DE3602402A1 - Cosmetic compositions based on N-hydroxyethylchitosans, N-hydroxyethylchitosans and a process for their preparation - Google Patents

Abstract

The invention relates to cosmetic compositions for treating the skin or the hair which are characterised by containing N-hydroxyethylchitosan derivatives consisting of a) 4 to 40 mol per cent of monomer units of the formula (I) <IMAGE> and b) 60 to 96 mol per cent of monomer units of the formula (II) <IMAGE> in which R<1> and R<2> are identical or different and are hydrogen or the group <IMAGE> with n equal to an integer from 1 to 5, with the condition that R<1> and R<2> are not both hydrogen in at least 50 per cent of the units of (II), or the salts thereof. It also relates to N-hydroxyethylchitosan derivatives and their salts and a process for preparing these compounds from ethylene oxide and chitosan.

Description

The invention relates to cosmetic agents for treatment of hair or skin containing new ones macromolecular compounds derived from chitosan, which in a suitable cosmetic base come into use.

The invention further relates to new N-hydroxyethyl chitosans and processes for their preparation.

It is already known in cosmetic products, in particular for the treatment of hair, cationic Polymers, especially polymers, the quaternary ammonium groups have to be used as a conditioning agent. Because of an interaction between theirs Ammonium groups and the anionic groups of the hair the cation-active polymers have a high affinity to the keratin fiber.

It has been found that the use of such cationic Polymers in such cosmetic products has numerous advantages: detangling the hair as well as their treatment is facilitated, and continues give the hair bounce and shine. These polymers tend to have an affinity for keratin however, when used repeatedly for accumulation the hair, so that they become heavier, which in the end is undesirable.

Furthermore, problems arise with synthetic polymers because of the physiological effect of possibly traces of monomer present that are difficult to remove from the polymer are removable.  

Attempts have already been made to address these disadvantages to remedy that water-soluble salts of chitosan, one that can be prepared by deacetylation of chitin Polyglucosamines, in such cosmetic products Find application. In this context, reference is made taken on its own European patent specification 00 02 506 and its own German patent 26 27 419.

In the same way as for the majority of the cationic Polymers with quaternary groups give chitosan also frequently the disadvantage that it with the anionic surfactants, usually in cosmetic products for the treatment of hair, little use, especially in shampoos is tolerated. It is therefore necessary to use the chitosan in separate treatments, namely before and / or after the shampooing to take effect.

The chitosan continues to prove itself in neutral and alkaline medium as practically insoluble, so that its Use, for example, in alkaline permanent waving agents or hair dye is not possible.

By using glycidylchitosans instead of Chitosan salts according to DE-OS 32 23 423 can be Avoid the disadvantages mentioned above. The implementation of chitosan with Gylcid is very expensive, since glycid is an expensive, not large-scale, Is raw material.

The object of the invention is therefore, more cost-effective To provide funds with which the Have the disadvantages listed above avoided.

If the investigation is continued with chitosan and the compounds derived from it have now been found  that certain chitosan derivatives, namely especially N-hydroxyethyl-chitosans, those listed above Also not have disadvantages and also much cheaper than the previously known Glycidal chitosans are available.

In contrast to synthetic polymers with finite These N-hydroxyethyl-chitosans contain residual monomers physiologically harmless and biodegradable. Because of their film and release properties, their Thickening effect and compatibility with anionic surfactants can not only as new, interesting raw materials for cosmetics, but also in pharmacy, as flocculant and thickeners in wastewater treatment, as Finishing and sizing agents in the textile industry as well as in papermaking.

With N-hydroxyethyl-chitosans or their salts with organic or inorganic acids can thus cosmetic products for the treatment of hair or the Produce skin that is surprisingly beneficial Characterize properties and are characterized by them are that they are in a suitable cosmetic base in N-hydroxyethyl chitosan consisting of

• a) 4 to 40 mole percent of monomer units of the formula (I)
• b) 60 to 96 mol percent of monomer units of the formula (II) wherein R ¹ and R ^{2 are the} same or different and hydrogen or the group where n is an integer from 1 to 5, provided that at least 50 percent of the units of the formula (II) R ¹ and R ² do not simultaneously represent hydrogen, or its soluble salts with organic or inorganic acids .

Suitable salts are, for example, those with the Acids lactic acid, formic acid, acetic acid or hydrochloric acid be formed.

The N-hydroxyethyl-chitosan containing invention Agents are generally suitable for treatment the skin and / or the hair. For example, you can are available as hair and / or body detergents, Tinting shampoos, hairdressing creams, hairdressing lotions, hairdryer lotions, Means for setting the hairstyle, washing lotions, Hair treatments, anti-dandruff remedies permanent hair shaping, coloring agent or Discoloration of hair, means of application before or after hair coloring and as a cosmetic for  Care, protection or cleaning of the skin such as facial tonic, Aftershave, moisturizing creams, cold creams, Body lotions, sunscreens or make-up up preparations such as make-up creams and blushes.

The content of the cosmetic agents according to the invention of N-hydroxyethyl-chitosan is advantageously 0.05 to 10 percent by weight, preferably 0.05 to 3.0 Percent by weight.

The cosmetic products according to the present invention in addition to the new active ingredient N- Hydroxyethyl chitosan for the preparation of a cosmetic base contain all those ingredients that commonly used in hair and skin treatment products are, especially anionic, cationic, amphoteric, zwitterionic or nonionic surface active Surfactants, foam synergists, stabilizers, Sequestering agents, pigments, thickeners, emulsifiers, Buffer substances, preservatives, dyes, Perfume oils, known cosmetic polymers such as anionic, non-ionic, cationic or amphoteric Polymers, natural products, cosmetic oils, fatty alcohols, Waxes, foam stabilizers, active substances against dandruff, Reducing agents and propellants.

The cosmetic compositions according to the invention have in preferably a pH of 2 to 11 and can be in the form of aqueous, alcoholic or aqueous alcoholic preparations, especially as solutions, Creams, gels, dispersions or emulsions are present. It is also possible to use these funds Atomizer or other suitable spray devices or mixed with usual under pressure liquefied propellants as aerosol spray (for Example aerosol hair spray) or aerosol foam from one Remove the pressure vessel.  

If it is in the cosmetic according to the invention Means for means of setting the hairstyle, such as liquid Hair fixers or hair sprays, then lie they usually as aqueous, alcoholic or aqueous-alcoholic solutions before by a content of N-hydroxyethyl-chitosan consisting of units of the above formulas (I) and (II) or its soluble salts with organic or inorganic Acids are marked. Here it can N-hydroxyethyl-chitosan itself as a film-forming or setting resin can be used; however it can also other natural or film forming synthetic cosmetic polymers in the invention Hair fixatives may be included. As natural polymers come for example shellac, Alginates, gelatins, pectins and cellulose derivatives in Consider. From the synthetic polymers to the Example polyvinylpyrrolidone, polyvinyl acetate, polyacrylic compounds, such as acrylic acid or Methacrylic acid polymers, basic polymers of Esters from acrylic acid or methacrylic acid with amino alcohols or the salts or quaternization products these basic polymers, polyacrylonitrile and Copolymers or terpolymers of such compounds, for example polyvinylpyrrolidone vinyl acetate, use.

The agents then have a pH in particular between 6 and 8. Such means of consolidating the Hairstyle usually contain the film-forming polymers in a total amount of about 0.05 to 3.0 percent by weight. Contain the funds in addition to that described here N-hydroxyethyl-chitosan from units of formulas (I) and (II) above are still other film-forming Polymers, so the content of N- Hydroxyethyl chitosan accordingly.  

In particular, those for cosmetic come as alcohols Purposes commonly used with lower alcohols 1 to 4 carbon atoms, such as ethanol and isopropanol.

If the means for setting the hairstyle are in the form of aerosol preparations, such as, for example, aerosol spray or aerosol foam, which are sprayed from a pressure container, they contain about 10 to 60 percent by weight of a propellant in the cosmetic base. Chlorofluoroalkanes, such as CCl ₃ F, CCl ₂ F ₂ , C ₂ Cl ₃ F ₃ , (CCl ₂ F) ₂ , CHCl ₂ F and (CClF ₂ ) ₂ , volatile hydrocarbons, such as n-butane, can be used as blowing agents and n-propane, or also dimethyl ether, carbon dioxide, nitrous oxide, nitrogen, methylene chloride and 1,1,1-trichloroethane can be used.

The hairstyling agent according to the invention can continue to be the usual additives for such agents, such as perfume oils, bactericides or Fungicides, combability-improving substances and Modifiers such as silicone oil or Plasticizers, such as isopropyl myristate, Diethyl phthalate and diethyl stearate.

The hairstyling agent according to the invention can optionally contain cosmetic Dyes dye the hair at the same time or sound. Such preparations are used, among other things, as color fixers or tinting agent known in the trade. they also contain the usual hair fixers known nitro dyes directly on the hair (for Example 1,4-diamino-2-nitro-benzene, picramic acid, 1-hydroxy-2-amino-4-nitro-benzene and 1,4-bis - [(2- hydroxyethyl) amino] -2-nitro-5-chlorobenzene), azo dyes (For example, C.I. 14 805-Acid Brown 4), anthraquinone dyes  (for example C.I. 61 105 disperse Violet 4) and triphenylmethane dyes (for example C. I. 42 535-Basic Violet 1), the dyes of this Classes acidic depending on the nature of their substituents, can have non-ionic or basic character. Your total concentration in these preparations is usually about 0.01 to 2.0 percent by weight.

The hairstyling agent according to the invention point towards the same good strengthening of the hair usual means a particularly good combability and a good grip of the hair when wet as well a particularly pleasant handle of the hair in the dried Condition on.

If the agents according to the invention are shampoos, they are in the form of aqueous solutions or Emulsions before and contain in addition to the N-hydroxyethyl chitosan at least one anionic, cationic, non-ionic or amphoteric surfactant.

The concentration in these shampoos is the surfactant generally about 3 to 50 percent by weight, preferably 3 to 20 weight percent, wherein the pH generally between 3 and 9 and preferably is between 4 and 7.

The inventive compositions in the form of shampoos are present, generally contain various Additives, especially perfumes, preservatives, Thickeners, foam stabilizers, buffer substances, cosmetic resins, pigments and dyes.

Among the foam stabilizers, the fatty amides and especially the mono- or diethanolamides of  Coconut fatty acids, lauric or oleic acid mono- or diethanolamide, which is conveniently in amounts of 1 to 10 and preferably from 1 to 3 weight percent use find, be led.

Acrylic polymers in particular can be among the thickeners and cellulose derivatives, such as carboxymethyl cellulose, Hydroxypropylmethyl cellulose and hydroxyethyl cellulose, be cited. The thickeners lie generally in a proportion of 0.1 to 5 percent by weight.

Among the surfactants or surfactants, which in combination with the new N-hydroxyethyl-chitosans can be used, for example the following are mentioned:

• a) the anionic surface-active agents, such as, for example, the alkali metal, alkaline earth metal, ammonium or alkanolamine salts of alkane sulfonates, alkyl sulfates and alkyl ether sulfates, the C ₁₂ to C ₁₈ alkyl and especially C ₁₂ to C ₁₄ alkyl sulfate sodium salts or triethanolamine salts , the sodium or triethanolamine salts of lauryl or tetradecyl ether sulfates, the disodium salt of the sulfosuccin half ester of alkanolamides, the soaps and the polyether carboxylic acids;
• b) the nonionic surfactants, such as for example, ethoxylated fatty alcohol with 12 to 18 carbon atoms, for example with up to 40 Moles of ethylene oxide per mole of fatty alcohol Lauryl, tetradecyl, cetyl, oleyl or stearyl alcohol, alone or in a mixture; the fatty alcohols of ethoxylated lanolin or ethoxylated lanolin; Polyglyceryl ether of saturated or unsaturated Fatty alcohols and alkylphenols with 8 to 30 carbon atoms in the alkyl radical and 1 to 10 glyceryl units  in the molecule; Fatty acid alkanolamides as well as ethoxylated sorbitan fatty acid esters;
• c) the cationic surfactants, such as for example dilauryldimethylammonium chloride, the chlorides or bromides of alkyldimethylbenzylammonium, the alkyltrimethylammonium salts, for example Cetyltrimethylammonium chloride or bromide, Tetradecyltrimethylammonium chloride or bromide, the alkyldimethylhydroxyethylammonium chlorides or bromides, the dialkyldimethylammonium chlorides or bromides, alkyl pyridinium salts, for example Lauryl or cetyl pyridinium chloride, the alkylamidethyltrimethylammonium ether sulfates, Imidazoline derivatives, Compounds with a cationic character such as amine oxides, for example alkyldimethylamine oxides or alkylaminoethyldimethylamine oxides;
• d) the amphoteric or zwitterionic surface-active agents, such as, for example, the carboxyl derivatives of imidazole, the N-alkylbetaines, the N-alkylaminobetaines, the N-alkylsulfobetaines, the N-alkylaminopropionates, the alkyldimethylammonium acetates, the C ₁₂ to C ₁₈ -alkyldimethylaloxylamylobenzine and fatty amine carboxamide for example dimethyl carboxymethylene propylene amido stearate betaine.

The cosmetic compositions according to the invention can also Creams or lotions for use as a hair treatment or Represent skin care products. They are usually in Form of oil-in-water or water-in-oil emulsions or suspensions and contain in addition to new N-hydroxyethyl-chitosan cationic, non-ionic, amphoteric or anionic emulsifiers and as Component of the oil phase for example fatty alcohols, Fatty acid esters or amides, also perfume oils, petroleum jelly,  Wool fatty alcohol or solid or liquid Paraffins. If the agents according to the invention or hair dye, so lie they are also preferred in the form of creams or Lotions before and also contain usual hair dyes from the group of aromatic nitro dyes, Azo dyes, anthraquinone dyes, triphenylmethane dyes or also oxidation dyes, for example Resorcinol and aromatic diamines or aminophenols. Furthermore, these agents can optionally contain alkalizing agents, Antioxidants and others for such Common cosmetic additives and auxiliaries contain.

The agents according to the invention can also be permanent shaping agents or represent fixative for hair. They then contain, in addition to the N-hydroxyethyl chitosan reducing agents, such as Thioglycolic acid, thiolactic acid and ammonium sulfite, or oxidizing agents, such as hydrogen peroxide or sodium bromate, and optionally Alkalizing agents or peroxide stabilizers, for Example phosphoric acid and other cosmetic auxiliaries and additives, such as perfume oils, Fragrances, care substances and dyes.

As already mentioned, the inventive cosmetic products also used to treat the skin will.

In fact, these cosmetic products make it easier Moisturize the skin, prevent it from drying out and give the skin excellent softness Handle.

The cosmetic compositions according to the invention are for this purpose  preferably in the form of creams, gels, emulsions or aqueous, alcoholic or aqueous-alcoholic solutions before the N-hydroxyethyl-chitosan in a Concentration of 0.1 to 10 percent by weight and preferably contain from 0.2 to 6 percent by weight.

The generally contained in these cosmetic preparations Auxiliaries are, for example, fragrances, Dyes, preservatives, thickeners, Sequestering agents, emulsifying agents, sun protection filters and similar.

These preparations for skin treatment are in particular in the form of creams or lotions for care hands or face or in the form of sunscreen creams, Bubble bath and shower bath preparations or also in the form of deodorant preparations.

These preparations become more classic using Procedures made. For example, one can to form a cream, an aqueous phase that the chitosan derivative according to the invention and optionally contains other constituents or auxiliary substances in solution, and emulsify an oily phase. For the oily phase you can use different types of compounds, for example Paraffin oil, vaseline oil, sweet almond oil, Avocado oil, olive oil, fatty acid esters, such as Glyceryl monostearate, ethyl palmitate and isopropyl palmitate, or alkyl myristates, such as propyl myristate, Butyl myristate and cetyl myristate. One can they also with fatty alcohols, for example Stearyl or cetyl alcohol, or waxes, for example Beeswax or wool wax, move.

The N-hydroxyethyl-chitosan derivatives can be used in these Cosmetic preparations for skin care both as  Main active ingredient as well as an auxiliary.

The contained in the cosmetic products according to the invention new chitosan derivatives are derived from chitosan ab, a material made by deacetylation of chitin, a naturally occurring acetylglucosamine, is obtained.

The chitosan is in the neutral and alkaline medium insoluble, but it forms due to its chemical Nature in acidic medium with organic and inorganic Acid salts. These can be found, for example, in the paper and textile industry as additives. They are also used as coagulants for suspensions, as a chelating agent for heavy metal ions as well used in medicine and cosmetics (see in this connection the publication of Muzarelli: "Chitin", Pergamon Press, 1977).

There are already some water-soluble chitosan derivatives known, for example carboxymethylchitosan (see Nud'ga, Plisko and Denilov, Zhur. Obsh. Khim. 43, No. 12, pages 2752 to 2756 (1973); SU-PS 3 25 234; such as Okimasu, Nippon Nogei Kagaku Kaishi 32, pages 383 to 389 and 471 to 473 (1958)) or sulfoethylchitosan (see Nud'ga, Plisko and Danilov, Zhur. Prikl. Khim. 47, No. 4, pages 872 to 875 (1974)). These water soluble However, chitosan derivatives are either in changed in ionic character or physiological questionable.

A hydroxyethylchitosan (glycol chitosan) was from Senju and Okimasu (Nippon Nogei Kagaku Kaishi 23, page 432 to 437 (1950)) in the glycolation of chitin in the presence of strong alkali through simultaneous deacetylation receive.

Due to low degrees of substitution respectively  Cross-linking of water-insoluble hydroxyalkyl derivatives of chitosan, its strong water-absorbing properties are of interest in terms of application technology mentioned in JP-PS 54-11 955 of 1979.

Finally, JP-PS 57-1 80 602 from 1982 describes the synthesis of water-soluble chitosan derivatives, the by reaction of alkylene oxides with chitosan in the presence of alkali in a mixture of water and an organic solvent can be obtained.

All of these more or less water-soluble derivatives is the reaction of chitosan with alkylating agents in the presence of strong alkali, which under the chosen reaction conditions exclusively or predominantly results in an O substitution. The for O-alkylation determines the necessary presence of alkali but not just the place of substitution, but moreover, especially at higher temperatures, degradation of the polymer chain. Furthermore represent the after the reaction by neutralizing the excess alkali salts formed by-products that require further cleaning steps.

In contrast, the DE-OS 32 23 423 reports EP-OS 00 97 229 of water-soluble N-substituted Chitosan derivatives, which are preferred by the reaction of an aqueous dispersion of chitosan can be obtained with glycid. The rapid hydrolysis of glycide in the presence of water, its high price and the fact that glycid is not manufactured on an industrial scale , however, make the manufacturing process more expensive of these derivatives.

If you transfer the specified in DE-OS 32 23 423, preferably chosen reaction conditions for the implementation  of chitosan with ethylene oxide, so you get none water-soluble derivatives.

Surprisingly, it has now been found that when using organic solvents chitosan in a simple and inexpensive way with ethylene oxide Hydroxyethyl derivatives with particularly advantageous film and convert solving properties.

In the absence of basic catalysts there is a substitution of the free amino groups, which can be determined by determining the primary amine nitrogen according to van Slyke (see KH Bauer and H. Moll, "Die organic Analyze", 2nd edition, pages 170 to 172 Akademische Verlagsgesellschaft Geest & Portig KG, Leipzig 1950 and H. Roth, E. v. Hulle et al. In "Analytical Methods", pages 674 to 676, Georg Thieme Verlag, Stuttgart 1953) and by ¹³ C-NMR spectra.

The present invention therefore also relates to both water and alcohol soluble, from chitosan derived N-hydroxyethylchitosans and their soluble Salts with organic or inorganic acids out

• a) 4 to 40 mole percent of monomer units of the formula (I)
• b) 60 to 96 mol percent of monomer units of the formula (II) wherein R ¹ and R ^{2 are the} same or different and either hydrogen or the group with n being an integer from 1 to 5, on the condition that R ¹ and R ² do not simultaneously represent hydrogen in at least 50 percent of the units of the formula (II).

The new chitosan derivatives are obtained according to the invention by deacetylating chitosan (60 to 96 percent Chitin) or its salts at temperatures between 20 and 120 degrees C, preferably between 40 and 100 degrees C, under pressure in the autoclave, in one suitable ratio with ethylene oxide over a period of time from 3 to 72 hours, preferably 6 to 48 hours, implements.

The reaction is preferably carried out in one Dispersion in an organic solvent in neutral Medium out. When using chitosan salts or of chitosan in the presence of acidic catalysts, such as hydrochloric acid, the reaction can also in a dispersion consisting of excess Ethylene oxide and water take place. The molar ratio  Chitosan to ethylene oxide is chosen between 1: 3 to 1:15.

When the reaction has ended, the excess is removed Alkylating agent, separates any insoluble ones Portions from the solutions of the chitosan derivative by filtration, neutralized if necessary, constricts on the rotary evaporator and the chitosan derivatives fall immediately or after dialysis in acetone out.

The salts of the N-hydroxyethyl Chitosans can be neutralized by the amino groups the N-hydroxyethyl chitosans with inorganic or organic acids can be obtained. According to the present According to the invention, however, only such salts can be used that are soluble in water. Suitable salts are for example those containing hydrochloric acid, glycolic acid, Lactic acid, formic acid, citric acid or acetic acid be formed.

The following examples are intended to illustrate the subject of Explain the invention in more detail without restricting it to this.

Manufacturing examples example 1

50 g (0.31 mol) of low molecular weight, ground chitosan with an intrinsic viscosity (Eta) of 160 ml / g, and a degree of deacetylation of 90 percent 200 ml of absolute ethanol dispersed and in an autoclave 79.2 g (1.80 mol) of ethylene oxide were added. The chosen one Reaction temperature of 100 degrees C leads to a Initial pressure of about 6.5 bar, which after 12- hour response time to a value of about 1.5 bar sinks. When the reaction has ended, remove it  excess alkylating agents by passing through of nitrogen or by brief heating for Boil after using the highly viscous reaction product diluted 1: 1 with ethanol / water.

After pressure filtration to remove unreacted portions the filtrate is concentrated on a rotary evaporator and then falls in 8 to 10 times the amount Acetone.

To remove trapped ethylene glycols the precipitated derivative using an Ultra-Turax fine dispersed.

The precipitate is collected on a glass sinter, washed thoroughly with acetone and at 50 ° C dried in a vacuum drying cabinet.

56 g of N-hydroxyethylchitosan are obtained.

Key data:

Intrinsic viscosity (Eta) = 74 ml / g Degree of substitution hydroxyethyl = 1.2 Pendulum hardness = 180 sec Water vapor absorption = 8.0 percent

Example 2

25 g (0.16 mol) of a high molecular weight chitosan, with an intrinsic viscosity (Eta) of 1600 ml / g and one Degree of deacetylation of 76 percent, in 300 ml Toluene dispersed in an autoclave with 84.5 g (1.92 mol) Ethylene oxide added and with stirring at 80 degrees C reacted for 24 hours. The workup takes place as described in Example 1.

The yield of N-hydroxyethyl-chitosan is 39.8 g.  

Key data:

Intrinsic viscosity (Eta) = 538 ml / g Degree of substitution hydroxyethyl = 0.9 Pendulum hardness = 176 sec Water vapor absorption = 12.0 percent

Example 3

50 g (0.31 mol) of low molecular weight chitosan as in Example 1 are in a mixture of 100 ml of ethanol and 43.8 g (0.3 mol) of 25 percent hydrochloric acid dispersed and in an autoclave at 100 degrees C with 79.2 g (1.8 mol) Ethylene oxide reacted for 24 hours. The workup takes place as described in Example 1.

49 g of N-hydroxyethylchitosan are obtained.

Key data:

Intrinsic viscosity (Eta) = 85 ml / g Degree of substitution hydroxyethyl = 1.0 Pendulum hardness = 176 sec Water vapor absorption = 8.8 percent

The degree of substitution for the hydroxyethyl residues was determined using the ¹ H-NMR spectra.

The intrinsic viscosity numbers were measured in an aqueous solution of 0.2 ml / l acetic acid and 0.1 mol / l Using sodium acetate at 25 degrees C of a DIN Ubbelohde viscometer.

The pendulum hardness was according to König (W. König, "hardness measurements with the pendulum hardness tester ", paint and varnish 65 (1959), pages 435 to 443; DIN 53 157).

Water vapor absorption became more relative at 70 percent  Air humidity compared to 30 percent relative air humidity determined.

Examples of cosmetic medium Example 4 Hair Fixer

0.6 g, 6N-hydroxyethyl-chitosan according to Example 1 (Eta = 74 ml / g, degree of substitution = 1.2)

25.0 g, 6 isopropanol

0.4 g, 6-formic acid (ten percent aqueous Solution)

0.2 g, 6 perfume oil 73.8 g , 6 water

100.0 g

20 ml of this solution are washed on towel-dried Spread hair. Then the hair inserted and dried in the usual way for hairstyle. With a good setting effect, the hair shows, in comparison to a hair fixer based on chitosan / Formic acid, a more pleasant and softer Handle.

Example 5 Tint Fixer

1.00 g, 6N-hydroxyethylchitosan according to Example 3 (Eta = 85 ml / g, degree of substitution = 1.0)

1.0 g, 6-lactic acid (ten percent aqueous solution)

0.10 g, 6-cetyltrimethylammonium chloride

0.05 g, 6Acid Brown 4 (CI 14 805) 97.85 , 6 water

100.00 g

20 ml of this solution are washed on the towel-dried  Spread hair and the hair in the usual Inlaid and dried. The hair then shows good strengthening and a slight red Brown color.

Example 6 Tint Fixer

0.60 g, 6N-hydroxyethyl-chitosan according to Example 3 (Eta = 85 ml / g, degree of substitution = 1.0)

0.15 g, 61,4-bis (2-hydroxyethyl) amino -2-nitro-5- chlorobenzene

25.00 g, 6 ethanol 74.25 g , 6 water

100.0 g

20 ml of this solution are washed on the towel-dried Given hair, then the hair is inserted and dried. The hair is colored red-violet and consolidated.

Example 7 Anionic shampoo

1.00 g, 6N-hydroxyethylchitosan according to Example 2 (Eta = 538 ml / g, degree of substitution = 0.9)

40.00 g, 6Lauryl alcohol diglycol ether sulfate sodium salt (28 percent aqueous solution)

4.00 g, 6 sodium chloride

0.05 g, 6 dye

54.85 g, 6 water 0.10 g , 6 formaldehyde (25 percent aqueous solution)

100.00 g

A clear shampoo will be obtained. The washed with it Hair is in terms of grip, shine and combability excellently conditioned.  

Example 8 Amphoteres, Toning Shampoo

2.00 g, 6N-hydroxyethylchitosan according to Example 2 (Eta = 538 ml / g, degree of substitution = 0.9)

40.00 g, 6 dimethyl carboxymethylene propylene amido stearate betaine (35 percent aqueous Solution)

5.06 g, 6-formic acid (ten percent aqueous Solution)

3.50 g, 6 coconut fatty acid diethanolamide

1.00 g, 6 picramic acid (one percent aqueous solution) 48.44 g , 6 water, fully desalinated

100.0 g

With about 15 to 20 g of the above shampoo hair shampooed. After an exposure time from 5 to 10 minutes you rinse with water. The hair is tinted yellow-orange and is in excellent condition.

Example 9 Cationic hair conditioner

0.30 g, 6N-hydroxyethyl-chitosan according to Example 1 (Eta = 74 ml / g, degree of substitution = 1.2)

4.00 g, 6-cetylstearyl alcohol

1.48 g, 6-lactic acid (ten percent aqueous solution)

2.50 g, 6 coconut (pentaethoxy) methylammonium chloride

1.00 g, 6 sorbitan monopalmitate, oxyethylated with 20 moles of ethylene oxide 90.72 g , 6 water, fully desalinated

100.00 g

35 g of the hair treatment composition according to Example 10 are washed Hair spreads and after a contact time rinsed again with water for 3 to 5 minutes. As Result will be excellent grip, shine as well  Maintain combability of the hair.

Example 10 Hair conditioner, gel-like

2.1 g, 6N-hydroxymethylchitosan according to Example 2 (Eta = 538 ml / g, degree of substitution = 0.9)

0.6 g, 6-hydroxypropylmethyl cellulose

0.5 g, 6 lauryl pyridinium chloride 96.8 g , 6 water, fully desalinated

100.0 g

The gel is used as described in Example 9 has been. As a result, grip, shine and Combability of the hair significantly improved.

Example 11 Hair Colorants

0.30 g, 6N-hydroxyethyl-chitosan according to Example 1 (Eta = 74 ml / g, degree of substitution = 1.2)

12.00 g, 6-cetylstearyl alcohol

0.10 g, 64-hydroxy-benzoic acid ethyl ester

6.00 g, 6 lauryl alcohol diglycol ether sulfate sodium salt (28 percent aqueous solution)

0.50 g, 6 perfume oil

0.50 g, 61-hydroxy-2-amino-4-nitro-benzene

0.85 g, 61,4-diamino-2-nitro-benzene

0.24 g, 6 sodium hydroxide 79.51 g , 6 water

100.00 g

30 to 40 g of the above hair dye are in distributed to washed hair and after a contact time of about 20 minutes. The hair is reddish in color and easy to comb a comfortable grip.  

Example 12 Oxidation hair dye

0.50 g, 6N-hydroxyethyl-chitosan according to Example 2 (Eta = 538 ml / g, degree of substitution = 0.9)

0.08 g, 63,5-diamino-2,6-dimethoxypyridine dihydrochloride

0.30 g, 61,4-diamino-benzene

0.25 g, 6 resorcinol

0.30 g, 6 sodium sulfite

3.50 g, 6 lauryl alcohol diglycol ether sulfate sodium salt (28 percent aqueous solution)

15.00 g, 6 cetyl alcohol

3.00 g, 6 ammonia 77.07 g , 6 water

100.00 g

50 g of this hair dye is 6 percent with 50 ml Hydrogen peroxide solution mixed and on white Hair applied. After 30 minutes the hair is with Rinsed water and dried. The hair has one natural-looking matt-blonde coloring and one Get a natural, pleasant grip.

Example 13 Permanent Wave Agent

0.5 g, 6N-hydroxyethyl-chitosan according to Example 1 (Eta = 74 ml / g, degree of substitution = 1.2)

10.0 g, 6thioglycolic acid

8.0 g, 6 ammonia (25 percent aqueous solution)

6.1 g, 6 ammonium bicarbonate 75.4 g , 6 water

100.0 g

To apply this perm is applied to the wrapped towel-dried hair evenly on and leave it on for about 20 minutes. After that, the hair  rinsed with water and oxidative in a known manner treated. It will get a good wave result and the hair feels natural and soft.

Example 14 Skin Cream

0.30 g, 6N-hydroxyethyl-chitosan according to Example 3 (Eta = 85 ml / g, degree of substitution = 1.0)

3.00 g, 6 stearyl alcohol

1.00 g, 6 wool wax (Adeps lanae)

1.00 g, 6 Vaseline

0.76 g, 6-lactic acid (ten percent aqueous solution)

1.00 g, 6 sodium acetylstearyl sulfate 92.94 g , 6 water, fully desalinated

100.00 g

5 g of this skin cream are applied to the skin and massaged in lightly. The skin feels soft and smooth to the touch.

Make all percentages in this application, unless otherwise stated, percentages by weight represents.

Claims (15)

1. Cosmetic agent for the treatment of hair or skin, characterized in that it is an N-hydroxyethyl chitosan consisting of in a suitable cosmetic base

• a) 4 to 40 mole percent of monomer units of the formula (I)
• b) 60 to 96 mol percent of monomer units of the formula (II) wherein R ¹ and R ^{2 are the} same or different and hydrogen or the group where n is an integer from 1 to 5, on the condition that R ¹ and R ² do not simultaneously represent hydrogen in at least 50 percent of the units of the formula (II), or contains its soluble salt with organic or inorganic acids.

2. Composition according to claim 1, characterized in that it's the N-hydroxyethyl chitosan in an amount contains from 0.05 to 10.0 percent by weight. 3. Composition according to claim 1 or 2, characterized in that it is in the form of an aqueous, alcoholic or aqueous-alcoholic preparation, in particular as a solution, cream, gel, dispersion or emulsion is present. 4. Composition according to claim 1 to 3, characterized in that the pH is 2 to 11. 5. Composition according to claim 1 to 4, characterized in that it is also a well-known film-forming synthetic or natural cosmetic polymer contains. 6. Composition according to claim 1 to 5, characterized in that there is additionally at least one cosmetic Dye in a concentration of 0.01 contains up to 2.0 percent by weight and in the form of a Color fixer or tint fixer is present. 7. Composition according to claim 1 to 4, characterized in that there is at least one cationic, non-ionic, amphoteric or anionic surfactant contains and is in the form of a shampoo. 8. Composition according to claim 7, characterized in that it is the surfactant in a concentration of 3 to Contains 50 percent by weight and a pH  has between 3 and 9. 9. Composition according to claim 1 to 6, characterized in that as a cosmetic base there is an aqueous, alcoholic or aqueous-alcoholic preparation contains that is mixed with a blowing agent, is filled in a pressure vessel and in shape an aerosol spray or foam. 10. Macromolecular, derived from chitosan N-hydroxyethyl compound consisting of

• a) 4 to 40 mole percent of monomer units of the formula (I)
• b) 60 to 96 mol percent of monomer units of the formula (II) wherein R ¹ and R ^{2 are the} same or different and either hydrogen or the group where n is an integer from 1 to 5, on the condition that R ¹ and R ² do not simultaneously represent hydrogen in at least 50 percent of the units of the formula (II), and their soluble salt with organic or inorganic acids.

11. Process for the preparation of the compounds according to Claim 10, characterized in that one Chitosan, consisting of 60 to 96 percent deacetylated Chitin or its salt with ethylene oxide in the appropriate ratio to the implementation. 12. The method according to claim 11, characterized in that chitosan with ethylene oxide in the form of a dispersion in an organic solvent in neutral Medium reacts. 13. The method according to claim 11, characterized in that you have the chitosan salt or chitosan in the presence acidic catalysts in the form of a dispersion in excess ethylene oxide to react. 14. The method according to claim 11 to 13, characterized in that you can chitosan or its salt with Ethylene oxide at a temperature of 20 to 120 Grade C is reacted for 3 to 72 hours. 15. The method according to claim 11 to 14, characterized in that, based on the amount used Chitosan, the ethylene oxide in three to fifteen times molar excess is used.