI names Quaternium-27 and quaternium-83 known imidazolium compounds. The long alkyl chains The above-mentioned surfactants preferably have 10 to 18 carbon atoms on.

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. Such products are marketed under the trade names Stepantex® ^{®, ®} and Dehyquart® Armocare® ^®. The products Armocare ^® VGH-70, a N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, as well as Dehyquart ^® F-75, Dehyquart ^® C-4046, Dehyquart ^® L80 and Dehyquart ^® AU-35 are examples of such esterquats.

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 is that available under the name Tegoamid ^® S 18 commercially stearamidopropyl dimethylamine.

In a preferred embodiment of the invention an inventive agent as anionic surfactant, an alkyl sulfate or alkyl polyglycol ether sulfate, as alkylpolyglycol ether sulfate, the sodium salt of two- or tri-ethoxylated lauryl or myristyl alcohol is particularly preferred is.

ever in the manner of the agent and the surfactant, the preferably anionic Surfactants in amounts of about 0.1 to about 30 wt.%, Preferably about From 1 to about 20 weight percent, and most preferably from about 5 to about 15 wt.%, Based on the total agent to be included.

Farther can the agents according to the invention still a natural one Emulsifier included. Preferred natural emulsifiers are phospholipids, in particular lecithin, saponins, bile acids and their derivatives, in particular cholic, deoxycholic, lithocholic and taurocholic acid, tannic acid and tertiary acid. Phospholipids and saponins are preferred natural emulsifiers.

The agents according to the invention can furthermore contain at least one fatty substance or one wax.

Preferred fatty substances are linear and branched, saturated and unsaturated fatty alcohols or fatty alcohol mixtures based on natural raw materials having 8 to 22 carbon atoms in the alkyl chain such as decanol, octanol, octenol, dodecenol, decenol, octadienol, dodecadienol, decadienol, oleyl alcohol, erucalcohol, ricinoleic alcohol, stearyl alcohol , Isostearyl alcohol, cetyl alcohol, lauryl alcohol, myristyl alcohol, arachidyl alcohol, capryl alcohol, capric alcohol, linoleyl alcohol, linolenyl alcohol and behenyl alcohol, as well as their Guerbet alcohols and fatty alcohol cuts, which are produced by reducing naturally occurring triglycerides such as beef tallow, palm oil, peanut oil, rapeseed oil, cottonseed oil, soybean oil, sunflower oil and linseed oil or from their transesterification products with corresponding alcohols resulting fatty acid esters and thus represent a mixture of different fatty alcohols. Monoesters of fatty acids with alcohols having 6 to 24 carbon atoms and triglycerides of natural origin can likewise be used as fatty substances.

Likewise Suitable as fatty substances are paraffin oils and vegetable oils such as jojoba oil, sunflower oil, orange oil, almond oil, wheat germ oil, peach kernel oil, henna oil from Lawsonia inermis as well as oil from Cassia auriculata.

fatty substances In the context of the invention, furthermore, silicone oils, in particular dialkyl and alkylaryl siloxanes, such as dimethylpolysiloxane and methylphenylpolysiloxane, and their alkoxylated and quaternized analogs. Examples of such Silicones are those of Dow Corning under the designations DC 190, DC 200, DC 344, DC 345 and DC 1401 distributed products.

• • pflanzliche Wachse, wie Candelillawachs, Carnaubawachs, Japanwachs, Espartograswachs, Korkwachs, Guarumawachs, Reiskeimölwachs, Zuckerrohrwachs, Ouricurywachs und Montanwachs,
• • tierische Wachse wie Bienenwachs, Schellackwachs, Walrat, Lanolin und Bürzelfett,
• • Mineralwachse wie Ceresin und Ozokerit
• • Petrochemische Wachse wie Petrolatum, Paraffinwachse und Mikrowachse,
• • Hartwachse wie Montanesterwachse, Sasolwachse und hydrierte Jojobawachse, sowie
• • Polyalkylenwachse und Polyethylenglykolwachse.

By definition, waxes are esters of long-chain fatty acids with long-chain fatty alcohols. Both natural waxes, chemically modified waxes and synthetic waxes can be used according to the invention. Examples of such waxes are

• Vegetable waxes such as candelilla wax, carnauba wax, japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugarcane wax, ouricury wax and montan wax,
• • animal waxes such as beeswax, shellac wax, spermaceti, lanolin and cudgel fat,
• • Mineral waxes such as ceresin and ozokerite
• Petrochemical waxes such as petrolatum, paraffin waxes and microwaxes,
• • Hard waxes such as montan ester waxes, Sasol waxes and hydrogenated jojoba waxes, as well
• • Polyalkylene waxes and polyethylene glycol waxes.

According to the invention preferred Waxes are vegetable waxes like candelilla wax, carnauba wax and Japan wax and beeswax.

The Fats or waxes usually become in amounts of from 0.01 to 15% by weight, preferably from 0.1 to 10% by weight and particularly preferably from 0.3 to 6 wt .-%, based on the total Medium, used. For special means may be the amount of fat but also up to 90 Wt .-% amount.

Farther can the agents according to the invention contain at least one protein hydrolyzate or a derivative thereof. Protein hydrolysates are product mixtures that are acidic, basic or enzymatically catalyzed degradation of proteins (proteins) become.

According to the invention, protein hydrolysates be used both of plant and animal origin.

Animal protein hydrolysates are, for example, elastin, collagen, keratin, silk and milk protein protein hydrolysates, which may also be present in the form of salts. Such products are, for example, under the trademarks Dehylan ^® (Cognis), Promois® ^© (Interorgana) Collapuron ^® (Cognis), Nutrilan® ^® (Cognis), Gelita-Sol ^® (German Gelatinefabriken Stoess & Co), Lexein ^® (Inolex) and kerasol tm ^® (Croda) sold.

Preferred according to the invention is the use of protein hydrolysates of plant origin, eg. Soybean, almond, rice, pea, potato and wheat protein hydrolysates. Such products are obtainable, for example, under the trademarks Gluadin ^® (Cognis), diamine ^® (Diamalt) ^® (Inolex) and Crotein ^® (Croda).

Although the use of the protein hydrolysates is preferred as such, amino acid mixtures or individual amino acids obtained otherwise, such as, for example, arginine, lysine, histidine or pyrroglutamic acid, may also be used in their place. Also possible is the use of derivatives of protein hydrolysates, for example in the form of their fatty acid condensation products. Such products are sold for example under the names Lamepon ^® (Cognis), Gluadin ^® (Cognis), Lexein ^® (Inolex), Crolastin ^® (Croda) or Crotein ^® (Croda).

Cationized protein hydrolysates can also be used according to the invention, the protein hydrolyzate on which the animal is based, for example from collagen, milk or keratin, from the plant, for example from wheat, maize, rice, potatoes, soy or almonds, from marine life forms, for example from fish collages or algae , or from biotechnologically derived protein hydrolysates, can originate. The protein hydrolyzates on which the cationic derivatives according to the invention are based can be obtained from the corresponding proteins by chemical, in particular alkaline or acid hydrolysis, by enzymatic hydrolysis and / or a combination of both types of hydrolysis. The hydrolysis of proteins usually results in a protein hydrolyzate having a molecular weight distribution of about 100 daltons up to several thousand daltons. Preference is given to those cationic protein hydrolyzates whose underlying protein content has a molecular weight of 100 to 25,000 daltons, preferably 250 to 5000 daltons. Furthermore, cationic protein hydrolyzates are to be understood as meaning quaternized amino acids and mixtures thereof. The quaternization of the protein hydrolyzates or amino acids is often carried out using quaternary ammonium salts such as N, N-dimethyl-N- (n-alkyl) -N- (2-hydroxy-3-chloro-n-propyl) ammonium halides. Furthermore, the cationic protein hydrolysates may also be further derivatized. As typical examples of the cationic protein hydrolysates and derivatives according to the invention, those mentioned under the INCI names in the "International Cosmetic Ingredient Dictionary and Handbook", (seventh edition 1997, The Cosmetic, Toiletry, and Fragrance Association 1101 17 ^th Street, NW, Suite 300 Cocodimonium Hydroxypropyl Hydrolyzed Casein, Cocodimonium Hydroxypropyl Hydrolyzed Collagen, Cocodimonium Hydroxypropyl Hydrolyzed Collagen, Cocodimonium Hydroxypropyl Hydrolyzed Hair Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Rice Protein, Cocodimonium Hydroxypropyl Hydrolyzed Silk, Cocodimonium Hydroxypropyl Hydrolyzed Soy Protein, Cocodimonium Hydroxypropyl Hydrolyzed Wheat Protein, Cocodimonium Hydroxypropyl Silk Amino Acids, Hydroxypropyl Arginine Lauryl / Myristyl Ether HCl, Hydroxypropyltrimonium Gelatin, Hydroxypropyltrimonium Hydrolyzed Cas Hydroxypropyltrimonium Hydrolyzed Collagen, Hydroxypropyltrimonium Hydrolyzed Conchiolin Protein, Hydroxypropyltrimonium Hydrolyzed Keratin, Hydroxypropyltrimonium Hydrolyzed Rice Bran Protein, Hydroxypropyltrimonium Hydrolyzed Silk, Hydroxypropyltrimonium Hydrolyzed Soy Protein, Hydroxypropyl Hydrolyzed Vegetable Protein, Hydroxypropyltrimonium Hydrolyzed Wheat Protein, Hydroxypropyltrimonium Hydrolyzed Wheat Protein / Siloxysilicate, Laurdimonium Hydroxypropyl Hydrolyzed Soy Protein, Lauridimonium Hydroxypropyl Hydrolyzed Wheat Protein, Laurydimium Hydroxypropyl Hydrolyzed Wheat Protein / Siloxysilicate, Lauryldimonium Hydroxypropyl Hydrolyzed Casein, Lauryldimonium Hydroxypropyl Hydrolyzed Collagen, Lauryldimonium Hydroxypropyl Hydrolyzed Keratin, Lauryldimonium Hydroxypropyl Hydrolyzed Silk, Lauryldimonium Hydroxypropyl Hydrolyzed Soy Protein, Steardimonium Hydroxypropyl Hydrolyzed Casein, Steardimonium Hydroxypropyl Hydrolyzed Collagen, Steardimonium Hydroxypropyl Hydrolyzed Kera Steardimonium Hydroxypropyl Hydrolyzed Rice Protein, Steardimonium Hydroxypropyl Hydrolyzed Silk, Steardimonium Hydroxypropyl Hydrolyzed Soy Protein, Steardimonium Hydroxypropyl Hydrolyzed Vegetable Protein, Steardimonium Hydroxypropyl Hydrolyzed Wheat Protein, Steardimonium Hydroxyethyl Hydrolyzed Collagen, Quaternium-76 Hydrolyzed Collagen, Quaternium-79 Hydrolyzed Collagen, Quaternium 79 Hydrolyzed Keratin, Quaternium-79 Hydrolyzed Milk Protein, Quaternium-79 Hydrolyzed Silk, Quaternium-79 Hydrolyzed Soy Protein, Quaternium-79 Hydrolyzed Wheat Protein. Very particular preference is given to the cationic protein hydrolysates and derivatives based on plants.

In the agents according to the invention can the protein hydrolysates and their derivatives in amounts of 0.01 to Be contained 10 wt .-% based on the total agent. amounts from 0.1 to 5% by weight, in particular from 0.1 to 3% by weight, are very particular prefers.

Farther can the agents according to the invention a conditioning agent selected from the group consisting of cationic surfactants, cationic polymers, alkylamidoamines and synthetic oils is formed.

• – quaternisierte Cellulose-Derivate, wie sie unter den Bezeichnungen Celquat^® und Polymer JR^® im Handel erhältlich sind. Die Verbindungen Celquat^® H 100, Celquat^® L 200 und Polymer JR^®400 sind bevorzugte quaternierte Cellulose-Derivate.
• – polymere Dimethyldiallylammoniumsalze und deren Copolymere mit Estern und Amiden von Acrylsäure und Methacrylsäure. Die unter den Bezeichnungen Merquat^®100 (Poly(dimethyldiallylammoniumchlorid)) und Merquat^®550 (Dimethyldiallylammoniumchlorid-Acrylamid-Copolymer) im Handel erhältlichen Produkte sind Beispiele für solche kationischen Polymere.
• – Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoacrylats- und -methacrylats, wie beispielsweise mit Diethylsulfat quaternierte Vinylpyrrolidon-Dimethylaminomethacrylat-Copolymere. Solche Verbindungen sind unter den Bezeichnungen Gafquat^®734 und Gafquat^®755 im Handel erhältlich.
• – Vinylpyrrolidon-Methoimidazoliniumchlorid-Copolymere, wie sie unter der Bezeichnung Luviquat^® angeboten werden.
• – quaternierter Polyvinylalkohol sowie die unter den Bezeichnungen
• – Polyquaternium 2,
• – Polyquaternium 17,
• – Polyquaternium 18 und
• – Polyquaternium 27 bekannten Polymeren mit quartären Stickstoffatomen in der Polymerhauptkette.

As conditioning agents, cationic polymers may be preferred. These are usually polymers containing a quaternary nitrogen atom, for example in the form of an ammonium group. Preferred cationic polymers are, for example

• - Quaternized cellulose derivatives, such as those under the names Celquat ^® and Polymer JR ^® commercially available. The compounds Celquat ^® H 100, Celquat L 200 and Polymer JR ^{® ®} 400 are preferred quaternized cellulose derivatives.
• - Dimethyldiallylammoniumsalze polymeric and their copolymers with esters and amides of acrylic acid and methacrylic acid. The products sold under the names Merquat ^® 100 (Poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) are examples of such cationic polymers.
• - Copolymers of vinylpyrrolidone with quaternized derivatives of Dialkylaminoacrylats- and -methacrylats, such as diethyl sulfate quaternized vinylpyrrolidone-dimethylaminomethacrylate copolymers. Such compounds are sold under the names Gafquat ^® 734 and Gafquat ^® 755 commercially.
• - Vinylpyrrolidone-Methoimidazoliniumchlorid copolymers, such as those offered under the name Luviquat ^® .
• - Quaternized polyvinyl alcohol and those under the names
• - Polyquaternium 2,
• - Polyquaternium 17,
• - Polyquaternium 18 and
• Polyquaternium 27 known polymers with quaternary nitrogen atoms in the polymer main chain.

Especially preferred are cationic polymers of the first four groups.

preferred cationic surfactants are those of the quaternary ammonium type, for example, ammonium halides, especially chlorides and bromides, such as alkyltrimethylammonium chlorides, Dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, z. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, Distearyldimethylammonium chloride, lauryldimethylammonium chloride, Lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, Behenyltrimethylammonium methosulfate, as well as those under the INCI names Quaternium-27 and quaternium-83 known imidazolium compounds.

In particular, for environmental reasons these quaternary ammonium compounds can also be so-called esterquats such as N obtainable under the name Armocare® ^® VGH-70 commercially, N-bis (2-palmitoyloxyethyl) dimethyl be used instead.

Another, also particularly interesting for ecological reasons group of conditioning agents are Alkylamidoamine as stearamidopropyl obtainable under the name Tegoamid ^® S 18 in the trade.

Also suitable as conditioning active ingredients are silicone oils, in particular dialkyl and alkylaryl siloxanes, for example dimethylpolysiloxane and methylphenylpolysiloxane, and also their alkoxylated and quaternized analogs. Examples of such silicones are the products marketed by Dow Corning under the designations DC 190, DC 200, DC 344, DC 345 and DC 1401 and the commercial products Q2-7224 (manufacturer: Dow Corning, a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion ( containing a hydroxylamino-modified silicone which is also known as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th Goldschmidt; diquaternary polydimethylsiloxanes. , Quaternium-80).

Also can be used as conditioning agents are paraffin oils as well vegetable oils like jojoba oil, Sunflower oil, Orange oil, Almond oil, Wheat germ oil and peach kernel oil.

Likewise suitable hair conditioning compounds are phospholipids, for example soya lecithin, egg lecithin and cephaline.

In the agents according to the invention can the conditioning agents in amounts of about 0.01 to about Be contained 10 wt .-% based on the total agent. amounts from about 0.1 to about 5 weight percent, more preferably from about 0.1 to about 3 Wt .-%, are very particularly preferred.

Compositions according to the invention, the hair dyeing or tinting agent can represent at least one developer-type oxidation dye precursor, optionally in combination with coupler type oxidation dye precursors, and / or a direct dye and / or one in nature occurring dye included.

In a further embodiment can the agents according to the invention, if necessary in addition, to serve permanent deformation of human hair.

A permanent hair deformation is carried out according to the known perm process in such a way that the hair is mechanically deformed and the deformation z. B. by winding on hair winder or Papilloten sets. Before and / or after this deformation, the hair is treated with the aqueous preparation of a keratin-reducing substance and rinsed after a contact time with water or an aqueous solution. In a second step, the hair is then treated with the aqueous preparation of an oxidizing agent. After a period of action, this is also rinsed out of the hair and the hair from the mechanical deformation aids (winder, papillots) freed.

The aqueous preparation of the keratin reducing agent is usually alkaline, so that the hair swells and in this way a deep penetration the keratin-reducing substance is allowed into the hair. The keratin-reducing substance cleaves some of the disulfide bonds keratin to -SH groups, causing a relaxation of the Peptide crosslinking and due to the tension of the hair by the mechanical Deformation comes to a reorientation of Keratingefüges. Under the influence of the oxidizing agent Again disulfide bonds are knotted, and in this way becomes the keratin paste Fixed anew in the given deformation.

The Copolymers of the invention can both in the keratin-reducing (corrugating) and in the Keratin oxidizing agents (fixing solution) of the permanent wave treatment be incorporated. Particularly preferred is the use of the polymers of the invention in fixative solutions.

When Waving agents today are almost exclusively alkaline (pH values from 8.5 to 9.5) solutions of thioglycolic acid or their salts or esters and also thiolactic acid, cysteamine, thiomalic acid or α-mercaptoethanesulfonic acid.

Mandatory component of the fixative are oxidizing agents, eg. As sodium bromate, potassium bromate, hydrogen peroxide, and the stabilizers customary for the stabilization of aqueous hydrogen peroxide preparations. The pH of such aqueous H ₂ O ₂ preparations, which usually contain about 0.5 to 3.0% by weight of H ₂ O ₂ , is preferably 2 to 4; it is adjusted by inorganic acids, preferably phosphoric acid. Bromate-based fixatives are usually used in concentrations of from 1 to 10% by weight and the pH of the solutions is adjusted to 4 to 7. Likewise suitable are enzymatic-based fixatives (peroxidases) which contain no or only small amounts of oxidizing agents, in particular H ₂ O ₂ .

Of the pH value of the agents according to the invention may in principle be between 2-11, the skilled person being the preferred pH ranges for knows the different means. The pH of the agents according to the invention, insofar as hair care products are concerned, preference is given to between 2 and 7, with values of 3 to 5 being particularly preferred. To adjustment This pH can be virtually any suitable for cosmetic purposes Acid used become. Usually are consumed acids used. Be under enjoyment of acids such acids understood that under the usual Food intake and positive effects to have the human organism. Acetic acids are, for example, acetic acid, lactic acid, tartaric acid, citric acid, malic acid, ascorbic acid and Gluconic. In the context of the invention is the use of citric acid and lactic acid particularly preferred. Hair Dye are preferably formulated in a pH range of about 7 to 11.

Farther can the agents according to the invention all for the usual purpose include customary additives. In particular, you can this cosmetic additives being a purifying, nurturing or otherwise external appearance hair changing Unfold their effect. Also such additives, which have no direct influence on the hair, but otherwise a positive effect on the scalp or, for example, the hair follicles unfold in the preparation according to the invention be included.

• – Anionische, zwitterionische, amphotere und nichtionische Polymere wie beispielsweise Vinylacetat/Crotonsäure-Copolymere, Polydimethylsiloxane, Vinylpyrrolidon/Vinylacrylat-Copolymere, Vinylacetat/Butylmaleat/Isobornylacrylat-Copolymere, Methylvinylether/Maleinsäureanhydrid-Copolymere und deren Ester, unvernetzte und mit Polyolen vernetzte Polyacrylsäuren, Acrylamidopropyl-trimethylammoniumchlorid/Acrylat-Copolymere, Octylacrylamid/-Methyl-methacrylat/tert.Butylaminoethylmethacrylat/2-Hydroxypropylmethacrylat-Copolymere, Polyvinylpyrrolidon, Vinylpyrrolidon/Vinylacetat-Copolymere, Vinylpyrrolidon/Dimethylaminoethylmethacrylat/Vinylcaprolactam-Terpolymere sowie gegebenfalls derivatisierte Celluloseether.
• – symmetrische und unsymmetrische, lineare und verzweigte Dialkylether mit insgesamt zwischen 12 bis 36 C-Atomen, insbesondere 12 bis 24 C-Atomen, beispielsweise Di-n-octylether, Di-n-decylether, Di-n-nonylether, Di-n-undecylether und 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,
• – Vaseline
• – Entschäumer wie Silikone,
• – Verdickungsmittel wie Gelatine oder Pflanzengumme, beispielsweise Agar-Agar, Guar-Gum, Alginate, Xanthan-Gum, Gummi arabicum, Karaya-Gummi, Johannisbrotkernmehl, Leinsamengummen, Dextrane, Cellulose-Derivate, z. B. Methylcellulose, Hydroxyalkylcellulose und Carboxymethylcellulose, Stärke-Fraktionen und Derivate wie Amylose, Amylopektin und Dextrine, Tone und Schichtsilikate wie z. B. Bentonit oder vollsynthetische Hydrokolloide wie z. B. Polyvinylalkohol, die Ca-, Mg- oder Zn – Seifen,
• – Rückfettungsmittel wie Fettsäurealkanolamide, Fettsäuren, Fettsäureester wie Isopropylmyristat, -palmitat, -oleat und -stearat, gegebenenfalls ethoxylierte Partialglyceride, Wollwachsderivate, Lecithin, Perhydrosqualen, Isopropyladipat oder die voranstehend beschriebenen Fettstoffe
• – Strukturanten wie Maleinsäure, Mono-, Di- und Oligosaccharide,
• – Parfümöle, Dimethylisosorbid und Cyclodextrine,
• – Lösungsvermittler, wie Ethanol, Isopropanol, Ethylenglykol, Propylenglykol, Glycerin und Diethylenglykol,
• – Farbstoffe zum Anfärben des Mittels,
• – Antischuppenwirkstoffe wie Piroctone Olamine, Zink Omadine und Climbazol,
• – weitere Substanzen zur Einstellung des pH-Wertes,
• – Vitamine und Vitaminvorstufen, wie Panthenol, dessen Derivate und Biotin,
• – Pflanzen- und Honigextrakte, wie insbesondere Extrakte aus Eichenrinden, Brennessel, Hamamelis, Hopfen, Kamille, Klettenwurzel, Schachtelhalm, Lindenblüten, Mandel, Aloe Vera, Kokosnuß, Mango, Aprikose, Limone, Weizen, Kiwi, Melone, Orange, Grapefruit, Salbei, Rosmarin, Birke, Wiesenschaumkraut, Quendel, Schafgarbe, Hauhechel, Meristem, Ginseng und Ingwerwurzel,
• – Weitere Wirkstoffe wie Ceramide, Allantoin, Pyrrolidoncarbonsäuren, und Bisabolol,
• – Lichtschutzmittel,
• – Konsistenzgeber wie Zuckerester, Polyolester oder Polyolalkylether,
• – Fettsäurealkanolamide,
• – physiologisch verträgliche anorganische oder organische Säuren,
• – Quell- und Penetrationsstoffe wie Glycerin, Propylenglykolmonoethylether, Carbonate, Hydrogencarbonate, Guanidine, Harnstoffe sowie primäre, sekundäre und tertiäre Phosphate,
• – Feuchthaltemittel wie Sorbit, Milchsäuresalze, Glycerin oder Polysaccharide
• – Trübungsmittel wie Latex, Styrol/PVP- und Styrol/Acrylamid-Copolymere,
• – Perlglanzmittel wie Ethylenglykolmono- und -distearat sowie PEG-3-distearat,
• – Komplexbildner wie EDTA, NTA, β-Alanindiessigsäure und Phosphonsäuren,
• – Reduktionsmittel wie z.B. Thioglykolsäure und deren Derivate, Thiomilchsäure, Cysteamin, Thioäpfelsäure und α-Mercaptoethansulfonsäure,
• – Oxidationsmittel wie Wasserstoffperoxid, Kaliumbromat und Natriumbromat,
• – Treibmittel wie Propan-Butan-Gemische, N₂O, Dimethylether, CO₂, N₂ und Luft sowie
• – Antioxidantien.

Further customary constituents of the agents according to the invention can be:

• - Anionic, zwitterionic, amphoteric and nonionic polymers such as vinyl acetate / crotonic acid copolymers, polydimethylsiloxanes, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and their esters, uncrosslinked and polyols crosslinked polyacrylic acids, acrylamidopropyl trimethyl ammonium chloride / acrylate copolymers, octyl acrylamide / methyl methacrylate / tert.butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, polyvinyl pyrrolidone, vinyl pyrrolidone / vinyl acetate copolymers, vinyl pyrrolidone / dimethylaminoethyl methacrylate / vinyl caprolactam terpolymers, and optionally derivatized cellulose ethers.
• Symmetrical and unsymmetrical, linear and branched dialkyl ethers having a total of from 12 to 36 carbon atoms, in particular 12 to 24 carbon atoms, for example di-n-octyl ether, di-n-decyl ether, di-n-nonyl ether, di-n- undecyl ether and di-n-dodecyl ether, n-hexyl n-octyl ether, n-octyl n-decyl ether, n-De cyl-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,
• - Vaseline
• Defoamers like silicones,
• Thickeners such as gelatin or vegetable gums, for example agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. As methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays and phyllosilicates such. As bentonite or fully synthetic hydrocolloids such. As polyvinyl alcohol, the Ca, Mg or Zn - soaps,
• Refatting agents such as fatty acid alkanolamides, fatty acids, fatty acid esters such as isopropyl myristate, palmitate, oleate and stearate, optionally ethoxylated partial glycerides, wool wax derivatives, lecithin, perhydrosqualene, isopropyl adipate or the above-described fatty substances
• - structurants such as maleic acid, mono-, di- and oligosaccharides,
• Perfume oils, dimethylisosorbide and cyclodextrins,
• Solubilizers, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,
• Dyes for staining the agent,
• Anti-dandruff agents such as Piroctone Olamine, Zinc Omadine and Climbazole,
• - other substances for adjusting the pH,
• - Vitamins and vitamin precursors, such as panthenol, its derivatives and biotin,
• - Plant and honey extracts, in particular extracts of oak bark, stinging nettle, witch hazel, hops, chamomile, burdock root, horsetail, lime blossom, almond, aloe vera, coconut, mango, apricot, lime, wheat, kiwi, melon, orange, grapefruit, sage , Rosemary, birch, meadowfoam, quenelle, yarrow, toadstool, meristem, ginseng and ginger root,
• - Other active ingredients such as ceramides, allantoin, pyrrolidonecarboxylic acids, and bisabolol,
• - sunscreen,
• Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers,
• Fatty acid alkanolamides,
• Physiologically compatible inorganic or organic acids,
• - swelling and penetrating substances such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
• Humectants such as sorbitol, lactic acid salts, glycerol or polysaccharides
• Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers,
• Pearlescing agents such as ethylene glycol mono- and distearate and PEG-3-distearate,
• Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids,
• Reducing agents such as thioglycolic acid and its derivatives, thiolactic acid, cysteamine, thiomalic acid and α-mercaptoethanesulfonic acid,
• Oxidizing agents such as hydrogen peroxide, potassium bromate and sodium bromate,
• - Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ , N ₂ and air and
• - antioxidants.

Regarding further Components as well as quantity ranges for the individual ingredients is based on the manuals known to those skilled in the art, e.g. K. Schrader, basics and formulations of cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989, referenced.

In an embodiment of the invention the agents are formulated in the form of foam aerosols. there is both the formulation with a liquefied gas as blowing agent as well as in the form of so-called pump sprays possible, where the pressure required for spraying is constructed by mechanical pumping. Nitrogen, air, carbon dioxide, Propane, butane, isobutane, pentane and dimethyl ether are preferred Propellant. Although chlorofluorocarbons and chlorinated hydrocarbons in terms the aerosol properties achieved are excellent propellants, so is their use as propellant in the inventive compositions less preferred due to the known ozone problem.

One Another object of the present invention is a method to improve the physical properties of keratin Fibers, in which one means according to the invention, as in the preceding Text is applied in an effective amount on the fibers. Subsequently the agent can be rinsed out again after a contact time or but until the next one shampooing to be left on the hair. In a preferred embodiment of the method, the agent is rinsed out again after a contact time.

Especially the process according to the invention is a process for styling and / or conditioning hair.

It was found in the invention that the use of the copolymers of the invention in the means described in the preceding text both for the manufacturer as well as the user of such means associated with benefits is.

For the formulation Such agents have advantages in terms of freedom from formulation, since the copolymers of the invention good with the usual ones Recipe components compatible and in general no incompatibilities, such as a Show precipitation with anionic components.

The Advantages in the application show up in particular in an increased wet and especially dry combing work of the hair, resulting in improved formability and stylability of the hair Hair means. This for the Users desired Effects are achieved without the means of the state the art known problems of impairment of hair shine or Hair volume can be observed. It also comes through the use the copolymers do not cause undesirable stress on the hair or a sticky handle. According to the teaching of the present invention In particular, improved hair-setting and styling shampoos can be used as well as shampoos for formulate fine hair.

By The invention will be the formulation of combination preparations allows the additional to a first effect, such as a hair cleanser or hair coloring, as a further effect have a hair setting. For the hair fixation Thus, no separate post-treatment is necessary, and the user saves an application step. At the same time, the packaging costs reduced because a product is needed less.

The The following examples are intended to explain the subject matter of the invention in more detail.

So far Unless otherwise indicated, all quantities are to be understood as wt .-%.

Examples

Example 1: Preparation of a copolymer with monomer ratio A: B = 4: 1 starting materials and amounts used: 1500 g least. H ₂ O 1.1 g Texapon K1296 (sodium lauryl sulfate) 3.4 g (0.022 mol) N, N-methylenebisacrylamide (crosslinker, MW: 154.17 g / mol) 54.3 g (0.48 mol) N-Isopropylacrylamide (monomer A, MW: 113.16 g / mol) 33.1 g (0.12 mol) (3-acrylamidopropyl) -trimethylammonium chloride (monomer B, used in the form of a 75% strength by weight solution in water, MW: 206.72 g / mol) 2.8 g Potassium peroxodisulfate (starter) 80 g least. H ₂ O

Execution:

In A 2 l four-neck round bottom flask was charged with 1.5 l of water for 2 h Flushed with nitrogen. Subsequently were stirred successively all three monomers at room temperature in nitrogen countercurrent added. The solution was at 70 ° C heated and treated with potassium peroxodisulfate solution. After 4 h was a stable dispersion obtained, the solid by freeze drying isolated and then in a laboratory mill crushed. The yield was 90 g (99%).

Analysis: the residual monomer contents were determined by HPLC analysis: N-isopropyl acrylamide: 13 μg / g (3-acrylamidopropyl) trimethylammonium chloride: <50 μg / g Example 2 Preparation of a Copolymer With A monomer Ratio A: B = 1: 1 starting materials and amounts used: 1500 g least. H ₂ O 1.1 g Texapon K1296 3.4 g (0.022 mol) N, N-methylenebisacrylamide 33.9 g (0.3 mol) N-Isopropylacrylamide (monomer A) 82.7 g (0.3 mol) (3-acrylamidopropyl) trimethylammonium chloride (monomer B, used in the form of a 75% by weight solution in water) 2.8 g potassium 80 g least. H ₂ O

Execution:

In A 2 l four-neck round bottom flask was charged with 1.5 l of water for 2 h Flushed with nitrogen. Subsequently were stirred successively all three monomers at room temperature in nitrogen countercurrent added. The solution was at 70 ° C heated and treated with potassium peroxodisulfate solution. After 4 h was a stable dispersion obtained, the solid by freeze drying isolated and then in a laboratory mill crushed. The yield was 105 g (88%).

Analysis: the residual monomer contents were determined by HPLC analysis: N-isopropyl acrylamide: 30 μg / g (3-acrylamidopropyl) trimethylammonium chloride: <50 μg / g

Example 3: Determination wet combability:

at the determination of wet combability the work became combing from wet strands of hair 20 hair strands each measured. The values of 10 combs on wet strands of hair were in each case before (Comparative value, corresponding to untreated hair) and after treatment with a 2 wt .-% aqueous Dispersion of the copolymer of Example 2 was determined and compared.

The following values of wet combing work [mJ] were determined: Hair untreated: 123 mJ Hair treated: 78.9 mJ

The Treatment according to the invention the strands of hair led to a significant reduction in wet combing work, as a sign of a clear care and conditioning effect is to interpret.

Example 4: Testing sensory effects

It were each the hair cosmetic sensory effects on wet strands of hair before (comparison value, according to untreated hair) and after Treatment with a 2 wt .-% aqueous dispersion of the copolymer determined and compared from Example 2. The treatment according to the invention resulted notice a much better grip of the hair.

Example 5: Testing sensory Effects from a shampoo recipe

The copolymers of the invention were incorporated into a shampoo formulation. With this shampoo hair was washed and the resulting sensory effects determined by means of a panel (Sensory Assessment Hair). Shampoo basic formulation: laureth 10% Cocoamidopropyl betaine 3% sodium benzoate 0.5% sodium salicylate 0.2% Perfume 0.2% sodium chloride 2.5% citric acid 0.4% water ad 100% V1 (comparison): Shampoo base formula
V2 (not according to the invention): Shampoo base formulation with 2% by weight copolymer of Example 1
E1 (according to the invention): shampoo base formulation with 2% by weight of copolymer

Example 2

Preparation of the hair:

To the Use came 2 g heavy, 18 cm long hair strands of the type 6634 of the company Alkinco. All hair was first cleaned 30 before treatment min with a 12 wt .-% Texapon NSO solution (pH 6.5) and rinsed it then 5 minutes with water. They then became 5 minutes long treated with the respective shampoo recipe, then for 1 min with Rinsed out with water and over Night hanging dried in the climate box.

Conducting the Sensory Assessment:

Around to ensure a defined environment The tests were carried out in a climate chamber at 23 ° C and about 40% relative humidity with standard daylight illumination carried out. Each subject received new hair strands. The test strands were in a pairwise comparison of 11 panelists sensory in the same way checked. The panelists assess the sensory parameters on a quantitative basis Rating scale. Statistical validation took place with the t-test for paired Rehearse.

Results:

• V2: Before combing showed the hair strands treated with V2 highly significantly less Volume as the reference (V1). The hair felt significantly smoother and were also significantly less styleable.
• E1: Before combing the hair strands treated with E1 showed highly significant more shine as the reference (V1). The hair was highly significantly worse comb and felt in the tips significantly rougher, which in terms of styling properties he wishes is. It was thus possible to increase the stylability become.

Example 6: Testing in Half-side test from a shampoo recipe

Methods Description:

• • Schaumanspringen
• • Schaumqualität
• • Griff des Schaumes
• • Schaummenge
• • Kämmarkeit nass
• • Griff nass
• • Kämmbarkeit trocken
• • Griff trocken
• • Volumen
• • Festigung/Lockenhaltbarkeit
• • Glanz

In the half-page test, hair products from volunteers are evaluated according to the following criteria:

• • Foaming
• • Foam quality
• • Handle of the foam
• • amount of foam
• • Kämmarkeit wet
• • Handle wet
• • combability dry
• • Handle dry
• • Volume
• • Firming / curl durability
• • Shine

The Application is performed on hairs of models that are equal left / right are long. To an objective examination to enable The hair must not be combed with Products have been pretreated. To be safe and objective To be able to make a statement At least 5 attempts should be made and the results of 4 judges independent be judged from each other.

Of the Hair of the model is in the half-side test by a center parting divided. 3 g of the product to be tested are placed on a previously to be determined head half Applied to wet hair and against a corresponding reference pattern on the other half of the head directly compared. Both halves of the head are synchronized via a Mirror massaged to possible occurring deviations in Schaumanspringen to keep low.

In the prewash Foaming, Foam Quality, Foam Handling and the amount of foam is assessed. After rinsing, a rewash takes place. 2g of the product are set on the same as in the pre-wash half head applied to wet hair and against the corresponding reference pattern on the other half of the head directly compared. This is also the Schaumanspringen, the foam quality, the handle of the foam and the amount of foam assessed.

To rinse again the head of hair gets from the forehead to the neck, while retaining of the middle parting, smooth combed, this is the combing wet judged. After wet combability the sensory grip is evaluated. Subsequently, with the help of round brushes and hair dryer the drying. Here, individual hair, always under Maintaining the middle parting, about a round brush "round" and dried.

In the dry state, the firmness / curl retention is first tested, in which case the crested halves are touched with the inner surfaces of the hands. The assessor compares the two halves of the head with the feeling of "hardness" of the hair, and compares the curl seat with the bounce and the shape of the curl.After combing (combing dry), the volume, the grip in the dry and dry are evaluated The scalp halves are evaluated according to the orientation of the hair of the scalp according to the following criteria: 0 equal 1 slightly differentiated 2 noticeably different 3 clearly distinguished

Experimental procedure:

The following shampoos were tested:
V1: current market product, which is proclaimed as a "firming shampoo"
E1: Shampoo formulation containing 2% by weight of copolymer according to the invention having a monomer ratio A: B = 1: 4

Results:

In the parameters volume and firmness / curl retention, the hair treated with the shampoo E1 according to the invention was appreciably better assessed than the reference V1, while the other parameters showed little to no differences. Examples 7.1-7.12: Hair treatment compositions with copolymers according to the invention: 7.1 Hair rinse Eumulgin ^® B2 0.3 Cetyl / stearyl 3.3 isopropyl 0.5 Paraffin oil perliquidum 15 cSt. DAB 9 0.3 Dehyquart® ^® A-CA 2.0 Copolymer from Example 2 1.0 Phenonip ^® 0.8 water ad 100 PH = 7.0 7.2 Hair Conditioner Tego amid S18 0.5 Eumulgin ^® B2 0.3 Cetyl / stearyl 3.3 isopropyl 0.5 Paraffin oil perliquidum 15 cSt. DAB 9 0.3 Dehyquart ^® L 80 2.0 Copolymer from Example 2 1.0 citric acid 0.4 Phenonip ^® 0.8 Rewoquat ^® W 575 0.5 water ad 100 PH = 7.0 7.3 Hair cure (rinse off) Dehyquart® ^® F75 4.0 Cetyl / stearyl 4.0 Paraffin oil perliquidum 15 cSt DAB 9 1.5 Dehyquart® ^® A-CA 4.0 Salcare ^® SC 96 0.5 Copolymer from Example 2 2.8 citric acid 0.15 Phenonip ^® 0.8 water ad 100 PH = 7.0 7.4 Hair Conditioner (rinse off) Dehyquart L80 4.0 Cetyl / stearyl 6.0 Paraffin oil perliquidum 15 cSt DAB 9 2.0 Rewoquat ^® W 575 2.0 Sepigel ^® 305 0.5 Copolymer from Example 2 2.8 citric acid 0.15 Phenonip ^® 0.8 water ad 100 PH = 7.0 7.5 hair cure (remaining on the hair) Dehyquart® ^® F75 0.3 Salcare ^® SC 96 5.0 Dow ^Corning® 200 Fluid, 5 cSt. 1.5 Gafquat ^® 755N 1.5 Biodocarb ^® 0.8 Copolymer from Example 2 0.7 perfume oil 0.25 water ad 100 PH = 7.0 7.6 Conditioner (remaining on the hair) Sepigel ^® 305 5.0 Dow Corning ^® Q2-5220 5 cSt. 1.5 Genamin ^® DSAC 0.3 Phenonip ^® 0.8 Copolymer from Example 2 0.8 perfume oil 0.25 water ad 100 PH = 7.0 7.7 Shampoo: Laureth sulfate 25% 40 citric acid 0.1 sodium benzoate 0.5 Disodium cocoamphodiacetate 6.0 salicylic acid 0.1 Hydrotriticum wq 1.0 Copolymer from Example 2 1.5 Cetiol HE 0.5 Perfume 0.4 NaCl 0.5 water ad 100 7.8 Shampoo: Laureth sulfate 25% (alkaline dilution) 25.0 Citric acid mono regular 0.3 Timiron® 0.5 sodium benzoate 0.5 Panthenol 75 L 0.2 Euperlan PK 3000 8.0 Plantacare 818 UP 2.0 Uvinul MS 40 1.0 salicylic acid 0.2 Ajidew NL-50 2.0 Ground Cutina HR 0.5 Cetiol HE 1.0 Citric acid mono regular 0.03 Jaguar excel 0.3 Copolymer from Example 2 1.5 sodium chloride 0.3 water ad 100 7.9 Shampoo Laureth sulfate 25% (alkaline dilution) 50 Citric acid mono regular 0.4 Arlypon F 0.5 Antil 171 0.3 Wheat protein hydrolyzate cationized 1.5 sodium benzoate 0.5 Euperlan PK 3000 6.0 Cocamidopropyl Betaine 45% 5.0 salicylic acid 0.2 DL-Pantolactone Flake 1.0 Gluadin WLM 3.0 Silsoft A-858 0.3 Copolymer from Example 2 2.0 Cutina HR 0.2 Cetiol HE 1.0 water ad 100 7.10 Hair styling gel: Desalinated water ad 100 Synthetic K 0.6 Neutrol TE 0.5 Glycerine DAB 9, 86.5 8.00 Ethyl alcohol denatures 96% by volume 30.00 Copolymer from Example 2 3.00 polyethylene glycol 2.00 PVP / VA W-635 6.50 Cremophor RH 40 1.00 Perfume 0.50 PH = 7.0 7.11 Hairspray: Amphomer.RTM 3.00 Luviskol VA 37 16.00 AMP amino methyl propanol 100 0.60 isopropyl 0.12 Copolymer from Example 2 1.00 Perfume 0.20 Desalinated water ad 100 Ethyl alcohol denatures 96% by volume 67,50 PH = 7.0 Hair Tonic: Desalinated water ad 100 Panthenol 75 0.1 Copolymer from Example 2 1.5 Carbopol 0.1 Neutrol TE 0.10 Ethyl alcohol denatures 96% by volume 30.0 PH = 7.0

Claims (19)

Cationic crosslinked copolymer obtainable by copolymerization of (a) at least one monomer A of the formula (I)

wherein R ¹ = H or methyl, X = O or NR ² , R ² = hydrogen or a linear or branched alkyl radical having 1 to 6 carbon atoms and R ^{3 is} a linear or branched alkyl radical having 1 to 12 carbon atoms, (b) at least one Monomer B of the formula (II)

wherein R ¹ = H or methyl, X = O or NR ² , R ² = hydrogen or a linear or branched alkyl radical having 1 to 6 carbon atoms, n is an integer from 1 to 8, R ⁴ , R ⁵ , R ^{6 is the} same or are each different and each represents an alkyl radical having 1 to 8 carbon atoms, which may each carry a hydroxyl or an amino group, and Y is a halogen or a monoalkyl sulfate, and (c) at least one at least diunsaturated monomer C, which with the monomers A and B is copolymerizable, wherein in the copolymer, the proportion of / of the monomer B between 35 and 99 wt .-% and the proportion of the / the monomer C is between 0.5 and 10 wt .-%, each based on the total weight of the monomers A and B. Copolymer according to claim 1, characterized in that that as Monomer A contains N-isopropylacrylamide is. Copolymer according to claim 1 or 2, characterized that as Monomer B is a 3-acrylamidopropyltrimethylammonium salt, in particular (3-acrylamidopropyl) trimethyl ammonium chloride is included. Copolymer according to one of Claims 1 to 3, characterized that monomer A N-isopropylacrylamide and monomer B a 3-acrylamidopropyl trimethylammonium salt mean. Copolymer according to one of Claims 1 to 4, characterized that the Amount of the monomer / B between 45 and 90, in particular between 50 and 80% by weight, based on the total weight of the monomers A and B. Copolymer according to one of Claims 1 to 5, characterized that this Monomer C selected is from the group formed by N, N-methylenebisacrylamide, ethylene glycol di (meth) acrylate, Polyethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Divinylbenzene, and mixtures thereof. Copolymer according to one of Claims 1 to 6, characterized that the Amount of the / the monomer C between 1 and 7 and in particular between 2 and 4 wt .-%, based on the total weight of the monomers A and B. Process for the preparation of a copolymer according to one of the claims 1 to 7, in which the monomers A, B and C with each other in an emulsion polymerization be polymerized in the presence of a polymerization initiator. Use of a cationic crosslinked copolymer obtainable by copolymerization of (a) at least one monomer A of the formula (I)

wherein R ¹ = H or methyl, X is O or NR ² , R ^{2 is} hydrogen or a linear or branched alkyl radical having 1 to 6 carbon atoms and R ^{3 is} a linear or branched alkyl radical having 1 to 12 carbon atoms, (b) at least one monomer B of the formula (II)

wherein R ¹ = H or methyl, X = O or NR ² , R ² = hydrogen or a linear or branched alkyl radical having 1 to 6 carbon atoms, n is an integer from 1 to 8, R ⁴ , R ⁵ , R ^{6 is the} same or are each different and each represents an alkyl radical having 1 to 8 carbon atoms, which may each carry a hydroxyl or an amino group, and Y is a halogen or a monoalkyl sulfate, and (c) at least one at least diunsaturated monomer C, which with the monomers A and B is copolymerizable, wherein in the copolymer, the proportion of / of the monomer B between 35 and 99 wt .-% and the proportion of the / the monomer C is between 0.5 and 10 wt .-%, each based on the total weight of the monomers A and B, to improve the physical properties of keratinous fibers. Use according to claim 9, characterized that it The keratinic fibers are hair, especially human Hair, act. Use according to claim 9 or 10, characterized that it improve the physical properties of keratin Fibers is a styling and / or a conditioning of hair. Keratin fiber treatment composition comprising at least one cationic crosslinked copolymer obtainable by copolymerization of (a) at least one monomer A of the formula (I)

wherein R ¹ = H or methyl, X = O or NR ² , R ² = hydrogen or a linear or branched alkyl radical having 1 to 6 carbon atoms and R ^{3 is} a linear or branched alkyl radical having 1 to 12 carbon atoms, (b) at least one Monomer B of the formula (II)

wherein R ¹ = H or methyl, X = O or NR ² , R ² = hydrogen or a linear or branched alkyl radical having 1 to 6 carbon atoms, n is an integer from 1 to 8, R ⁴ , R ⁵ , R ^{6 are the} same or different and each represents an alkyl radical having 1 to 8 carbon atoms, each a hydroxy or an amino group, and Y is a halogen or a monoalkyl sulfate, and (c) at least one at least diunsaturated monomer C, which is copolymerizable with the monomers A and B, wherein in the copolymer, the proportion of the / the monomer B between 35 and 99% by weight and the proportion of the monomer C between 0.5 and 10% by weight, based in each case on the total weight of the monomers A and B. Agent according to claim 12, characterized in that that it represents a cosmetic hair treatment and a physiological acceptable carrier includes. Agent according to claim 13, characterized that this Means a conditioning hair treatment agent, in particular a conditioning hair conditioner is. Agent according to claim 13 or 14, characterized that this Agent is a firming hair treatment agent, in particular Firming hair shampoo, a conditioner, a hair conditioner, a hair toning or a hair foam. Agent according to one of claims 12 to 15, characterized that this at least one copolymer to 0.01 to 10, but especially 0.1 contain up to 5 wt .-% is based on the total weight of the agent. Agent according to one of claims 12 to 16, characterized that 0.01 to 30, but especially 0.01 to 20 wt .-% of at least one surfactant are included, based on the total weight of the agent. Process for improving the physical properties keratinic fibers, wherein one comprises an agent according to any one of claims 12 to Apply 17 in an effective amount to the fibers. Method according to claim 18, characterized that it is a procedure for styling and / or conditioning of Hair acts.