DE19748399A1 - Production of sulphated pseudoceramides - Google Patents

Abstract

Process for preparing sulphated pseudoceramides comprises reacting pseudoceramides of formula (Ia) and (Ib) with a sulphating agent: R<1>-Y-CO-CHR<4>-CH2-CO-NR<2>R<3> (Ia) R<1>-Y-CO-CH2-CHR<4>-CO-NR<2>R<3> (Ib) R<1> and R<4> = 6-30C alkyl or alkenyl; Y = O or NR<5>; R<2> = H or optionally OH-substituted 1-30C alkyl; R<3> = 2-12C hydroxyalkyl (containing 1-10 OH groups) or glycosyl; R<5> = H or optionally OH-substituted 1-6C alkyl. Also claimed are sulphated pseudoceramides obtainable as above.

Description

Field of the Invention

The invention relates to sulfated pseudoceramides which are obtained by using pseudoceramides sulfated, a process for producing the sulfated pseudoceramides and their use as Emulsifiers for the formation of lamellar dispersions and liposomes.

State of the art

A balanced water balance plays a role in the elasticity and appearance of the skin individual layers of skin play an important role. In the dermis and in the boundary layer close to the epidermis In the basement membrane, the bound water content is greatest. The skin elasticity will decisively shaped by the collagen fibrils in the dermis, the specific conformation of the Collagen is achieved through the incorporation of water molecules. Destruction of the lipid barrier in the Stratum corneum (SC), for example, by surfactants leads to an increase in transepidermal Water loss, which disturbs the aqueous environment of the cells. Because that in deeper Water bound to the skin layers only via vessels via the body fluid, but not from the outside can be supplied, it becomes clear that the preservation of the barrier function of the stratum corneum is essential for the overall condition of the skin [cf. S.E. Friberg et al., C.R. 23rd CED Congress, Barce lona, 1992, p. 29].

Ceramides are lipophilic amides of long-chain fatty acids, which are generally derived from sphingosine or derive phytosphingosine. This class of the body's own fatty substances is of considerable importance since they were used as a key comm in the intercellular space between the corneocytes components for the construction of the lipid bilayer, i.e. the permeability barrier, in the stratum corneum human skin. Ceramides have molecular weights of well below 1000, so that with external supply in a cosmetic formulation it is possible to reach the site of action. The External application of ceramides leads to the restoration of the lipid barrier, whereby the ge  described skin function disorders can be causally counteracted [cf. R.D. Petersen, Cosm.Toil. 107, 45 (1992)].

So far, the use of ceramides has been limited due to their lack of availability. It has therefore already attempted to use ceramide-analogous structures, so-called "synthetic barrier lipids (SBL) "or" pseudoceramides "and use them for skin care [see G.Imokawa et al. J. Soc. Cosmet. Chem 40, 273 (1989)].

For example, ceramamide analogs of the following structure are proposed in European laid-open publications EP-A 0277641 and EP-A 0227994 (Kao):

Where R and R 'are the same or different and each is a linear or branched, saturated or are unsaturated hydrocarbon group with 9 to 39 carbon atoms, which are unsubstituted or is substituted with one or more hydroxyl groups and where R # is a hydrogen. From US 5641495 (Kao) the sulfated analogs are known in which R # is a hydrogen Sugar residue, a phosphate or a sulfate group.

Structures of the following formula, which are related to ceramides, are known from the European patent applications EP-A1 0482860 and EP-A1 0495624 (Unilever):

Where R # stands for a hydrogen, a sugar residue, a phosphate or a sulfate group.

In order to protect skin and hair, sugar derivatives of the following composition are also proposed in European patent application EP-A2 0455429 (Unilever):

Here, R ^a stands for hydrogen or an unsaturated fatty acyl radical, z for numbers from 7 to 49, R ^b for a hydroxyalkyl and Z for a sugar or phosphate radical.

Sulfated pseudoceramides are also known from WO 92/6982 (Kao) and WO 92/6674 (Unilever) and European patent application EP-A1 0482860 (Unilever) is known, the sulfation here only serves to improve the skin-care properties of the pseudeceramides.

Powerful pseudoceramides of the following formulas are known from German patent DE-C1 44 07 016,

R ¹ -Y-CO-CH ₂ -CHR ⁴ -CO-NR ² R ³ (a)

R ¹ -Y-CO-CHR ⁴ -CH ₂ -CO-NR ² R ³ (b)

in which R ^{1 is} a linear or branched alkyl and / or alkenyl radical having 6 to 30 carbon atoms, Y is oxygen or an NR ⁵ group, R ^{2 is} hydrogen or an optionally hydroxyl-substituted alkyl radical having 1 to 30 carbon atoms, R ^{3 is} a hydroxyalkyl radical with 2 to 12 carbon atoms and 1 to 10 hydroxyl groups or a glycosyl radical, R ⁴ for an alkyl and / or alkenyl radical with 6 to 30 carbon atoms and R ⁵ for hydrogen or an optionally hydroxy-substituted alkyl radical with 1 to 6 carbon atoms.

Regardless of the success of these attempts, particularly with regard to the performance of the Pseudoceramide, when used in cosmetic preparations, is the addition of an emulsifier indispensable. The object of the invention was therefore to so the pseudoceramides modify them at the same time while maintaining their skin care properties Have emulsifier properties. A suitability as an emulsifier would also be desirable especially for lamellar dispersions and liposomes.

Description of the invention

The invention relates to sulfated pseudoceramides of the sulfated alkylsuccinic acid type monofatty alkyl ester-N-alkyl-N-oligohydroxyalkylamides and sulfated alkylsuccinic acid mono fatty alkylamides-N-alkyl-N-oligohydroxyalkylamides which are obtained by using pseudoceramides of the formulas (Ia) and (Ib) sulfated.

R ¹ -Y-CO-CHR ⁴ -CH ₂ -CO-NR ² R ³ (1a)

R ¹ -Y-CO-CH ₂ -CHR ⁴ -CO-NR ² R ³ (Ib).

Where R ¹ and R ^{4 is} a linear or branched alkyl and / or alkenyl radical having 6 to 30 carbon atoms, Y is oxygen or an NR ⁵ group. R ² represents a hydrogen or an optionally hydroxy-substituted alkyl radical having 1 to 30 carbon atoms, preferably having 1 to 4 carbon atoms. R ³ represents a hydroxyalkyl radical with 2 to 12 carbon atoms and 1 to 10 hydroxyl groups or a glycosyl radical, R ⁵ stands for hydrogen or an optionally hydroxy-substituted alkyl radical with 1 to 6 carbon atoms. The sulfated pseudoceramides can carry the sulfate group on all free hydroxyl groups in the molecule, but preferably on the ω-hydroxy group of the hydroxyalkylamide group. Secondary components of the reaction are salts of alkylsuccinic acid monoalkyl esters and sulfated N, O-diacylation products of oligohydroxyalkylamines, such as. B.

Surprisingly, it was found that the sulfated to be used in the context of the invention Good pseudoceramides in addition to the well-known skin care properties of pseudoceramides Emulsifiers are especially used to form lamellar dispersions and liposomes.

Manufacturing process

Another object of the invention relates to a method for producing sulfated Pseudoceramides by using pseudoceramides of the alkyl succinic acid monofatty alkyl ester-N type alkyl-N-oligohydroxyalkylamides and alkylsuccinic acid mono-fatty alkylamides-N-alkyl-N-oligohydrox reacts yalkylamides with sulfation reagents so that a degree of sulfation of 0.5 to 2.0, preferably 0.8 to 1.3 arises.

Pseudoceramides

Pseudoceramides of the alkyl succinic acid monofatty alkyl ester-N-alkyl-N-oligohydroxyalkyl amide type and alkyl succinic acid mono-fatty alkyl amide N-alkyl-N-oligohydroxy alkyl amides of the formulas (Ia) and (Ib) are suitable for the purposes of the process according to the invention

R ¹ -Y-CO-CH ₂ -CHR ⁴ -CO-NR ² R ³ (Ia)

R ¹ -Y-CO-CHR ⁴ -CH ₂ -CO-NR ² R ³ (Ib)

in which R ^{1 represents} a linear or branched alkyl and / or alkenyl radical having 6 to 30 carbon atoms, Y represents oxygen or an NR ⁵ group, R ^{2 represents} hydrogen or an optionally hydroxyl-substituted alkyl radical having 1 to 30 carbon atoms, R ^{3 represents} a Hydroxyalkyl radical having 2 to 12 carbon atoms and 1 to 10 hydroxyl groups or a glycosyl radical, R ^{4 is} an alkyl and / or alkenyl radical with 6 to 30 carbon atoms and R ^{5 is} hydrogen or an optionally hydroxy-substituted alkyl radical with 1 to 6 carbon atoms.

Typical examples of the alkyl succinic acid monofatty alkyl esters N-alkyl-N-oligohydroxyalkylamides are esters of hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl and / or octadecyl succinic acid with capron alcohol, capryl alcohol, 2-ethyl hexyl alcohol, cap , Lauryl alcohol, isotridecyl alcohol, myristyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol and arachyl alcohol as well as their technical mixtures such as those used in the high-pressure hydrogenation of fatty alcohols from ethoxylation of fatty alcohols from the high-pressure hydrogenation of fatty acids. Esters of hexadecyl- and / or octadecylsuccinic acid with technical C _12/18 coconut, C _16/18 palm, C _16/18 tallow or behenyl fatty alcohol cuts are particularly preferred.

Typical examples of the alkylsuccinic acid monofatty alkylamide-N-alkyl-N-oligohydroxyalkylamides are amides of hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl and / or octadecyl succinic acid with hexylamine, decylamine, dodecylamine, hexadecylamine, tetradecylamine , Octadecylamine, behenylamine, C _16/18 palm fatty alkylamine, C _16/18 tallow fatty alkylamine, N-methyldodecylamine, N-methyloctadecylamine, N-octadecylethanolamine and / or N-octadecylpropanolamine.

In both cases, the oligohydroxyalkylamides are N-alkylglucosylamides and N-alkylsorbitylamides preferred, both the glycosylamides and the glycamides can, for example, also differ from Derive maltose, fructose or palatinose. Also come as further hydroxyalkylamides hydroxyalkyl-substituted alkanolamides, for example ethanolamide, propanolamide, 1,1- Bis (hydroxymethyl) -2-ethanolamide, 2,2-bis (hydroxymethyl) 2-ethanolamide and 2,2-bis- (hydroxymethyl) -3-propanolamide into consideration.

Sulphation, neutralization and bleaching

The reaction of the pseudoceramides with gaseous sulfur trioxide can be carried out in the manner known for fatty acid lower alkyl esters [J.Falbe (ed.), "Surfactants in consumer products"; Springer Verlag, Berlin-Heidelberg, 1987, p. 61], with reactors that work according to the falling film principle being preferred. The sulfur trioxide is diluted with an inert gas, preferably air or nitrogen, and used in the form of a gas mixture which contains the sulfating agent in a concentration of 1 to 8, in particular 2 to 5,% by volume. The starting material is usually in an inert solvent, for. B. a chlorinated hydrocarbon, THF or DMF. The molar ratio of starting material and sulfating agent can be set between 1.0: 0.5 and 1.0: 2.0, preferably between 1.0: 0.8 and 1: 1.3. The reaction can be carried out between 0 and 60 ° C, preferably between 18 and 30 ° C. It is also possible to add acid scavengers. The acidic sulfation products obtained in the reaction are stirred into aqueous bases, neutralized and adjusted to a pH of 6.5 to 8.5. The neutralization can be carried out with bases selected from that of alkali metal hydroxides such as sodium, potassium and lithium hydroxide; Alkaline earth metal oxides and hydroxides such as magnesium oxide, magnesium hydroxide, calcium oxide and calcium hydroxide; Alkali alcoholates, such as sodium methoxide or ethanolate; Ammonia; Mono-, di- and tri-C _2-4 -alkanolamines, for example mono-, di- and triethanolamine as well as primary, secondary or tertiary C _1-4 -alkylamines formed group are carried out. The neutralization bases are preferably used in the form of 5 to 55% by weight aqueous solutions, with 25 to 50% by weight aqueous sodium hydroxide solution being preferred.

The sulfation products obtainable by the process according to the invention are inferior Neutralization as aqueous solutions with an active substance content of 20 to 80, preferably 30 to 50% by weight. After neutralization, the sulfation products can be carried out in a manner known per se be bleached by adding hydrogen peroxide or sodium hypochlorite solution to make one for many applications to achieve further color brightening. Here, based on the Solids content in the solution of the sulfation products, 0.2 to 2% by weight of hydrogen peroxide, calculated as 100 wt .-% substance, or appropriate amounts of sodium hypochlorite used. The pH of the solutions can be adjusted using suitable buffering agents, e.g. B. with sodium phosphate or citric acid can be kept constant. To stabilize against bacterial infestation is recommended preservation, e.g. B. with formaldehyde solution, p-hydroxybenzoate, sorbic acid or others known preservatives.

If a solvent was used, this is either evaporated completely or after addition a certain amount of water is distilled off until the solvent has been completely removed. So get either a water dispersible product or an emulsifier dispersion directly.

Instead of sulfur trioxide, chlorosulfonic acid can also be used, preferably in one organic solvents, such as. B. chlorinated hydrocarbons, is being worked on and In addition to alkali metal salt hydroxides, neutralization also uses alkali metal alkoxide.  

Industrial applicability

The substances to be used in the sense of the invention as sulfated pseudoceramides combine the positive properties of pseudoceramides (strengthening the natural barrier function of the skin towards external stimuli; Improving the firmness, suppleness and elasticity of the skin, Increase in moisture content; Protection against dehydration; Smoothing fine wrinkles) with excellent emulsifier properties. You can therefore z. B. to form lamellar dispersions and liposomes can be used in cosmetic products, in particular skin care products.

Cosmetic products

Cosmetics can the sulfated pseudoceramides in amounts of 1 to 30, preferably from Contain 2 to 10 wt .-% - based on the agent - and both as "water-in-oil" and "oil in water "emulsions are present; further customary auxiliaries and additives in amounts of 5 to 95, preferably 10 to 80 wt .-% can also be included. Furthermore, the formulations Have water in an amount up to 99 wt .-%, preferably 5 to 80 wt .-%.

The preparations according to the invention, such as hair shampoos, hair lotions, foam Baths, creams, lotions or ointments can also be used as further auxiliaries and additives, mild surfactants, Oil bodies, emulsifiers, superfatting agents, pearlescent waxes, stabilizers, consistency agents, ver thickeners, cation polymers, silicone compounds, biogenic agents, antidandruff agents, film formers, preservatives, hydrotropes, solubilizers, UV light protection filters, insect repellents, Contain self-tanners, perfume oils, dyes and the like.

Typical examples of suitable mild, i.e. H. Surfactants that are particularly compatible with the skin are fatty alcohol poly glycol ether sulfates, monoglyceride sulfates, mono- and / or dialkyl sulfosuccinates, fatty acid isethionates, Fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, ether carboxylic acids, alkyl oligoglucosides, Fatty acid glucamides, alkylamido betaines and / or protein fatty acid condensates, the latter preferably based on wheat proteins.

Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C ₆ -C ₂₂ fatty acids with linear C ₆ -C ₂₂ fatty alcohols, esters of branched C ₆ -C ₁₃ carboxylic acids are, for example, oil bodies with linear C ₆ -C ₂₂ fatty alcohols, esters of linear C ₆ -C ₂₂ fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of linear and / or branched fatty acids with polyhydric alcohols (such as propylene glycol, dimer diol or trimer triol) and / or Guerbet alcohols, triglycerides based on C ₆ -C ₁₀ fatty acids, liquid mono- / di- / triglyceride mixtures based on C ₆ -C ₁₈ fatty acids, esters of C ₆ -C ₂₂ fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, especially benzoic acid, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear C ₆ -C ₂₂ fatty alcohol carbonates, Guerbet carbonates, esters of benzoic acid with linear and / or branched n C ₆ -C ₂₂ alcohols (e.g. B. Finsolv® TN), dialkyl ethers, ring opening products of epoxidized fatty acid esters with polyols, silicone oils and / or aliphatic or naphthenic hydrocarbons.

Examples of suitable emulsifiers are nonionic surfactants from at least one of the following groups:

• (1) Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear Fatty alcohols with 8 to 22 carbon atoms, on fatty acids with 12 to 22 carbon atoms and on alkylphenols with 8 to 15 carbon atoms in the alkyl group;
• (2) C _12/18 fatty acid _monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol;
• (3) glycerol monoesters and diesters and sorbitan monoesters and diesters of saturated and unsaturated Fatty acids with 6 to 22 carbon atoms and their ethylene oxide addition products;
• (4) Alkyl mono- and oligoglycosides with 8 to 22 carbon atoms in the alkyl radical and their ethoxy analogs;
• (5) adducts of 15 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil;
• (6) polyol and especially polyglycerol esters, such as. B. polyglycerol polyricinoleate, polyglycerol poly 12-hydroxystearate or polyglycerol dimerate. Mixtures of Verbin are also suitable doses from several of these classes of substances;
• (7) adducts of 2 to 15 moles of ethylene oxide with castor oil and / or hardened castor oil;
• (8) _{partial esters} based on linear, branched, unsaturated or saturated C _6/22 fatty acids, ricinoleic acid as well as 12-hydroxystearic acid and glycerin, polyglycerin, pentaerythritol, dipentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glycosides (e.g. Methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (e.g. cellulose);
• (9) trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates;
• (10) wool wax alcohols;
• (11) polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;
• (12) Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE-PS 11 65 574 and / or mixed esters of fatty acids with 6 to 22 carbon atoms, methyl glucose and Polyols, preferably glycerin as well
• (13) Polyalkylene glycols.

The adducts of ethylene oxide and / or of propylene oxide with fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters as well as sorbitan mono- and diesters of fatty acids or with castor oil are known, commercially available products. These are homologous mixtures of which average degree of alkoxylation corresponds to the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out. C _12/18 fatty acid _monoesters and diesters of adducts of ethylene oxide with glycerol are known from DE-PS 20 24 051 as refatting agents for cosmetic preparations.

C _8/18 alkyl mono- and oligoglycosides, their preparation and their use are known from the prior art. They are produced in particular by reacting glucose or oligosaccharides with primary alcohols with 8 to 18 carbon atoms. Regarding the glycoside residue, both monoglycosides in which a cyclic sugar residue is glycosidically bonded to the fatty alcohol and oligomeric glycosides with a degree of oligomerization of up to about 8 are suitable. The degree of oligomerization is a statistical mean value which is based on a homolog distribution customary for such technical products.

Zwitterionic surfactants can also be used as emulsifiers. Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example coconut alkyldimethylammonium glycinate, N-acylamino propyl-N, N-dimethylammonium glycinate, for example coconut acylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxylm -hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. The fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine is particularly preferred. Suitable emulsifiers are ampholytic surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a C _8/18 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-alkyl aminopropionic acid and alkyl amino acetic acid each with about 8 up to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C _12/18 acylsarcosine. In addition to the ampholytic emulsifiers, quaternary emulsifiers are also suitable, those of the ester quat type, preferably methyl quaternized difatty acid triethanolamine ester salts, being particularly preferred.

Substances such as lanolin and lecithin as well as polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and Fatty acid alkanolamides are used, the latter at the same time as foam stabilizers to serve.  

Pearlescent waxes, for example, are: alkylene glycol esters, especially ethylene glycol distearate; Fatty acid alkanolamides, especially coconut fatty acid diethanolamide; Partial glycerides, especially stea rinic acid monoglyceride; Esters of polyvalent, optionally hydroxy-substituted carboxylic acids Fatty alcohols with 6 to 22 carbon atoms, especially long-chain esters of tartaric acid; Fatty substances like for example fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which in total min have at least 24 carbon atoms, especially lauron and distearyl ether; Fatty acids such as stea rinsic acid, hydroxystearic acid or behenic acid, ring opening products of olefin epoxides with 12 to 22 carbon atoms with fatty alcohols with 12 to 22 carbon atoms and / or polyols with 2 to 15 carbon atoms and 2 to 10 hydroxyl groups and mixtures thereof.

The main consistency agents are fatty alcohols with 12 to 22 and preferably 16 to 18 Carbon atoms and also partial glycerides into consideration. A combination of these is preferred Substances with alkyl oligoglucosides and / or fatty acid N-methylglucamides of the same chain length and / or Polyglycerol poly-12-hydroxystearates. Suitable thickeners are, for example, polysaccha ride, especially xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, also higher molecular weight polyethylene glycol mono- and diesters of Fatty acids, polyacrylates (e.g. Carbopole® from Goodrich or Synthalene® from Sigma), polyacrylic amides, polyvinyl alcohol and polyvinyl pyrrolidone, surfactants such as ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as pentaerythritol or trimethylolpropane, Fatty alcohol ethoxylates with a narrow homolog distribution or alkyl oligoglucosides as well as electrolytes like table salt and ammonium chloride.

Suitable cationic polymers are, for example, cationic cellulose derivatives, such as. Legs quaternized hydroxyethyl cellulose obtained from Amerchol under the name Polymer JR 400® Lich, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized Vinyl pyrrolidone / vinyl imidazole polymers, such as. B. Luviquat® (BASF), condensation products from Poly glycols and amines, quaternized collagen polypeptides such as lauryldimonium hydroxy propyl hydrolyzed collagen (Lamequat®L / Grünau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers, such as. B. amidomethicones, copolymers of adipic acid and dimethyl aminohydroxypropyldiethylenetriamine (Cartaretine® / Sandoz), copolymers of acrylic acid with Dime thyldiallylammonium chloride (Merquat® 550 / Chemviron), polyaminopolyamides, such as. B. described in FR-A 2252840 and its crosslinked water-soluble polymers, cationic chitin derivatives such as for example quaternized chitosan, optionally microcrystalline, condensation products from dihaloalkylene, such as. B. dibromobutane with bisdialkylamines, such as. B. bis-dimethylamino-1,3- propane, cationic guar gum, such as B. Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 from the company Celanese, quaternized ammonium salt polymers such as B. Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 from Miranol.  

Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones as well as amino, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and / or alkyl modified silicone compounds that are both liquid and resinous at room temperature can lie. Typical examples of fats are glycerides. a. Beeswax, Carnauba wax, candelilla wax, montan wax, paraffin wax or micro waxes if necessary in Combination with hydrophilic waxes, e.g. B. cetylstearyl alcohol or partial glycerides in question. As Stabilizers can metal salts of fatty acids, such as. B. magnesium, aluminum and / or zinc stearate can be used. Examples of biogenic active ingredients are tocopherol and tocopherol acetate, tocopherol palmitate, ascorbic acid, deoxyribonucleic acid, retinol, bisabolol, allantoin, phy tantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plants to understand extracts and vitamin complexes. Climbazol, octopirox and zinc pyrethione can be used. Common film formers are, for example, chitosan, micro crystalline chitosan, quaternized chitosan, carboxymethyl, hydroxyethyl, Hydroxypropylchitin / chitosan, polyvinylpyrrolidone, vinyl-pyrrolidone-vinyl acetate copolymers, poly mers of the acrylic acid series, quaternary cellulose derivatives, collagen, hyaluronic acid or their salts and similar compounds. Montmorillonite, clay can be used as swelling agents for aqueous phases Minerals, pemules and alkyl-modified carbopol types (Goodrich) are used.  

UV light protection filters are organic substances that are able to absorb ultra violet rays and absorb the energy in the form of longer-wave radiation, e.g. B. to release heat again. UVB filters can be oil-soluble or water-soluble. As oil-soluble substances are z. B. To name:

• - 3-Benzylidene camphor and its derivatives, e.g. B. 3- (4-methylbenzylidene) camphor;
• - 4-aminobenzoic acid derivatives, preferably 4- (dimethylamino) benzoic acid 2-ethylhexyl ester, 4- (Dimethylamino) 2-octyl benzoate and 4- (dimethylamino) benzoic acid amyl ester;
• - Esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, iso-4-methoxycinnamate pentyl ester, 2-cyano-3-phenyl-cinnamic acid 2-ethylhexyl ester (octocrylene);
• - Esters of salicylic acid, preferably salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropylbene methyl ester, salicylic acid homomethyl ester;
• - Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-meth oxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone;
• - Esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate;
• - Triazine derivatives, such as. B. 2,4,6-Trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine and octyltriazone.
• Propane-1,3-diones, such as e.g. B. 1- (4-tert-butylphenyl) -3- (4'methoxyphenyl) propane-1,3-dione;

Possible water-soluble substances are:

• - 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammonium, Alkanolammonium and glucammonium salts;
• - Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sul fonic acid and its salts;
• - Sulfonic acid derivatives of 3-benzylidene camphor, such as. B. 4- (2-oxo-3-bornylidenemethyl) benzenesul fonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and their salts.

Derivatives of benzoylmethane, such as, for example, are particularly suitable as typical UV-A filters wise 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione or 1-phenyl-3- (4'-isopropylphenyl) - propane-1,3-dione. The UV-A and UV-B filters can of course also be used in mixtures become. In addition to the soluble substances mentioned, insoluble pigments are also used for this purpose, namely finely dispersed metal oxides or salts, such as titanium dioxide, zinc oxide, Iron oxide, aluminum oxide, cerium oxide, zirconium oxide, silicates (talc), barium sulfate and zinc stearate. The Particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They can have a spherical shape have, however, such particles can be used that have an ellipsoid or in otherwise have a shape deviating from the spherical shape. In addition to the two The aforementioned groups of primary light stabilizers can also be secondary light stabilizers of the type  of the antioxidants that interrupt the photochemical reaction chain, which is triggered when UV radiation penetrates the skin. Typical examples are superoxide Dismutase, tocopherols (vitamin E) and ascorbic acid (vitamin C).

Hydrotropes such as ethanol, isopropyl alcohol or polyols can also be used to improve the flow behavior. Polyols that come into consideration here preferably have 2 to 15 carbon atoms and at least two hydroxyl groups. Typical examples are

• - glycerin;
• Alkylene glycols, such as, for example, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, Hexylene glycol and polyethylene glycols with an average molecular weight of 100 to 1,000 daltons;
• - Technical oligoglycerol mixtures with a degree of self-condensation of 1.5 to 10 such as technical diglycerol mixtures with a diglycerol content of 40 to 50% by weight;
• Methyl compounds, such as in particular trimethylolethane, trimethylolpropane, trimethylolbutane, Pentaerythritol and dipentaerythritol;
• - Lower alkyl glucosides, especially those with 1 to 8 carbons in the alkyl radical, such as wise methyl and butyl glucoside;
• Sugar alcohols with 5 to 12 carbon atoms, such as sorbitol or mannitol,
• - Sugar with 5 to 12 carbon atoms, such as glucose or sucrose;
• - aminosugars, such as glucamine.

Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, para benzene, pentanediol or sorbic acid. As insect repellents there are N, N-diethyl-m-touluamid, 1,2- Pentanediol or Insect repellent 3535 in question, dihydroxyacetone is suitable as a self-tanner.

Perfume oils include extracts from flowers (lavender, roses, jasmine, neroli), stems and Leaves (geranium, patchouli, petitgrain), fruits (anise, coriander, caraway, juniper), fruit peel (bergamot, lemon, oranges), roots (mace, angelica, celery, cardamom, costus, iris, Calmus), woods (sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, lemon grass, sage, thyme), needles and twigs (spruce, fir, pine, mountain pine), resins and balsams (Galbanum, Elemi, Benzoe, Myrrh, Olibanum, Opoponax). Furthermore animal raw materials come in Question, such as musk, civet and castoreum. As a synthetic or semi-synthetic par Ambroxan, Eugenol, Isoeugenol, Citronellal, Hydroxycitronellal, Geraniol, Citronellol, Geranyl acetate, citral, ionone and methyl ionone.

As dyes, the substances suitable and approved for cosmetic purposes can be used as used in the publication "Cosmetic Colorants" the dye  Commission of the German Research Foundation, Verlag Chemie, Weinheim, 1984, pp. 81-106 are put together. These dyes are usually used in concentrations of 0.001 to 0.1 % By weight, based on the mixture as a whole.

In a preferred embodiment of the invention, the sulfated pseudoceramides can also conventional ceramides, other pseudoceramides, cholesterol, cholesterol fatty acid esters, fat acids - also in a mixture with their alkali salts -, triglycerides, cerebrosides, phospholipids and the like substances are mixed.

In a further preferred embodiment of the invention, the sulfated pseudoceramides with accelerators, in particular with essential oils, such as eucalyptol, Menthol and the like can be mixed.

In a third preferred embodiment, the sulfated pseudoceramides can finally dissolved in squalene or squalane and optionally with the other ingredients mentioned together with volatile or non-volatile silicone compounds as anhydrous or almost anhydrous single-phase systems can be formulated. Other examples of ingredients and typical Compositions can be found, for example, in WO 90/01323 (Bernstein).

Examples example 1 Sulphated hexadecylsuccinic acid monobehenyl ester N-methylsorbitylamide. Na salt; Degree of sulfation 1.0

To a stirred solution of 10 g (10 mmol) 79 wt .-% hexadecylsuccinic acid mono behenyl ester-N-methylsorbitylamide in 90 ml dichloromethane was 1.4 g (12 mmol) chlorosulfonic acid slowly added dropwise in 10 ml dichloromethane and the mixture was stirred for 5 h. After The addition of 50 ml of dichloromethane was followed by 2.8 g of 30% by weight sodium methylate solution until the pH was reached of 8.0 was added and the mixture was evaporated to dryness. There could be 10.2 g of glassy mass isolated from the flask and ground to a colorless, water-dispersible powder. The Elemental analysis and sulfate determination showed a degree of sulfation of 1.0.

Example 2 Sulphated hexadecylsuccinic acid monobehenyl ester N-methylsorbitylamide, Na salt, Degree of sulfation 1.4

Example 1 was repeated, but instead of 1.4 g (12 mmol) of chlorosulfonic acid, 1.86 g (16 mmol) of chlorosulfonic acid. A product similar to that described in Example 1 was used obtained, the degree of sulfation was 1.4.

Example 3

Formulation example for an aqueous liposome gel

The sulfated pseudoceramide is dispersed in water at 60 ° C. After cooling the at 40 ° C cold polyacrylate swelling added. Then is with 10 wt .-% aqueous Neutralized sodium hydroxide solution (to pH 6.5) and cooled to room temperature with stirring. If necessary, water- or oil-soluble active ingredients (e.g. vitamin E, panthenol, vitamin A- palmitate or water-soluble sun protection filters) can be incorporated.  

Example 4

Formulation example for an oil-in-water PIT cream

In a first step, the emulsion concentrate is after the phase inversion temperature process (PIT). The phase inversion temperature is between 70 and 84 ° C. The hot Emulsion concentrate is cooled and the cold 20% liposome dispersion is added at 40 ° C Stir gently. Here too, active substances can be used in a known manner preferred solubility to be added to the emulsion or liposome phase.

Claims (7)

1. sulfated pseudoceramides, obtainable by sulfating pseudoceramides of the formulas (Ia) and (Ib),
R ¹ -Y-CO-CHR ⁴ -CH ₂ -CO-NR ² R ³ (Ia)
R ¹ -Y-CO-CH ₂ -CHR ⁴ -CO-NR ² R ³ (Ib)
where R ¹ and R ^{4 represent} a linear or branched alkyl and / or alkenyl radical having 6 to 30 carbon atoms, Y represents oxygen or an NR ⁵ group, R ² represents a hydrogen or an optionally hydroxy-substituted alkyl radical having 1 to 30 carbon atoms , R ^{3 represents} a hydroxyalkyl radical having 2 to 12 carbon atoms and 1 to 10 hydroxyl groups or a glycosyl radical and R ^{5 represents} hydrogen or an optionally hydroxy-substituted alkyl radical having 1 to 6 carbon atoms. 2. Process for the preparation of sulfated pseudoceramides, characterized in that pseudoceramides of the formulas (Ia) and (Ib),
R ¹ -Y-CO-CHR ⁴ -CH ₂ -CO-NR ² R ³ (Ia)
R ¹ -Y-CO-CH ₂ -CHR ⁴ -CO-NR ² R ³ (Ib)
where Y, R ¹ , R ² , R ³ , R ⁴ and R ^{5 have} the meanings given above, reacted with sulfating reagents. 3. The method according to claim 2, characterized in that SO ₃ or chlorosulfonic acid is used as the sulfating agent. 4. The method according to claim 2, characterized in that pseudoceramides and Sulphating agent used in a molar ratio between 1.0: 0.5 and 1.0: 2.0. 5. The method according to claim 2, characterized in that the reaction between 0 and 60 ° C. 6. Use of the sulfated pseudoceramides according to claim 1 as emulsifiers. 7. Use according to claim 6, characterized in that they are used together with auxiliaries and additives selected from the group formed by ceramides, Pseudoceramides, fatty acids, fatty acid esters, sterols, neutral fatty substances, cerebrosides, Phospholipids and hydrocarbons.