EP1419137A2 - Method for producing acyl amino acids - Google Patents

Abstract

The invention relates to a method for producing acyl amino acids, according to which a mixture of at least one amino acid or the salt thereof and an alkali source is introduced into a reactor and said mixture is added to a polyisotopic element containing fatty acid halides of formula (I): R1COX, wherein R1 represents an alkyl or alkenyl group with between 6 and 22 carbon atoms and X represents chlorine, bromine or iodine. The invention also relates to the resultant products and to the use thereof in cosmetic products and in detergents, dishwashing detergents and cleaning agents.

Description

Process for the preparation of acylamino acids

Field of the Invention

The invention relates to a process for the preparation of acylamino acids in which the fatty acid halide is metered into a circuit line provided with a mixer, while the mixture of an amino acid and an alkali source is placed in the reactor, the product obtained therefrom and the use of these acylamino acids in surfactant-containing preparations ,

State of the art

N-acylamino acids, such as N-acylglutamates, are known from the prior art as mild co-surfactants for use in cosmetic preparations. They are obtained by reacting fatty acid chlorides with the amino group of the glutamic acid sodium salt in the presence of bases such as e.g. NaOH, made in aqueous medium. A disadvantage of this process is that the lipophilic fatty acid chloride can only be reacted with the hydrophilic amino acid or the underlying salt in an aqueous medium with difficulty. One tries to avoid this problem by adding organic solvents such as acetone, methyl ethyl ketone, dioxane, polyols, tetrahydrofuran, t-butanol or cyclohexane.

However, acylation without the addition of solvents is known from European patent EP 0827950 A1 using high stirring energy. A disadvantage of this process is the high level of foam formation, so that this process appears unsuitable for large-scale industrial purposes.

This foam formation can also lead to mixing problems when acid chloride or lye are introduced. Accordingly, this process is not suitable for the large-scale production of acylamino acids.

Patent application EP 0857717 A1 describes a process for the preparation of acylamino acids by reacting amino acids with fatty acid halides in the presence of water, alkali and polyols in conventional stirred tanks in the sense of a one-pot reaction. Disadvantages of this process are the sometimes very high amounts of polyol, which are necessary for a sufficient yield, and the inadequate mixing. The high contents of the polyols described there are sometimes undesirable for the use of the resulting acylated amino acids. However, lowering the polyol content is detrimental to the cold behavior of the product.

The object of the invention was therefore to provide a process for the preparation of acylamino acids which ensures the most uniform possible mixing of the reaction components without foam, as can be observed in traditional stirred reactors, and to provide a product which is characterized by good cold and storage stability.

Description of the invention

The present invention relates to a process for the preparation of acylamino acids, in which a mixture of at least one amino acid or its salt and an alkali source is placed in a reactor and this in a mixing element with fatty acid halides of the formula

(I).

R COX (I)

in which R ^{1 represents} an alkyl or alkenyl radical having 6 to 22 carbon atoms and X represents choir, bromine iodine.

Surprisingly, it has been found that acylamino acids can be produced without excessive foaming developing during their production, as is observed in traditional stirred reactors, and thus a thorough mixing of the reaction components, i.e. amino acids, alkali sources and fatty acid halides.

Another object of the invention is an acylamino acid mixture containing

(a) 3 to 10% by weight sodium chloride,

(b) 0.1 to 4% by weight of free fatty acids,

(c) 1 to 11% by weight of free amino acids,

(d) 0.1 to 6% by weight of low molecular weight alcohol and

(e) 30 to 80 weight percent water. This product is obtainable by not removing the added water-soluble and / or water-dispersible organic solvents after the process according to the invention has been carried out.

The acylamino acid product obtained thereby has a content of water-soluble and / or water-dispersible solvents, preferably low molecular weight monoalcohols, in the range from 0.1 to 6%, preferably 0.2 to 3 and particularly preferably in the range from 0.5 to 2.0 %, based on the aqueous surfactant paste, which in turn has a water content of 30 to 80% by weight, preferably 45 to 70% by weight, particularly preferably 50 to 65% by weight. The content of subsequently added solvents required to adjust the resistance to cold can thereby be markedly reduced. For example, only a maximum of 6% by weight, preferably a maximum of 4% by weight and particularly preferably 3% by weight, of polyols are subsequently added to achieve good low-temperature behavior. In the most favorable cases, even subsequently added solvents can be dispensed with.

Amino acids or their salts

As amino acids or their salts, all α-amino acids known to the person skilled in the art from the literature, which can be acylated with fatty acid halides to N-acylamino acids, are suitable for the purposes of the invention. Preferred amino acids are glutamic acid, sarcosine, aspartic acid, alanine, valine, leucine, isoleucine, proline, hydroxyproline, glycine, serine, cysteine, cystine, threonine, histidine and their salts and in particular glutamic acid, sarcosine, aspartic acid, glycine, lysine and their salts in question, particularly preferred are glutamic acid, sarcosine, aspartic acid, glycine and lysine. The amino acids can be used in optically pure form or as racemic mixtures.

The amino acids or their salts are used in the preparation of the surfactant mixtures according to the invention in amounts of 20 to 70% by weight, preferably 35 to 60 and in particular 40 to 50% by weight, based on the starting mixture, i.e. before adding acid chloride.

fatty acid halides

For the process according to the invention, fatty acid halides which form component (b) are of the formula (I)

R ¹ COX (I) used, in which R ^{1 is} an alkyl or alkenyl radical having 6 to 22, preferably 8 to 18 and in particular 8 to 16 carbon atoms and X is chlorine, bromine or iodine and preferably chlorine. Typical acid halides are octanoyl chloride, nonanoyl chloride, decanoyl chloride, undecanoyl chloride, lauroyl chloride, tridecanoyl chloride, myristoyl chloride, palmitoyl chloride, stearoyl chloride, oleoyl chloride and also mixtures thereof.

The fatty acid halides are used in the preparation of the surfactant mixtures according to the invention in a molar ratio of acylatable compound / acid halide = 1 to 1.5, particularly preferably from 1.15 to 1.3.

alkali source

An alkali source is placed in the reactor for the process according to the invention. For the purposes of the invention, the alkali source is understood to mean alkali hydroxide or carbonate dissolved in water or in a mixture of water and / or at least one water-soluble organic solvent. An aqueous solution of alkali hydroxide or alkali hydroxide dissolved in water and water-soluble organic solvents, in particular sodium hydroxide, is preferably used (cf. process).

In the process according to the invention, the amount of alkali is dimensioned such that a pH of the starting mixture of amino acid or amino acid salt of 10 to 12.5, preferably 11.5 to 12.5, is established.

Water soluble organic solvents

Examples of suitable water-soluble or water-dispersible organic solvents are acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, methanol, ethanol, propanol, i-propanol, butanol, t-butanol, pentanol, isopentanol, trimethylhexanol, glycerol, ethylene glycol, 2-methyl propane. diol-1, 3, propylene glycol, dipropylene glycol, 1, 3 butylene glycol, 1, 2-butanediol, 1, 4-butanediol, isopentyldiol, sorbitol, xylitol, mannitol, erythritol, pentaerythritol, ethanolamine, triethanolamine, 2-amino-2 -methyl propanol, 1-amino-propanol-2, 1-amino-butanol-2, 1-methoxy-2-propanol, 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol , 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-propoxy-2-propanol, 1-isopropoxy-2-propanol, 1-butoxy-2-propanol, 1-isobutoxy-2-propanol, methoxyisopropanol , Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monisopropyl ether, diethylene glycol monobutyl ether, triethyl englycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monisopropyl ether, triethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monisopropyl ether, dipropylene glycol monobutyl ether, hexylene glycol, triacetin, propylene carbonate, glycerol carbonate. Ethanol, isopropanol, diethylene glycol monoethyl ether and triethanolamine are used as preferred solvents. These solvents are also placed in the reactor together with the amino acid and the alkali source.

The water-soluble organic solvents are used in the process according to the invention in amounts of 0.1 to 15, preferably 0.2 to 7 and in particular 0.2 to 4.0% by weight.

method

A mixture of at least one amino acid or its salt, preferably an aqueous solution of an amino acid or its salt and an alkali source, preferably alkali metal hydroxide or alkali metal carbonate dissolved in water and / or aqueous organic solvents, is placed in a reactor (Fig. 1) and made up to 10 cooled to 20 ° C. In a particular embodiment of the invention, water-soluble organic, preferably volatile solvents can also be added, as described above. The reactor and the circulation system are provided with a cooling jacket, which ensures that the heat of reaction is dissipated and a maximum temperature of 20 to 25 ° C is guaranteed. Before the start of the reaction, the pH is adjusted to approximately 12 using an alkali solution, preferably sodium hydroxide solution. The fatty acid halide and the alkali solution are then metered in simultaneously (see plant concept) in such a way that the reactor temperature does not exceed 20 to 25 ° C and the pH is between 11.5 and 12.5. In the case of the alkali source, the two reactants are preferably immersed in the reactor, ie below the surface of the reaction mixture, and in the case of the fatty acid chloride from the storage container into or in front of the mixing element (mixer). Dynamic or static mixers are understood as a mixing element in the sense of the invention. Mixers are encapsulated units that prevent air from entering during the mixing process. These can be dynamic mixers with movable and possibly additional fixed installations or static mixers with only fixed installations (mixing using the flow energy). The reactor and the mixing element are connected to one another via a circulatory system. A circulation pump ensures that the reaction mixture is circulated throughout the reaction, the return of the mixture taking place submerged in the reactor, ie below the surface of the reaction mixture. After the fatty acid chloride has been added, the mixture is stirred for a further 2 to 5, preferably 2, hours at 20 to 25 ° C. and then heated to 60 to 80 ° C. for a further 2 to 5, preferably 2 hours. If organic solvents have been added as further components, these can be made from the reaction mixture can be removed again by distillation, preferably vacuum distillation or steam distillation.

Since these solvents generally distill over as water as an azeotrope, the associated increase in concentration is compensated for by adding an adequate amount of water. This distillation is preferably carried out with simultaneous metering of water vapor, which on the one hand reduces the amount of foam during the distillation and on the other hand compensates for the loss of water. The distillation is preferably carried out at 60 to 80 ° C and a pressure of 200 to 400 mbar.

In a particular embodiment of the invention, after the end of the reaction, the organic solvents are largely removed from the mixture by distillation and then small amounts of solvent still present using a so-called Fryma system. In a further embodiment of the invention, the solvent can also be removed from the mixture by means of a membrane process. However, preference is given to removing the solvent, in particular when using low molecular weight monoalcohols.

The mixture is then allowed to cool to room temperature and the pH of the reaction mixture is adjusted to approximately 10 by adding dilute hydrochloric acid. The reaction solution contains about 20 to 45% by weight, preferably 25 to 30% by weight, of acylated amino acid.

In order to keep the generation of foam as low as possible, the reactor is only stirred at a speed of <60 / min, preferably <30 / min. Mixing in the absence of air prevents foaming during the entire journey.

Industrial applicability

Contain the acylamino acid mixtures produced by the process according to the invention

3 to 10% by weight sodium chloride, 0.1 to 4% by weight free fatty acids,

1 to 11% by weight of free amino acids

0.1 to 6% by weight of low molecular weight alcohol and

30 to 80% by weight of water.

Contain preferred acylamino acid mixtures

4 to 7% by weight sodium chloride, 0.5 to 3% by weight free fatty acids, 1.5 to 8% by weight of free amino acids

0.2 to 3% by weight of low molecular weight alcohol and

45 to 70% by weight of water,

and particularly preferred included

4 to 5.5% by weight sodium chloride,

1 to 2.5% by weight of free fatty acids,

3 to 6% by weight of free amino acids

0.5 to 2% by weight of low molecular weight alcohol and

50 to 65% by weight of water.

When isopropanol and / or ethanol are used as the low molecular weight alcohol, a maximum of 6% by weight, preferably a maximum of 4% by weight and particularly preferably a maximum of 3% by weight of 1,2-propylene glycol is added to this product to adjust the resistance to cold.

The product can be used in surface-active preparations, such as detergents and dishwashing detergents, household detergents and cosmetic and / or pharmaceutical preparations in amounts of 0.1 to 30% by weight, preferably 0.5 to 10% by weight and particularly preferably 1 to 5% by weight .% are used. These may include, as further auxiliaries and additives, mild surfactants, oil bodies, emulsifiers, pearlescent waxes, consistency agents, thickeners, superfatting agents, stabilizers, polymers, silicone compounds, fats, waxes, lecithins, phospholipids, biogenic active ingredients, UV light protection factors, antioxidants, deodorants, Antiperspirants, antidandruff agents, film formers, swelling agents, insect repellents, self-tanners, tyrosine inhibitors (depigmentation agents), hydrotropes, solubilizers, preservatives, perfume oils, dyes and the like. Cosmetic and / or pharmaceutical cleaning agents include, for example, hair shampoos, oral and dental care products, hair lotions, foam baths, shower baths, creams, gels, lotions, alcoholic and aqueous / alcoholic solutions and emulsions.

surfactants

Anionic, nonionic, cationic and / or amphoteric or amphoteric surfactants may be present as surface-active substances, the proportion of which in the compositions is usually about 1 to 70, preferably 5 to 50 and in particular 10 to 30% by weight. Typical examples of anionic surfactants are soaps, alkylbenzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerin ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerin ether sulfates, fatty acid ether sulfates, hydroxymethyl ether sulfates, hydroxymethyl ether sulfates, hydroxymethyl ether sulfates, (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid ethionates, fatty acid sarcosinates, fatty acid taurides, N-acyl amino acids, such as, for example, acyl amino acids, such as, Acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially vegetable products based on wheat) and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution. Typical examples of non-ionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, optionally partially oxidized alk (en) yl oligoglycosides or especially glucoric acid amide hydrolysate protein derivatives, glucorucid amide hydrolysis acid, vegetable gluco acid amide, vegetable gluco acid amide, vegetable gluconic acid amide, vegetable gluconic acid amide, vegetable glucoric acid amide, vegetable gluconic acid amide, vegetable glucoric acid amide, vegetable glucoric acid amide, vegetable glucoric acid amide, vegetable glucoric acid amide, and Wheat-based products), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution. Typical examples of cationic surfactants are quaternary ammonium compounds, such as, for example, dimethyldistearylammonium chloride and esterquats, in particular quaternized fatty acid trialkanolamine ester salts. Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. The surfactants mentioned are exclusively known compounds. With regard to the structure and manufacture of these substances, reference is made to relevant reviews, for example, J.Falbe (ed.), "Surfactants in Consumer Products", Springer Verlag, Berlin, 1987, pp. 54-124 or J.Falbe (ed.), "Catalysts, Tenside und Mineralöladditive ", Thieme Verlag, Stuttgart, 1978, pp. 123-217. Typical examples of particularly suitable mild, ie particularly skin-compatible, surfactants are fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and / or dialkyl sulfosuccinates, fatty acid taurides, fatty acid glutamates, α-olefin sulfonates, ethercarboxylic acids, alkyl oligoglucosides, fatty acid glucamides, alkylamidobetaines, amphoacetals and / or protein fatty acid condensates , the latter preferably based on wheat proteins.

Olkörper

Guerbet alcohols based on fatty alcohols with 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C6-C22 fatty acids with linear or branched C6-C22 fatty alcohols or esters of branched C6-Ci3 carboxylic acids with linear or branched C6-C22 fatty alcohols, such as myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, Ce tylstearat, Cetylisostearat, cetyl oleate, cetyl behenate, Cetylerucat, Stearylmyristat, stearyl palmitate, stearyl stearate, Stearylisostearat, stearyl oleate, stearyl behenate, Stearylerucat, isostearyl, isostearyl palmitate, Isostearylstearat, isostearyl isostearate, Isostearyloleat, isostearyl behenate, Isostearyloleat, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, Oleylbehenat, Oleylerucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenylerucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate and erucyl bucate. In addition, esters of linear C6-C22 fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of Ci8-C ₃ 8-alkylhydroxycarboxylic acids with linear or branched C6-C22 fatty alcohols (cf. DE 19756377 A1) are suitable, in particular dioctyl malates, 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 Cδ-cio fatty acids, liquid mono- / di- / triglyceride mixtures based of Cδ-Ciβ fatty acids (cf. EP 97/00434), esters of C6-C22 fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, esters of C2-Ci2-dicarboxylic acids with linear or branched alcohols with 1 to 22 carbon atoms or polyols with 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C6-C22 fatty alcohol carbonates, such as, for example, dic aprylyl carbonates (Cetiol® CC), Guerbet carbonates based on fatty alcohols with 6 to 18, preferably 8 to 10 C atoms, esters of benzoic acid with linear and / or branched C6-C ₂ alcohols (e.g. Finsolv® TN), linear or branched, symmetrical or asymmetrical dialkyl ethers with 6 to 22 carbon atoms per alkyl group, such as, for example, dicaprylyl ether (Cetiol® OE), ring opening products of epoxidized fatty acid esters with polyols, silicone oils (cyclomethicones, silicon methoxide types, etc.) and / or aliphatic or naphthenic hydrocarbons, such as for example, like squalane, squalene or dialkylcyclohexanes.

Emulqatoren

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

> 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 C atoms, with fatty acids with 12 to 22 C atoms, with alkylphenols with 8 to 15 C atoms in the Alkyl group and alkylamines with 8 to 22 carbon atoms in the alkyl radical;

> Alkyl and / or alkenyl oligoglycosides with 8 to 22 carbon atoms in the alk (en) yl radical and their ethoxylated analogs; > Addition products of 1 to 30 moles of ethylene oxide with fatty acids. Insert products of 1 to 30 moles of ethylene oxide in fatty acid methyl ester

> Adducts of 1 to 15 moles of ethylene oxide with castor oil and / or hardened castor oil;

> Adducts of 15 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil;

> Partial esters of glycerol and / or sorbitan with unsaturated, linear or saturated, branched fatty acids with 12 to 22 carbon atoms and / or hydroxycarboxylic acids with 3 to 18 carbon atoms and their adducts with 1 to 30 moles of ethylene oxide;

> Partial esters of polyglycerol (average degree of self-condensation 2 to 8), polyethylene glycol (molecular weight 400 to 5000), trimethylolpropane, pentaerythritol, sugar alcohols (eg sorbitol), alkyl glucosides (eg methyl glucoside, butyl glucoside, lauryl glucoside) and poly (eg cellulose) saturated and / or unsaturated, linear or branched fatty acids with 12 to 22 carbon atoms and / or hydroxycarboxylic acids with 3 to 18 carbon atoms and their adducts with 1 to 30 mol ethylene oxide;

> Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE 1165574 PS and / or mixed esters of fatty acids with 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol or polyglycerol.

> Mono-, di- and trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates and their salts;

> Wool wax alcohols;

> Polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;

> Block copolymers e.g. Polyethylene glycol 30 dipolyhydroxystearate;

> Polymer emulsifiers, e.g. Pemulen types (TR-1, TR-2) from Goodrich;

> Polyalkylene glycols as well

> Glycerine carbonate.

The adducts of ethylene oxide and / or of propylene oxide with fatty alcohols, fatty acids, alkylphenols or with castor oil are known, commercially available products. These are mixtures of homologs whose average degree of alkoxylation is the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate, with which the addition reaction is carried out. Ci2 / i8 fatty acid monoesters and diesters of adducts of ethylene oxide with glycerol are known from DE 2024051 PS as refatting agents for cosmetic preparations.

Alkyl and / or alkenyl 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 The rest applies that 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 preferably 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.

Typical examples of suitable partial glycerides are hydroxystearic acid monoglyceride, stearic acid diglyceride hydroxy, isostearic acid, Isostearinsäurediglycerid, Ölsäuremonoglyce- chloride, oleic acid diglyceride, Ricinolsäuremoglycerid, Ricinolsäurediglycerid, Linolsäuremonoglycerid, Linolsäurediglycerid, Linolensäuremonoglycerid, Linolensäurediglycerid, Erucasäuremonoglycerid, Erucasäurediglycerid, Weinsäuremonoglycerid, Weinsäurediglycerid, Citronensäuremonoglycerid, Citronendiglycerid, Äpfelsäuremonoglycerid, malic acid diglyceride and their technical mixtures, which may still contain small amounts of triglyceride from the manufacturing process. Addition products of 1 to 30, preferably 5 to 10, mol of ethylene oxide onto the partial glycerides mentioned are also suitable.

As sorbitan sorbitan, sorbitan sesquiisostearate, Sorbitan, sorbitan triisostearate, sorbitan monooleate, sorbitan, sorbitan, Sorbitanmonoerucat, Sorbitansesquierucat, Sorbitandierucat, Sorbitantrierucat, Sorbitanmonorici- come noleat, Sorbitansesquiricinoleat, Sorbitandiricinoleat, Sorbitantriricinoleat, Sorbitanmonohydro- xystearat, Sorbitansesquihydroxystearat, Sorbitandihydroxystearat, Sorbitantrihydroxystearat, sorting bitanmonotartrat , Sorbitan sesquitartrate, sorbitan ditartrate, sorbitan tritartrate, sorbitan monocitrate, sorbitan sesquicitrate, sorbitan dicitrate, sorbitan tricitrate, sorbitan monomaleate, sorbitan sesquimaleate, sorbitan dimaleate, sorbitan trimaleate and their technical mixtures. Addition products of 1 to 30, preferably 5 to 10, mol of ethylene oxide onto the sorbitan esters mentioned are also suitable.

Typical examples of suitable polyglycerol esters are polyglyceryl-2 dipolyhydroxystearates (Dehymuls® PGPH), polyglycerol-3-diisostearates (Lameform® TGI), polyglyceryl-4 isostearates (Isolan® Gl 34), polyglyceryl-3 oleates, diisostearoyl polyglyceryl polyglyceryl 3 diisostearates (Isolan® PDI), polyglyceryl-3 methylglucose distearate (Tego Care® 450), polyglyceryl-3 beeswax (Cera Bellina®), polyglyceryl-4 caprate (polyglycerol caprate T2010 / 90), polyglyceryl-3 cetyl ether ( Chimexane® NL), Polyglyceryl-3 Distearate (Cremophor® GS 32) and Polyglyceryl Polyricinoleate (Admul® WOL 1403) Polyglyceryl Dimerate Isostearate and their mixtures. Examples of other suitable polyol esters are the mono-, di- and triesters of trimethylolpropane or pentaerythritol with lauric acid, coconut fatty acid, taig fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like which are optionally reacted with 1 to 30 mol of ethylene oxide. 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-acylaminopropyl-N, N-dimethylammonium glycinate, for example coconut acylaminopropyldimethylammonium glycinate, and 2-alkylmethyl-carboxylate -3-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 of Cocamidopropyl Betaine is particularly preferred. Suitable emulsifiers are ampholytic surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a Cβ / iβ alkyl or acyl group, contain at least one free amino group and at least one -COOH or -Sθ3H group in the molecule 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 with about 8 to 18 C. Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C12 / 18-acylsarcosine. Finally, cationic surfactants are also suitable as emulsifiers, those of the ester quat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, being particularly preferred.

Fats and waxes

Typical examples of fats are glycerides, ie solid or liquid vegetable or animal products which essentially consist of mixed glycerol esters of higher fatty acids, waxes include natural waxes, such as candelilla wax, camauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax , Ouricury wax, montan wax, beeswax, shellac wax, walrus, lanolin (wool wax), pretzel fat, ceresin, ozokerite (earth wax), petrolatum, paraffin waxes, micro waxes; chemically modified waxes (hard waxes), such as montan ester waxes, Sasol waxes, hydrogenated jojoba waxes and synthetic waxes, such as polyalkylene waxes and polyethylene glycol waxes. In addition to fats, fat-like substances such as lecithins and phospholipids can also be used as additives. The person skilled in the art understands the term lecithins as those glycerophospholipids which are formed from fatty acids, glycerol, phosphoric acid and choline by esterification form. Lecithins are therefore often referred to in the art as phosphatidylcholines (PC) and follow the general formula

where R typically represents linear aliphatic hydrocarbon radicals with 15 to 17 carbon atoms and up to 4 cis double bonds. Examples of natural lecithins are the cephalins, which are also referred to as phosphatidic acids and are derivatives of 1,2-diacyl-sn-glycerol-3-phosphoric acids. In contrast, phospholipids are usually understood to be mono- and preferably diesters of phosphoric acid with glycerol (glycerol phosphates), which are generally classed as fats. In addition, sphingosines or sphingolipids are also suitable.

pearlescent

Pearlescent waxes, for example, are: alkylene glycol esters, especially ethylene glycol distearate; Fatty acid alkanolamides, especially coconut fatty acid diethanolamide; Partial glycerides, especially stearic acid monoglyceride; Esters of polyvalent, optionally hydroxy-substituted carboxylic acids with fatty alcohols having 6 to 22 carbon atoms, especially long-chain esters of tartaric acid; Fatty substances, such as, for example, fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which have a total of at least 24 carbon atoms, especially lauron and distearyl ether; Fatty acids such as stearic 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.

Consistency and thickening agents

Suitable consistency agents are primarily fatty alcohols or hydroxy fatty alcohols with 12 to 22 and preferably 16 to 18 carbon atoms and, in addition, partial glycerides, fatty acids or hydroxy fatty acids. A combination of these substances with alkyl oligoglucosis the and / or fatty acid N-methylglucamides of the same chain length and / or polyglycerol poly-12-hydroxystearates. Suitable thickeners are, for example, Aerosil types (hydrophilic silicas), polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tylos, carboxymethyl cellulose and hydroxyethyl cellulose, and also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates , (e.g. Carbopole® and Pemulen types from Goodrich; Synthalene® from Sigma; Keltrol types from Kelco; Sepigel types from Seppic; Salcare types from Allied Colloids), polyacrylamides, polymers, polyvinyl alcohol and polyvinylpyrrolidone, 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 and electrolytes such as sodium chloride and ammonium chloride.

superfatting

Substances such as, for example, lanolin and lecithin and polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides can be used as superfatting agents, the latter simultaneously serving as foam stabilizers.

stabilizers

Metal salts of fatty acids, such as e.g. Magnesium, aluminum and / or zinc stearate or ricinoleate are used.

polymers

Suitable cationic polymers are, for example, cationic cellulose derivatives, such as, for example, a quaternized hydroxyethyl cellulose, which is available under the name Polymer JR 400® from Amerchol, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone / vinylimidazole polymers, such as, for example, Luviquat® (BASF) , Condensation products of polyglycols and amines, quaternized collagen polypeptides, such as, for example, lauryl-dimonium hydroxypropyl hydrolyzed collagen (Lamequat®L / Grünau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers, such as, for example, amodimethicones, copolymers of adipic acid / dimethylamino-hydroxypropyl (dimethylamino-hydroxypropyl) ), Copolymers acrylic acid with dimethyldiallylammonium chloride (Merquat® 550 / Chemviron), polyaminopolyamides, as described, for example, in FR 2252840 A and their crosslinked water-soluble polymers, cationic chitin derivatives such as, for example, quaternized chitosan, optionally microcrystalline, condensation products from dihaloalkylene, such as dibromobutane with bisdialkylamines, such as, for example, bis-dimethylamino-1, 3-propane, cationic guar gum, such as, for example, Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 from Celanese, quaternized ammonium salt polymers, such as, for example, Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 from Miranol.

Anionic, zwitterionic, amphoteric and nonionic polymers include, for example, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and their polyols, acrylamides and non-reacted polyamides with unreacted polyamides and acrylates, and non-crosslinked polyols, and non-crosslinked polyols, and non-crosslinked polyols, and non-crosslinked polyols, and non-crosslinked polyols with acrylates and their polyols, non-crosslinked polyamides, and non-crosslinked polyols with acrylates and their esters, uncommonized polyacrylates - umchloride / acrylate copolymers, octylacrylamide / methyl methacrylate / tert. Butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymers, vinylpyrrolidone / dimethylaminoethyl methacrylate / vinylcaprolactam terpolymers and optionally derivatized cellulose ethers and silicones in question. Further suitable polymers and thickeners are listed in Cosmetics & Toiletries Vol. 108, May 1993, page 95ff.

Silicone Compounds

Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones and amino, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and / or alkyl-modified silicone compounds, which can be both liquid and resinous at room temperature. Simethicones, which are mixtures of dimethicones with an average chain length of 200 to 300 dimethylsiloxane units and hydrogenated silicates, are also suitable. A detailed overview of suitable volatile silicones can also be found by Todd et al. in Cosm.Toil. 91, 27 (1976).

UV protection filter and antioxidants

UV light protection factors are understood to mean, for example, organic substances (light protection filters) which are liquid or crystalline at room temperature and which are able to absorb ultraviolet rays and release the absorbed energy in the form of longer-wave radiation, for example heat. UVB filters can be oil-soluble or water-soluble. Examples of oil-soluble substances are: > 3-benzylidene camphor or 3-benzylidene norcampher and its derivatives, for example 3- (4-methylbenzylidene) camphor as described in EP 0693471 B1;

> 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and amyl 4- (dimethylamino) benzoate;

> Esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, propyl 4-methoxycinnamate, 2-cyano-3,3-phenylcinnamate-2-ethylhexyl ester (octocrylene) 4-methoxycinnamate;

> Esters of salicylic acid, preferably salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropyl benzyl ester, salicylic acid homomethyl ester;

> Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone;

> Esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate;

> Triazine derivatives, such as 2,4 ₎ 6-trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1, 3,5-triazine and octyl triazone, as described in EP 0818450 A1 or dioctyl butamido Triazone (Uvasorb® HEB);

> Propane-1,3-dione, e.g. 1 - (4-tert-butylphenyl) -3- (4'methoxyphenyl) propane-1,3-dione;

> Ketotricyclo (5.2.1.0) decane derivatives, as described in EP 0694521 B1.

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-sulfonic acid and its salts;

> Sulfonic acid derivatives of 3-benzylidene camphor, e.g. 4- (2-oxo-3-bornylidene methyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and their salts.

Derivatives of benzoylmethane, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1, 3-dione, 4-tert-butyl, are particularly suitable as typical UV-A filters -4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) propane-1, 3-dione and enamine compounds as described in DE 19712033 A1 (BASF). The UV-A and UV-B filters can of course also be used in mixtures. Particularly favorable combinations consist of the derivatives of benzoylmethane, e.g. 4-tert-butyl-4'-methoxydibenzoylmethane (Parsol 1789) and 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene) in combination with esters of cinnamic acid , preferably 4-methoxycinnamic acid-2-ethylhexyl ester and / or 4-methoxycinnamic acid propyl ester and / or 4-methoxycinnamic acid isoamyl ester. Such combinations are advantageous nations combined with water-soluble filters such as 2-phenylbenzimidazole-5-sulfonic acid and their alkali, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts.

In addition to the soluble substances mentioned, insoluble light protection pigments, namely finely dispersed metal oxides or salts, are also suitable for this purpose. Examples of suitable metal oxides are, in particular, zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof. Silicates (talc), barium sulfate or zinc stearate can be used as salts. The oxides and salts are used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics. 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, but it is also possible to use particles which have an ellipsoidal shape or a shape which differs from the spherical shape in some other way. The pigments can also be surface treated, i.e. are hydrophilized or hydrophobized. Typical examples are coated titanium dioxides, e.g. Titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Silicones, and in particular trialkoxyoctylsilanes or simethicones, are particularly suitable as hydrophobic coating agents. So-called micro- or nanopigments are preferably used in sunscreens. Micronized zinc oxide is preferably used. Further suitable UV light protection filters can be found in the overview by P.Finkel in SÖFW Journal 122, 543 (1996) and Perfumery and Cosmetics 3 (1999), page 11ff.

In addition to the two aforementioned groups of primary light stabilizers, secondary light stabilizers of the antioxidant type can also be used, which interrupt the photochemical reaction chain which is triggered when UV radiation penetrates the skin. Typical examples include amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (e.g. urocanic acid) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L-carosin and their derivatives (e.g. Anserine), carotenoids, carotenes (e.g. α-carotene, ß-carotene, lycopene) and their derivatives, chlorogenic acid and their derivatives, lipoic acid and their derivatives (e.g. dihydroliponic acid), aurothioglucose, propylthiouracil and other thiols (e.g. thioredoxin, glu tathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters ) and their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) as well as sulfoximine compounds (e.g. buthioninsulfoximines, homocysteine sulfoximine, butioninsulfones, penta-, hexa-, hexathion) gerin compatible doses (eg pmol to μmol / kg), (metal) chelators (eg α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (eg citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts , Bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (e.g. γ-linolenic acid, linoleic acid, oleic acid), folic acid and their derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and derivatives (e.g. ascorbyl palmitate, Mg-ascorbyl phosphate, ascorbyl acetate), Tocopherols and derivatives (eg vitamin E acetate), vitamin A and derivatives (vitamin A palmitate) and coniferyl benzoate of benzoin, rutinic acid and its derivatives, α-glycosyl rutin, ferulic acid, furfurylidene glucitol, camosine, butylated hydroxytoluene, butylated hydroxyanisole , Nordihydroguajakarzäure, Nordi- hydroguajaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, superoxide dismutase, zinc and its derivatives (e.g. ZnO, ZnS0 ₄ ) selenium and its derivatives (e.g. selenium methionine), stilbenes and their derivatives ( eg stilbene oxide, trans-stilbene oxide) and the derivatives suitable according to the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these Active substances.

Bioqene active ingredients

Biogenic active substances are, for example, tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, deoxyribonucleic acid, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts and vitamin complexes to understand.

Deodorants and germ inhibitors

Cosmetic deodorants counteract, mask or eliminate body odors. Body odors arise from the action of skin bacteria on apocrine sweat, whereby unpleasant smelling breakdown products are formed. Accordingly, deodorants contain active ingredients which act as germ-inhibiting agents, enzyme inhibitors, odor absorbers or odor maskers. In principle, all substances effective against gram-positive bacteria are suitable as germ-inhibiting agents, such as. B. 4-hydroxybenzoic acid and its salts and esters, N- (4-chlorophenyl) -N ^' - (3,4 dichlorophenyl) urea, 2,4,4 ^' trichloro-2 ^' hydroxydiphenyl ether (triclosan), 4-chloro -3,5-dimethylphenol, 2,2 ^{'-methylene-bis} (6-bromo-4-chlorophenol), 3-methyl-4- (1-methylethyl) phenol, 2-benzyl-4-chlorophenol, 3- (4 -Chlorphenoxy) -1, 2-propanediol, 3-iodo-2-propynyl butyl carbamate, chlorhexidine, 3,4,4 ^' trichlorocarbanilide (TTC), antibacterial fragrances, thymol, thyme oil, eugenol, clove oil, menthol, mint oil, farnesol , Phenoxyethanol, glycerol monocaprinate, glycerol monocaprylate, glycerol monolaurate (GML), diglycerol monocaprinate (DMC), salicylic acid N-alkylamides such as, for. B. salicylic acid-n-octylamide or salicylic acid-n-decylamide. Esterase inhibitors, for example, are suitable as enzyme inhibitors. These are preferably trialkyl citrates such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and in particular triethyl citrate (Hydagen® CAT, Henkel KGaA, Düsseldorf / FRG). The substances inhibit enzyme activity and thereby reduce odor. Other substances which can be considered as esterase inhibitors are sterol sulfates or phosphates, such as, for example, lanosterol, cholesterol, campesteric, stigmasterol and sitosterol sulfate or phosphate, dicarboxylic acids and their esters, such as, for example, glutaric acid, glutaric acid monoethyl ester, glutaric acid diethyl ester, Adipic acid, adipic acid monoethyl ester, adipic acid diethyl ester, malonic acid and malonic acid diethyl ester, hydroxycarboxylic acids and their esters such as citric acid, malic acid, tartaric acid or tartaric acid diethyl ester, and zinc glycinate.

Suitable odor absorbers are substances that absorb odor-forming compounds and can retain them to a large extent. They lower the partial pressure of the individual components and thus also reduce their speed of propagation. It is important that perfumes must remain unaffected. Odor absorbers are not effective against bacteria. They contain, for example, a complex zinc salt of ricinoleic acid or special, largely odorless fragrances, which are known to the person skilled in the art as "fixators", such as, for example, the main component. B. extracts of Labda- num or Styrax or certain abietic acid derivatives. Fragrance agents or perfume oils act as odor maskers and, in addition to their function as odor maskers, give the deodorants their respective fragrance. Perfume oils are, for example, mixtures of natural and synthetic fragrances. Natural fragrances are extracts of flowers, stems and leaves, fruits, fruit peels, roots, woods, herbs and grasses, needles and branches as well as resins and balms. Animal raw materials, such as civet and castoreum, are also suitable. Typical synthetic fragrance compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Fragrance compounds of the ester type are, for example, benzyl acetate, p-tert-butylcyclohexyl acetate, linalyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, the aldehydes include, for example, the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones include, for example, the jonones and methylcedryl ketone, and the alcohols are anethole, citronellellone Eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the teφene and balsams. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Essential oils of lower volatility, which are mostly used as aroma components, are also suitable as perfume oils, e.g. sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, oliban oil, gal Banum oil, Labdanum oil and Lavandin oil. Bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, -hexylcinnamaldehyde, geraniol, benzylacetone, cyclamenaldehyde, linalool, boisambrene forte, ambroxan, indole, hedione, sandelice, lemon oil, mandarin allyl oil, allyl oil alcohol, orangolamine oil, orangolamine oil, orangolamine oil, orangolamine oil, orangolamine oil, orangolamine oil, Lavandin oil, muscatel sage oil, ß-damascone, geranium oil bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, evernyl, iraline gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilate, irotyl and floramate alone used in mixtures.

Antiperspirants (antiperspirants) reduce sweat formation by influencing the activity of the eccrine sweat glands and thus counteract armpit wetness and body odor. Aqueous or anhydrous formulations of antiperspirants typically contain the following ingredients:

astringent active ingredients,

> Oil components,

> nonionic emulsifiers,

> Co-emulsifiers,

> Consistency generator,

> Auxiliaries such as B. thickeners or complexing agents and / or

> non-aqueous solvents such as As ethanol, propylene glycol and / or glycerin.

Salts of aluminum, zirconium or zinc are particularly suitable as astringent antiperspirant active ingredients. Such suitable antiperspirant active ingredients are e.g. Aluminum chloride, aluminum chlorohydrate, aluminum dichlorohydrate, aluminum sesquichlorohydrate and their complex compounds e.g. B. with propylene glycol-1, 2nd Aluminum hydroxyallantoinate, aluminum chloride tartrate, aluminum zirconium trichlorohydrate, aluminum zirconium tetrachlorohydrate, aluminum zirconium pentachlorohydrate and their complex compounds z. B. with amino acids such as glycine. In addition, customary oil-soluble and water-soluble auxiliaries can be present in smaller amounts in antiperspirants. Such oil soluble aids can e.g. his:

> anti-inflammatory, skin-protecting or fragrant essential oils,

> synthetic skin-protecting agents and / or

> Oil-soluble perfume oils.

Usual water-soluble additives are, for example, preservatives, water-soluble fragrances, pH-adjusting agents, for example buffer mixtures, water-soluble thickeners, for example water-soluble natural ones or synthetic polymers such as xanthan gum, hydroxyethyl cellulose, polyvinyl pyrrolidone or high molecular weight polyethylene oxides.

film formers

Common film formers are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives, collagen, hyaluronic acid or its salts and similar compounds.

Antidandruff agents

Piroctone olamine (1-hydroxy-4-methyl-6- (2,4,4-trimythylpentyl) -2- (1 H) -pyridinone monoethanolamine salt), Baypival® (climbazole), Ketoconazol®, (4-acety I - 1 - {-4- [2- (2.4-dichlorophenyl) r-2- (1 H -imidazol-1-ylmethyl) -1, 3-dioxylan-c-4-ylmethoxyphenyl} piperazine, ketoconazole, elubiol, selenium disulfide , Sulfur colloidal, sulfur polyethylene glycol sorbitan monooleate, sulfur ricinole polyhexylate, sulfur tar distillates, salicylic acid (or in combination with hexachlorophene), undexylenic acid monoethanolamide sulfosuccinate sodium salt, Lamepon® UD (protein undecylenate pyrithione pithionate) Magnesium sulfate in question.

swelling agent

Montmorillonites, clay minerals, pemulene and alkyl-modified carbopol types (Goodrich) can serve as swelling agents for aqueous phases. Further suitable polymers or swelling agents can be found in the overview by R. Lochhead in Cosm.Toil. 108, 95 (1993).

Insect repellents

Suitable insect repellents are NN-diethyl-m-toluamide, 1, 2-pentanediol or ethyl butylacetylaminopropionate Self-tanners and depiqmentants

Dihydroxyacetone is suitable as a self-tanner. Arbutin, kojic acid, coumaric acid and ascorbic acid (vitamin C) can be used as tyrosine inhibitors, which prevent the formation of melanin and are used in depigmenting agents.

Hvdrotrope

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. The polyols can also contain further functional groups, in particular amino groups, or be modified with nitrogen. Typical examples are

> Glycerin;

> Alkylene glycols, such as 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 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;

> Dialcohol amines, such as diethanolamine or 2-amino-1, 3-propanediol.

preservative

Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid and the other classes of substances listed in Appendix 6, Parts A and B of the Cosmetics Ordinance. perfume oils

Perfume oils include mixtures of natural and synthetic fragrances. Natural fragrances are extracts of flowers (lily, lavender, roses, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, coriander, caraway, juniper), fruit peel (bergamot, lemon, Oranges), roots (mace, angelica, celery, cardamom, costus, iris, calmus), wood (pine, sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme), Needles and twigs (spruce, fir, pine, mountain pine), resins and balms (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials, such as civet and castoreum, are also suitable. Typical synthetic fragrance compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalylbenzoate, benzyl formate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallyl propylate and benzylate propionate. The ethers include, for example, benzyl ethyl ether, the aldehydes e.g. the linear alkanals with 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the Jonone, α-lsomethylionon and Methylcedrylketon, to the alcohols Anethol, Citronellol, Eugenol, Isoeugenol, Geraniol, Linalool, Phenylethylalkohol and Teφineol, to the hydrocarbons belong mainly the Terpenes and Balsame. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Essential oils of lower volatility, which are mostly used as aroma components, are also suitable as perfume oils, e.g. Sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labolanum oil and lavandin oil. Bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, α-hexylcinnamaldehyde, geraniol, benzylacetone, cyclamenaldehyde, linalool, boi sambrene forte, ambroxan, indole, hedione, sandelice, lemon oil, mandarine oil, cycloamyl alcohol, orange amyl glycol, orange oil, almond oil, orange oil, are preferred , Lavandin oil, muscatel sage oil, ß-damascone, geranium oil bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilllate, irotyl and floramate alone Mixtures used.

dyes

Dyes which can be used are those which are suitable and approved for cosmetic purposes, as described, for example, in the publication "Cosmetic Dyes" of Substance commission of the Deutsche Forschungsgemeinschaft, Verlag Chemie, Weinheim, 1984, pp.81-106. These dyes are usually used in concentrations of 0.001 to 0.1% by weight, based on the mixture as a whole.

The total proportion of auxiliaries and additives can be 1 to 80, preferably 5 to 50 and in particular 7 to 10% by weight, based on the composition. The agents can be produced by customary cold or hot emulsions or else by the PIT process.

Examples

I. Production of acylamino acids

Example 1: Preparation of Ci2-Ci8-Acylglutamate-di-sodium salt without removal of the solvent

1300 kg of water, 10 kMol = 1870 kg of monosodium glutamate (x 1 H2O), 100 kg of isopropyl alcohol and 1100 kg of 33% sodium hydroxide solution are placed in a 15 m ³ reactor (Fig. 1) and stirred until a bright solution is formed. Then it is cooled to 10 to 20 ° C. The reactor and also the circuit are provided with a cooling jacket, which ensures the removal of the heat of reaction and a maximum temperature of 20 to 25 ° C. The pH is adjusted to about 12 with 11% sodium hydroxide solution before the start of the reaction. Then 7.7 kMol = 1825 kg cocoyl fatty acid chloride and 4500 kg 11% NaOH simultaneously (see plant concept) so that the reactor temperature does not exceed 20 to 25 ° C and the pH is between 11, 5 and 12.5. In the case of the sodium hydroxide solution, the two reactants are preferably dipped into the reactor, ie below the surface of the reaction mixture, and in the case of the acid chloride from the storage container in or in front of the mixer. A circulation pump ensures that the reaction mixture is circulated throughout the reaction, the return of the mixture taking place submerged in the reactor, ie below the surface of the reaction mixture. After the fatty acid chloride has been added, the mixture is stirred for a further 2 hours at 20 to 25 ° C. and then heated to 60 to 80 ° C. for a further 2 hours. The mixture is then allowed to cool to room temperature and the pH of the reaction mixture is adjusted to approximately 10 by adding dilute hydrochloric acid.

The content of Ci2-Ci8-acylglutamate-di-sodium salt in the finished product is 26%.

Example 2: Preparation of Ci2-Ci8-Acylglutamate-di-sodium salt without removal of the solvent

1300 kg of water, 10 kmol = 1870 kg of monosodium glutamate (x 1 H2O), 135 kg of ethanol and 1100 kg of 33% sodium hydroxide solution are placed in a 15 m ³ reactor (FIG. 1) and stirred until a bright solution is formed. Then it is cooled to 10 to 20 ° C. The reactor and also the circuit are provided with a cooling jacket, which ensures the removal of the heat of reaction and a maximum temperature of 20 to 25 ° C. The pH value is checked before the start of the reaction 11% sodium hydroxide solution adjusted to approx. 12. Then 7.7 kMol = 1825 kg cocoyl fatty acid chloride and 4500 kg 11% NaOH simultaneously (see plant concept) so that the reactor temperature does not exceed 20 to 25 ° C and the pH is between 11, 5 and 12.5. The two reactants are preferably dipped into the reactor in the case of the sodium hydroxide solution, ie below the surface of the reaction mixture, and in the case of the acid chloride from the container in or in front of the mixer. A circulation pump ensures that the reaction mixture is circulated throughout the reaction, the return of the mixture taking place submerged in the reactor, ie below the surface of the reaction mixture. After the fatty acid chloride has been added, the mixture is stirred for a further 2 hours at 20 to 25 ° C. and then heated for a further 2 hours to 60 to 80 ° C. The mixture is then allowed to cool to room temperature and the pH of the reaction mixture is adjusted Add diluted hydrochloric acid to about 10.

The content of Ci2-Ci8-acylglutamate-di-sodium salt in the finished product is 27.6%.

Example 3: Preparation of Ci2-Ci8-acylglutamate-di-sodium salt without removal of the solvent

In a 15 m ³ reactor (Fig. 1), 1300 kg of water, 10 kMol = 1870 kg of monosodium glutamate (x 1 H2O), 160 kg of diethylene glycol monoethyl ether and 1100 kg of 33% sodium hydroxide solution are introduced and stirred until a bright solution is formed. Then it is cooled to 10 to 20 ° C. The reactor and also the circuit are provided with a cooling jacket, which ensures the removal of the heat of reaction and a maximum temperature of 20 to 25 ° C. The pH is adjusted to about 12 with 11% sodium hydroxide solution before the start of the reaction. Then 7.7 kMol = 1825 kg cocoyl fatty acid chloride and 4500 kg 11% NaOH simultaneously (see plant concept) so that the reactor temperature does not exceed 20 to 25 ° C and the pH is between 11, 5 and 12.5. The two reactants are preferably dipped into the reactor in the case of the sodium hydroxide solution, ie below the surface of the reaction mixture, and in the case of the acid chloride from the container in or in front of the mixer. A circulation pump ensures that the reaction mixture is circulated throughout the reaction, the return of the mixture taking place submerged in the reactor, ie below the surface of the reaction mixture. After the fatty acid chloride has been added, the mixture is stirred for a further 2 hours at 20 to 25 ° C. and then heated to 60 to 80 ° C. for a further 2 hours. The mixture is then allowed to cool to room temperature and the pH of the reaction mixture is adjusted to approximately 10 by adding dilute hydrochloric acid.

The content of Ci2-Ci8-acylglutamate-di-sodium salt in the finished product is 27.6%. Example 4: Preparation of Ci2-Ci8-Acylglutamate-di-sodium salt with removal of the solvent

1300 kg of water, 10 kMol = 1870 kg of monosodium glutamate (x 1 H2O), 160 kg of isopropanol and 1100 kg of 33% sodium hydroxide solution are placed in a 15 m ³ reactor (FIG. 1) and stirred until a bright solution is formed. Then it is cooled to 10 to 20 ° C. The reactor and also the circuit are provided with a cooling jacket, which ensures the removal of the heat of reaction and a maximum temperature of 20 to 25 ° C. The pH is adjusted to about 12 with 11% sodium hydroxide solution before the start of the reaction. Subsequently, 7.7 kMol = 1825 kg cocoyl fatty acid chloride 4500 kg 11% NaOH are metered in simultaneously (see plant concept) so that the reactor temperature does not exceed 20 to 25 ° C and the pH is between 11, 5 and 12.5. The two reactants are preferably dipped into the reactor in the case of the sodium hydroxide solution, ie below the surface of the reaction mixture, and in the case of the acid chloride from the container in or in front of the mixer. A circulation pump ensures that the reaction mixture is circulated throughout the reaction, the return of the mixture taking place submerged in the reactor, ie below the surface of the reaction mixture. After the fatty acid chloride has been added, the mixture is stirred for a further 2 hours at 20 to 25 ° C. and then heated to 60 to 80 ° C. for a further 2 hours.

If desired, the pressure is reduced to 300 to 400 mbar and a mixture of isopropanol / water is distilled off at 60 to 80 ° C. In order to avoid concentrating the reaction mixture and to make the distillation more effective, steam is metered in at the same time. About 1845 kg of isopropanol / water distill off within one hour. The isopropanol content is reduced from 1.5% to approximately 9 ppm.

After cooling to room temperature, the solution is adjusted to about pH = 10 with dilute hydrochloric acid and optionally adjusted to the desired final concentration by adding water.

Example 5:

540 kg of 1,2-propylene glycol are added to the product prepared according to Example 2. Comparative Example 1: Preparation of Ci2-Ci8-Acylglutamate disodium salt

In a 15 m ³ reactor (Fig. 2), 2279 kg of water, 10 kMol = 1870 kg of monosodium glutamate (x 1 H2O) and 1870 kg of 25% sodium hydroxide solution are introduced and stirred until a bright solution is formed. Then it is cooled to 10 to 20 ° C. The reactor is equipped with a cooling jacket, which ensures that the heat of reaction is dissipated and a maximum temperature of 20 to 25 ° C is guaranteed. Before the start of the reaction, the pH is adjusted to about 12 using 25% sodium hydroxide solution. Then 7.7 kMol = 1825 kg cocoyl fatty acid chloride and 1540 kg 25% NaOH are metered in simultaneously so that the reactor temperature does not exceed 20 to 25 ° C and the pH is between 11, 5 and 12.5. The two reactants are preferably metered into the reactor, ie below the surface of the reaction mixture. The reaction mixture is stirred intensively with an Ikato-Intermig stirrer at a speed of 120 / min.

After dosing 208 kg of acid chloride and 180 kg of 25% sodium hydroxide solution, the experiment must be stopped because the foam is up to the edge of the 15 m ³ reactor (net content: 6407 kg).

Claims

claims

1. A process for the preparation of acylamino acids, in which a mixture of at least one amino acid or its salt and an alkali source is placed in a reactor and this is placed in or before a mixing element with fatty acid halides of the formula (I),

R ¹ COX (I)

in which R ^{1 represents} an alkyl or alkenyl radical having 6 to 22 carbon atoms and X represents choir, bromine iodine.

2. The method according to claim 1, characterized in that the amino acids used are glutamic acid, sarcosine, aspartic acid, alanine, valine, leucine, isoleucine, proline, hydroxyproline, glycine, serine, cysteine, cystine, threonine, histidine and salts thereof.

3. The method according to claims 1 and / or 2, characterized in that alkali metal hydroxide or carbonate or amines or mixtures thereof are used as alkali sources in water and / or water-soluble organic solvents.

4. The method according to at least one of claims 1 to 3, characterized in that dynamic or static mixers are used as the mixing element.

5. The method according to at least one of claims 1 to 4, characterized in that the reactor and the mixing element are connected to one another via a circulation system.

6. The method according to at least one of claims 1 to 5, characterized in that in the reactor further water-soluble or water-dispersible organic solvents are selected which are selected from the group consisting of acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, methanol, ethanol, Propanol, i-propanol, butanol, t-butanol, pentanol, isopentanol, trimethylhexanol, glycerin, ethylene glycol, 2-methyl-propanediol-1, 3, propylene glycol, dipropylene glycol, 1, 3 butylene glycol, 1, 2-butanediol , 1, 4-butanediol, isopentyldiol, sorbitol, xylitol, mannitol, erythritol, pentaerythritol, ethanolamine, triethanolamine, 2-amino-2-methyl-propanol, 1-amino-propanol-2, 1-amino-butanol-2 , 1-methoxy-2-propanol, 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1 -Propoxy-2-propanol, 1-isopropoxy-2-propanol, 1-butoxy-2-propanol, 1-isobutoxy-2-propanol, methoxyisopropanol, diethylene glycol colmonomethy- ether, diethylene glycol monoethyl ether, Diethylenglycolmonopropylether, Diethylenglycolmoni- sopropylether, diethylene glycol mono-butyl ether, triethylene glycol monomethyl ether, triethylene lenglycolmonoethylether, Triethylenglycolmonopropylether, Triethylenglycolmonisopropylether, triethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, Dipropylenglycolmo- noethylether, Dipropylenglycolmonopropylether, Dipropylenglycolmonisopropylether, dipropylene lenglycolmonobutylether, hexylene glycol, triacetin, Propylenncarbonat, glycerol

7. The method according to at least one of claims 1 to 6, characterized in that after the reaction of the amino acids with fatty acid halide has ended, the residual content of water-soluble or water-dispersible organic solvent is not separated.

8. The method according to at least one of claims 1 to 7, characterized in that after the reaction of the amino acids with fatty acid halide has ended, one or more of the following solvents are mixed into the finished product: trimethylhexanol, glycerol, ethylene glycol, 2-methyl-propanediol-1, 3 , Propylene glycol, dipropylene glycol, 1, 3 butylene glycol, 1, 2-butanediol, 1, 4-butanediol, isopentyldiol, sorbitol, xylitol, mannitol, erythritol, pentaerythritol, 1-methoxy-2-propanol, 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-propoxy-2-propanol,

1-isopropoxy-2-propanol, 1-butoxy-2-propanol, 1-isobutoxy-2-propanol, methoxy isopropanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylenglycolmonopropylether, Diethylenglycolmonisopropylether.Diethylenglycolmonobutylether, Triethylenglycolmo- monomethyl ether, triethylene glycol monoethyl ether, Triethylenglycolmonopropylether, triethylene lenglycolmonisopropylether, triethylene glycol monobutyl ether , Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monisopropyl ether, dipropylene glycol monobutyl ether, hexylene glycol,

9. containing acylamino acid preparations,

(a) 3 to 10% by weight sodium chloride,

(b) 0.1 to 4% by weight of free fatty acids,

(c) 1 to 11% by weight of free amino acids,

(d) 0.1 to 6% by weight of low molecular weight alcohol and

(e) 30 to 80 weight percent water.

10. Use of acylamino acids according to claim 9 for use in cosmetic products and in detergents, dishwashing detergents and cleaning agents.