DE19949518A1 - Novel primary mono-fatty acid esters of glycerol self-condensation products, useful as surfactants in cosmetics, pharmaceuticals, foods, detergents or cleaning compositions, comprises specific structure - Google Patents

Abstract

Certain primary mono-fatty acid esters of glycerol self-condensation products are new. Primary mono-fatty acid esters of formula (I)-(VI) of glycerol self-condensation products are new. R<1> = 1-22C alkyl and/or alkenyl; a, b, p, q, r, s, t and u = 0-8, with only p or q being 0 in the case of compound (IV); and n and m = 1-8.

Description

Field of the Invention

The invention relates to new primary mono fatty acid esters of glycerol and their mixtures and their Use as an emulsifier and / or surfactant for the production of surface-active preparations.

State of the art

Surface-active preparations, especially those in the field of washing and cleaning agents as well as used in personal care mostly contain emulsifiers, such as for the game polyglycerol fatty acid esters (Manufacturing Chemist 11/1997, 30; H. Behrens, G. Mieth, Die Nah tion 1984, 28, 815). However, products are usually used which, due to their Production (alkaline catalyzed condensation of glycerol to polyglycerol, "statistical" esterifications tion of polyglycerol with fatty acids, cf. e.g. B. EP 19941228 B1) no structurally defined pure represent substances, but contain a large number of isomeric compounds as technical mixtures (linear, branched, cyclic polyglycerols and their mono-, di-, oligoester). They also show significant disadvantages with regard to emulsifier effect, toxicity, biodegradation, and Color and smell.

The object of the present invention was therefore to determine certain, structurally defined To provide mono fatty acid esters of self-condensation products of glycerol, which in Compared to the prior art, a particularly good skin tolerance and excellent Have emulsifying power and a better smell and a light color.

Description of the invention

The invention relates to primary monofatty acid esters of self-condensation products of glycerol of the formulas (I) to (VI) and mixtures thereof

in which R ^{1 is} a linear and / or branched alkyl and / or alkenyl radical having 1 to 22 carbon atoms and preferably 6 to 18 carbon atoms and a and b independently of one another for numbers from 0 to 8, q and p independently of one another for numbers from 0 to 8, with the proviso that only q or p can be 0, n and m independently of one another are numbers from 1 to 8 and r and s and t and u independently of one another from numbers from 0 to 8.

Surprisingly, it was found that certain, structurally defined primary Monofatty acid esters of self-condensation products of glycerol according to the literature Have the process produced in good yields as part of multi-stage organic synthesis. It could be found that such structurally defined primary monoesters are not only a particularly good skin tolerance but also by an excellent  Emulsifying power compared to established products, the corresponding secondary ones Award monoesters or the corresponding diesters. In addition, these products show smell better and have a lighter color.

Primary monofatty acid esters of self-condensation products of glycerol

Linear and / or branched monoesters based on linear or branched or cyclic polyglycerol with a degree of condensation of 1 to 7, in particular 2 to 4, and linear, branched and / or unsaturated fatty acids with 1 to 22, preferably 6 to 18 and especially 12 to 16 carbon atoms. Primary monofatty acid esters are preferably the Formula (I) in which a and b independently of one another represent 0 or 1, of the formula (II) and / or (III), in the n and m independently of one another represent numbers from 1 to 4, preferably 2 to 3 and / or the Formula (IV) in which p represents numbers from 1 to 4, preferably 2 to 3 and q represents 0 or 1 and / or of the formula (V) in which r and s independently of one another are 0 to 4, preferably 1 to 3 and / or of the formula (VI) in which t and u independently of one another for 0 to 4, preferably 1 to 3 stand, used.

The ester structures (I) to (VI) preferred according to the invention are characterized in that the Linking the acyl residue of the fatty acid with the polyglycerol skeleton via a terminal, primary -OH group, in the immediate vicinity of only one secondary, free -OH group (in the case of linear or branched polyglycerols) or without further free -OH groups in the immediate aftermath partnership (in the case of branched or cyclic polyglycerols, e.g. fatty acid monoesters of β, β- Diglycerin or fatty acid monoester of 2,6-di (hydroxymethyl) -1,4-dioxane) takes place. Especially The very good skin tolerance and the excellent emulsifier effect have proven to be advantageous of these products compared to products from the prior art.

Another object of the invention is therefore the use of the primary according to the invention Monofatty acid esters (I) to (VI) and their mixtures for the preparation of surface-active Preparations, preferably cosmetic and / or pharmaceutical formulations or Food preparations and in particular as surfactants in detergents and cleaning agents.

Manufacturing

The following are examples of some manufacturing examples of mono fatty acid esters from Self-condensation products of glycerol, which follow the formulas (I) to (VI), in more detail  described. Other primary monofatty acid esters not listed here can be analogously processes known from the literature are produced in the context of multi-stage organic syntheses.

Preparation of branched primary polyglycerol fatty acid monoesters of the formula (I)

Preparation of a β, β-diglycerol: The individual reaction steps are described in more detail in the Examples chapter (Example I), preparation of diglycerol lauryl monoester, formula (I) with a and b equal to 0). The esterification is preferably carried out enzymatically with trifluoroethyl laurate or other linear, branched and / or unsaturated fatty acid esters of trifluoroethanol with a fatty acid residue with 1 to 22 carbon atoms with lipase catalysis (Novozym® 435).

Production of (higher) branched oligomeric polyglycerol esters (I) a) Synthesis of a branched sec, sec, prim, prim triglycerol from 2,5-anhydro-D-mannitol with sol ketaltosylate (tosylated isopropylidene glycerol)

2,5-Anhydro-D-mannitol and solketal tosylate are etherified in the presence of NaH in DMF, in a phase transfer-catalyzed reaction with tetrabutylammonium iodide (TBAI, phase transfer catalyst, room temperature, 18 h). This is followed by ring opening with oxidation with NalO ₄ , reduction with NaBH ₄ , cleavage of the isopropylidene protecting group and peracetylation with acetic anhydride in pyridine. The sec, sec, prim, prim-triglycerin thus protected is deacetylated with sodium methoxide in methanol to give the desired compound (branched triglycerol). Esterification with N-alkoyl-thiazolidin-2-thione, where alkoyl is a linear, branched and / or unsaturated fatty acid residue with 1 to 22 carbon atoms, for the primary sec, sec, prim, prim triglycerol monofatty acid ester (formula (I) with a = 0 and b = 1).

b) Synthesis of a branched prim, prim, sec, sec, prim, prim tetraglycerol from 2,5-anhydro-D-man nitol with brine tosylate

As under a), 2,5-anhydro-D-mannitol is now with 2 equivalents of solketal tosylate in the presence of NaH etherified in DMF, in a phase transfer catalyzed reaction with tetrabutylammonium iodide (TBAI, phase transfer catalyst). This is followed by ring opening, reduction, and splitting off as in a) Isopropylidene protecting groups, peracetylation and then deacetylation to the desired prim, prim, sec, sec, prim, prim tetraglycerin. Esterification with N-alkoyl-thiazolidin-2-thione, where under Alkoyl is a linear, branched and / or unsaturated fatty acid residue with 1 to 22 carbon atoms understands, to the primary prim, prim, sec, sec, prim, prim tetraglycerol monofatty acid ester (formula (I) with a = 1 and b = 1).

Preparation of branched primary polyglycerol fatty acid monoesters of the formula (II)

Solketal and toluenesufonyl chloride are converted to 1,2-isopropylidene-3-O-p- in a substitution reaction. toluenesufonylglycerol implemented (Verb. A). Benzyl alcohol and epichlorohydrin are under phases transfer conditions etherified with tetrabutylammonium iodide (TBAI) to 1,3-di-O-benzylglycerol (Verb. B). A and B are converted to 1,2- under tetrabutylammonium bromide (TBAB) under phase transfer conditions. Etherified O-isopropylidene-6-O-benzyl-5-benzyloxymethyl-4-oxahexane-1,2,6-mol.

• a) 1,2-O-isopropylidene-6-O-benzyl-5-benzyloxymethyl-4-oxahexane-1,2,6-triol is boiled with acidic ion exchange resin in methanol to remove the isopropylidene protective group. 6-O-Benzyl-5-benzyloxymethyl-4-oxahexane-1,2,6-triol is obtained. This product is preferably esterified enzymatically with trifluoroethyl laurate or longer-chain linear, branched and / or unsaturated fatty acid esters of trifluoroethanol with lipase catalysis (Novozym® 435). Alternatively, a "classic" chemical esterification under basic conditions (NaH in THF) with 2-alkoyl-thiazolidin-2-thione is possible, where alkoyl is understood to mean a linear, branched and / or unsaturated fatty acid residue with 1 to 22 carbon atoms. The protected ester is obtained: 1-alkoyloxy-6-O-benzyl-5-benzyloxymethyl-4-oxapentane-2,6-diol. The benzyl groups are removed under reducing conditions (Pd / C, H ₂ -Atm.). The ester 1-alkoyl-5-hydroxymethyl-4-oxahexane-2,6-diol (formula (II) with n = 1) is obtained.
• b) Higher homologs can e.g. B. by etherification of 6-O-benzyl-5-benzyloxymethyl-4-oxahexane 1,2,6-triol with Solketal under phase transfer conditions (TBAB or TBAI), benzylation of the free OH group and subsequent removal of the isopropylidene groups among the above given conditions. Esterification is either chemical or before increases enzymatically possible. The benzyl protective groups are then cleaved off under redu decorative conditions (see above). The ester (II) with n = 2 is obtained.
• c) If 6-O-benzyl-5-benzyloxymethyl-4-oxahexane-1,2,6-triol is ring-opened with 1,2-epoxy-6,7-O- Isopropylidene-4-oxaheptane reacted, so after benzylation of the free OH groups, Removal of the isopropylidene group, subsequent esterification and debenzylation of the ester (II) with n = 3 u. s. w.

Production of linear primary polyglycerol fatty acid monoesters of the formula (III) 1. Primary diglycerol mono fatty acid ester

Starting with solketal and epichlorohydrin, tetrabutyl is obtained with phase transfer catalysis ammonium bromide (TBAB) 1,2-epoxy-6,7-O-isopropylidene-4-oxaheptane. This connection can then ring-opened directly with the desired fatty acid to the diglycerol monofatty acid ester the. The isopropylidene protecting group is then split off under acidic conditions. Alternatively the ring opening of 1,2-epoxy-6,7-O-isopropylidene-4-oxaheptane is carried out under basic conditions gene (NaOH, KOH) and then esterified with N-alkoyl-thiazolidin-2-thione, under Alkoyl is a linear, branched and / or unsaturated fatty acid residue with 1 to 22 carbon atoms understands. The isopropylidene protecting group is then split off under acidic conditions. Man receives the ester (III) with m = 1.

2. Primary triglycerol monofatty acid ester

In the chapter Examples (II) the individual reactions starting from Solketal for the production of Triglycerolmonolaurylester described in more detail. In reaction step (E), instead of N-lauroyl-  thiazolidin-2-thione generally N-alkoyl-thiazolidin-2-thione can be used, with alkoyl a linear, branched and / or unsaturated fatty acid residue with 1 to 22 carbon atoms understands. The ester (III) with m = 2 is obtained.

3. Primary tetraglycerol mono fatty acid ester

Starting from allyl glycidyl ether (from allyl alcohol and epichlorohydrin by etherification), m- Chloroperbenzoic acid epoxidizes to 1,2: 6,7-diepoxi-4-oxaheptane. This product comes with Solketal under phase transfer conditions (Cat .: Aliquat® 336) to 6,10-dihydroxy-1,2: 14,15-di-O- Isopropylidene-4,8,12-trioxapentadecane ring opened. Then the free OH groups are under Phase transfer conditions (Cat .: TBAB) benzylated (protected) with benzyl bromide. The Isopropylidene groups are split off with acidic ion exchange resin in boiling methanol and then with N-alkoyl-thiazolidine-2-thione becomes the primary, benzyl-protected tetraglycerol ester esterified. The benzyl protective groups are split off under reducing conditions with Pd / C under a hydrogen atmosphere to the free linear primary tetraglycerol ester (III) with m = 3.

4. Primary pentaglycerol mono fatty acid ester

Epichlorohydrin and allyl alcohol are converted to 6-hydroxy under phase transfer conditions (cat .: TBAB) 4,8-dioxaundecan-1,10-dien etherified, then the free OH group with phase transferbebe conditions (Cat .: TBAB) benzylated (protected) with benzyl bromide to 6-O-benzyl-4,8-dioxaundecane 1.10-dien. Then the double bonds are epoxidized with m-chloroperbenzoic acid to give 6-O-benzyl 1,2: 10,11-diepoxy-4,8-dioxaundecane. This product is using Solketal under phase transfer conditions (Cat .: Aliquat® 336) for 10-O-benzyl-6,14-dihydroxy-1,2: 18: 19-diisopropylidene 4,8,12,16-tetraoxanonadecane ring opened. Then the Isopropylidene groups under acidic conditions, esterification with N-alkoyl-thiazolidin-2-thione to primary benzyl-protected pentaglycerol esters and debenzylation under reducing Conditions with Pd / C under hydrogen atmosphere to the free linear primary pentaglycerol ester (III) with m = 4.

5. Higher oligomers

By combining allyl alcohol, epichlorohydrin and solketal accordingly build higher linear polyglycerol units.  

Preparation of branched primary polyglycerol fatty acid monoesters of the formula (IV)

Solketal and toluenesufonyl chloride are converted to 1,2-isopropylidene-3-O-p- in a substitution reaction. toluenesufonylglycerol implemented (Verb. A). Benzyl alcohol and epichlorohydrin are under phases transfer conditions etherified with tetrabutylammonium iodide (TBAI) to 1,3-di-O-benzylglycerol (Verb. B). A and B are converted to 1,2- under tetrabutylammonium bromide (TBAB) under phase transfer conditions. Etherified O-isopropylidene-6-O-benzyl-5-benzyloxymethyl-4-oxahexane-1,2,6-triol.

• a) 1,2-O-isopropylidene-6-O-benzyl-5-benzyloxymethyl-4-oxahexane-1,2,6-mol is treated with Pd / C under H ₂ atmosphere under reducing conditions to remove the benzyl groups. 1,2-O-isopropylidene-5-hydroxymethyl-4-oxahexane-1,2,6-triol is obtained. This is followed by esterification with 2-alkoyl-thiazolidin-2-thione. The isopropylidene-protected ester 1,2-O-isopropylidene-6-lauroyloxy-5-hydroxymethyl-4-oxahexane-1,2-diol is boiled in methanol with acidic ion exchange resin to remove the isopropylidene group. The free primary ester (IV) according to the invention with p = 1 and q = 0: 6-alkoyloxy-5-hydroxymethyl-4-oxahexane-1,2-diol is obtained.
• b) Higher homologues can be etherified by etherification of 6-O-benzyl-5-benzyloxymethyl-4-oxahexane-1,2,6-triol with solketal under phase transfer conditions (TBAB or TBAI). After debenzylation of the OH groups under reducing conditions (Pd / C, H ₂ atmosphere), esterification and subsequent removal of the isopropylidene group as described above, the invention. Esters (IV) with p = 2 and q = 0).
• c) If 6-O-benzyl-5-benzyloxymethyl-4-oxahexane-1,2,6-triol is ring-opened with 1,2-epoxy-6,7-O- Isopropylidene-4-oxaheptane implemented, so you get after debenzylation of the OH groups reducing conditions, esterification and subsequent removal of the isopropylidene group the ester (IV) with p = 3 and q = 0 u. s. w.
• d) synthesis of a branched sec, prim, prim, sec triglycerol from epichlorohydrin and benzyl alcohol
  

Epichlorohydrin is ring-opened with benzyl alcohol under phase transfer catalysis with TBAI (KOH, water, 70 ° C, 48 h) and etherified to 1,3-dibenzylglycerol. 1,3-Dibenzylglycerol is ring-opened with further epichlorohydrin under phase transfer catalysis with TBAI (KOH, water, 70 ° C., 48 h) and etherified to tetrabenzyl-sec, prim, prim, sec-triglycerin.

This benzyl derivative is deprotected (cleavage of the benzyl groups under reducing conditions with Pd / C under a hydrogen atmosphere) and with N-alkoyl-thiazolidin-2-thione (alkoyl = linear, branched and / or unsaturated fatty acid residue with 1 to 22 carbon atoms) or as in the example represented with N-lauroyl-thiazolidin-2-thione for the primary sec, prim, prim, sec Triglycerol monofatty acid ester esterified (formula (IV) with p = 1 and q = 1).

Preparation of cyclic primary polyglycerol fatty acid monoesters of the formulas (V) and (VI)

Allyl glycidyl ether is ring-opened with basic benzyl alcohol under basic conditions (NaH, room temperature, 4 hours) and terminally benzylated. The 6-hydroxy-7-O-benzyl-4-oxahept-1-ene thus obtained is iodocyclized with N-iodosuccinimide (NIS) (allylic iodination and ring closure) to give 2-iodomethyl-6-O-benzylmethyl-1,4- dioxane. Alternatively, the reaction can also be carried out with N-bromosuccinimide. The protected ester is then prepared by reaction with the corresponding fatty acid in a nucleophilic substitution under basic conditions (K ₂ CO ₃ ). Under reducing conditions (Pd / C, H ₂ , CH ₃ OH) the benzyl protecting group is split off and the desired free ester 2-hydroxymethyl-6-O-alkoylmethyl-1,4-dioxane is obtained in 83% yield (formula ( V) with r and s = 0).

The 2,5-disubstituted monoester is obtained from the six-membered benzaldehyde acetal of glycerol: by etherification of the free 2-OH group of 1,3-acetalized glycerol with allyl bromide under phase transfer conditions (NaH, TBAB) and subsequent reduction of the acetal to the benzyl ether with DIBAH 5-hydroxymethyl-6-O-benzyl-4-oxahex-1-ene is obtained. This is iodocyclized with NIS to give 2-iodomethyl-5-O-benzylmethyl-1,4-dioxane. The protected ester is then prepared by reaction with the corresponding fatty acid in a nucleophilic substitution under basic conditions (K ₂ CO ₃ ). Under reducing conditions (Pd / C, H ₂ , CH ₃ OH) the benzyl protecting group is split off and the desired free ester 2-hydroxymethyl-5-O-alkoylmethyl-1,4-dioxane (formula (VI) with t and u = 0).

Higher homologs are obtained, for example, by etherification (nucleophilic substitution) of 2- Iodomethyl-6-O-benzylmethyl-1,4-dioxane or 2-iodomethyl-5-O-benzylmethyl-1,4-dioxane with Solketal under phase transfer conditions (NaH, TBAB or TBAI), subsequent debenzylation under reducing conditions (Pd / C) and esterification of the free OH group with N-alkoylthiazolidin-2- thion, wherein under alkoyl a linear, branched and / or unsaturated fatty acid residue with 1 understands up to 22 carbon atoms. Then the isopropylidene group with acid Cleaved ion exchange resin in methanol and you get the desired free ester of Formula (V) with r = 1 and s = 0, or formula (VI) with t = 1 and u = 0). Will with after etherification Solketal first cleaved the isopropylidene group, then enzymatically esterified with Novozym® 435 and trifluoroethyl laurate or other linear, branched and / or unsaturated fatty acid esters of Trifluoroethanol with a fatty acid residue with 1 to 22 carbon atoms, you get after Debenzylation under reducing conditions the esters of formula (V) with r = 0 and s = 1 or (VI) with t = 0 and u = 1.

Lipases

In some of the reactions described above, lipases are used as the catalyst, which differs from Candida cylindracea, Candida lipolytica, Candida rugosa, Candida antarctica B, Candida utilis, Chro mobacterium viscosum, Geotrichum viscosum, Geotrichum candidum, Mucor javanicus, Mucor miehei, Porcine pancreas, Pseudomonas species, Pseudomodas fluorescens, Pseudomodas cepacia, Rhi zomucor miehei, Rhizopus arrhizus, Rhizopus delemar, Rhizopus niveus, Rhizopus oryzae, Aspergillus niger, Penicillium roquefortii, Penicillum cambertii, Pseudodomas fluorescens or an esterase Bacillus sp., Bacillus thermoglucosidasius, Mucor miehei, Horse liver, Saccharomyces cerevisiae, Pig derive liver. Both the lipases and a combination can be used here. The lipases are used in amounts which ensure adequate catalysis of the reaction. Lipases derived from Mucor miehei and Aspergillus niger are preferably used.  

In particular, Novozym® 388 L (Rhizomucor miehei Lipase, free), Lipozym® IM (Rhizomucor miehei lipase, immobilized), Novozym® 735 L (Candida antarctica B lipase, free), Novozym® 525 L (Candida antarctica B lipase, free) and / or Novozym® 435 (Candida antarctica B lipase, immobili siert) which products from Novo Nordisk (Denmark) represent.

Surface-active preparations

The polyglycerol monofatty acid esters according to the invention with a defined structure can be used for the preparation of surface-active preparations such as washing, rinsing, cleaning and fabric softening agents and cosmetic and / or pharmaceutical preparations for the care and cleaning of skin, Hair, mouth and teeth, such as hair lotions, foam baths, shower baths, creams, Gels, lotions, alcoholic and aqueous / alcoholic solutions, emulsions, wax / fat masses, Stick preparations or ointments, preferably hair shampoos, are used. These funds can also be as white tere auxiliaries and additives mild surfactants, oil bodies, emulsifiers, superfatting agents, pearlescent waxes, consistency agents, thickeners, polymers, silicone compounds, fats, waxes, lecite into it, phospholipids, stabilizers, biogenic agents, deodorants, antiperspirants, antiperspirants Pen agents, film formers, swelling agents, UV light protection factors, antioxidants, hydrotropes, preserves agents, insect repellents, self-tanners, tyrosine inhibitors (depigmentation agents), solubilis sators, perfume oils, dyes and the like contain.

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, α-olefin sulfonates, ether carboxylic acids and / or their alkali, alkaline earth and / or (alkyl) ammonium salts, 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 with 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 with linear C ₆ -C ₂₂ fatty alcohols, such as. B. myristyl myristate, myristyl palmitate, myristyl stearate, Myristylisostearat, myristyl, Myristylbehenat, Myristylerucat, cetyl myristate, cetyl palmitate, cetyl stearate, Cetylisostearat, cetyl oleate, cetyl behenate, Cetylerucat, Stearylmyristat, stearyl palmitate, stearyl stearate, Stearylisostearat, stearyl oleate, tribehenate Stearylbe, Stearylerucat, isostearyl, isostearyl palmitate, Isostearylstearat , isostearyl isostearate, Isostearyloleat, isostearyl behenate, Isostearyloleat, oleyl myristate, oleyl palmitate, oleyl stearate, Oley lisostearat, oleyl oleate, Oleylbehenat, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl, Behenylisostearat, behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate, erucyl, erucyl, erucyl, erucyl oleate, erucyl behenate and Erucylerucate. In addition, esters of linear C ₆ -C ₂₂ fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of hydroxycarboxylic acids with linear or branched C ₆ -C ₂₂ fatty alcohols, in particular dioctyl malates, esters of linear and / or branched fatty acids are also suitable 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, esters of C ₂ -C ₁₂ 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 C ₆ -C ₂₂ fatty alcohol carbonates, Guerbet carbonates, esters of benzoic acid e with linear and / or branched C ₆ -C ₂₂ alcohols (e.g. B. Finsolv® TN), linear or branched, symmetrical or asymmetrical dialkyl ether with 6 to 22 carbon atoms per alkyl group, ring opening products of epoxidized fatty acid reesters with polyols, silicone oils and / or aliphatic or naphthenic hydrocarbons, such as. B. as squalane, squalene or dialkylcyclohexane.

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 to linear Fatty alcohols with 8 to 22 carbon atoms, with fatty acids with 12 to 22 carbon atoms, with alkylphenols with 8 up to 15 carbon 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;
• - Adducts of 1 to 15 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;
• - Adducts of 15 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil;
• - Partial esters of glycerin and / or sorbitan (as technical mixtures) 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 mol Ethylene oxide;
• - Partial esters of polyglycerol (as technical mixtures, average degree of self-condensation 2 to 8), polyethylene glycol (molecular weight 400 to 5000), trimethylolpropane, pentaerythritol, Sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. methyl glucoside, butyl glucoside, lauryl glucoside) as well as polyglucosides (e.g. cellulose) with 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 moles of ethylene oxide;  
• - Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE 11 65 574 PS and / or mixed esters of fatty acids with 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerin or polyglycerin;
• - Mono-, di- and trialkyl phosphates as well as mono-, di- and / or tri-PEG-alkyl phosphates and their Salts;
• - wool wax alcohols;
• - Polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;
• - 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 substance quantities of ethylene oxide and / or propylene oxide and Substrate with which the addition reaction is carried out corresponds. C _12/18 fatty acid _monoesters and diesters of adducts of ethylene oxide with glycerol are known from DE 20 24 051 PS as refatting agents for cosmetic preparations.

Alkyl and / or alkenyl oligoglycosides, their preparation and their use are known from the prior art known in the art. They are produced in particular by reacting glucose or oligo saccharides with primary alcohols with 8 to 18 carbon atoms. Regarding the glycoside residue, that both monoglycosides, in which a cyclic sugar residue glycosidically attached to the fatty alcohol is bound, as well as oligomeric glycosides with a degree of oligomerization up to preferably about 8 are suitable. The degree of oligomerization is a statistical mean, one for such technical products are based on the usual homolog distribution.

Typical examples of suitable partial glycerides (industrial mixtures) are Hydroxystearic acid monoglyceride, hydroxystearic acid diglyceride, isostearic acid monoglyceride, Isostearic acid diglyceride, oleic acid monoglyceride, oleic acid diglyceride, ricinoleic acid moglyceride, Ricinoleic acid diglyceride, linoleic acid monoglyceride, linoleic acid diglyceride, linolenic acid monoglyceride, Linolenic acid diglyceride, erucic acid monoglyceride, erucic acid diglyceride, tartaric acid monoglyceride, Tartaric acid diglyceride, citric acid monoglyceride, citric diglyceride, malic acid monoglyceride, Malic acid diglyceride and their technical mixtures, which are subordinate to the Manufacturing process can still contain small amounts of triglyceride. Are also suitable Addition products of 1 to 30, preferably 5 to 10, moles of ethylene oxide onto the par tialglycerides.

Sorbitan monoisostearate, sorbitan sesquiisostearate, sorbitan diisostearate, Sorbitan triisostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, Sorbi tanmonoerucate, sorbitan sesquierucate, sorbitan dierucate, sorbitan trierucate, sorbitan monoricinoleate, Sor  bitansesquiricinoleate, sorbitan diricinoleate, sorbitan triricinoleate, sorbitan monohydroxystearate, sorbitan sesquihydroxystearate, sorbitan dihydroxystearate, sorbitan trihydroxystearate, sorbitan monotartrate, Sor bitansesquitartrate, sorbitan ditartrate, sorbitan tritartrate, sorbitan monocitrate, sorbitan sesquicitrate, sorbi tandicitrate, sorbitan tricitrate, sorbitan monomaleate, sorbitan sesquimaleate, sorbitan dimaleate, sorbitan tri maleate and their technical mixtures. Addition products from 1 to 30 are also suitable, preferably 5 to 10 moles of ethylene oxide to the sorbitan esters mentioned.

Typical examples of suitable polyglycerol esters (industrial mixtures) are polyglyceryl-2 Dipolyhydroxystearate (Dehymuls® PGPH), polyglycerol-3-diisostearate (Lameform® TGI), Polyglyceryl-4 isostearate (Isolan® GI 34), Polyglyceryl-3 oleate, Diisostearoyl Polyglyceryl-3 Diisostearate (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 those with 1 to 30 mol of ethylene oxide, if appropriate set mono-, di- and triesters of trimethylolpropane or pentaerythritol with lauric acid, coconut fat acid, tallow fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like.

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-dimethylam monium glycinate, for example the cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example the cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxyl -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 also 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 are. 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-alkylaminopropionic acid and alkylaminoacetic acid each with about 8 to 18 C atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-coconut alkylaminopropionate, coconut acylaminoethylaminopropionate and C _12/18 acyl sarcosine.

Finally, cationic surfactants are also suitable as emulsifiers, those of the Esterquats, preferably methylquaternized difatty acid triethanolamine ester salts, especially before are moving.

Substances such as lanolin and lecithin and polyethoxy can be used as superfatting agents lated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid al kanolamides are used, the latter also serving as foam stabilizers.

Pearlescent waxes, for example, are: alkylene glycol esters, especially ethylene glycol di stearate; 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 stearin 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 or hydroxy fatty alcohols with 12 to 22 and preferably 16 to 18 carbon atoms and in addition partial glycerides, fatty acids or hydroxy fat acids into consideration. A combination of these substances with alkyl oligoglucosides and / or is preferred Fatty acid N-methylglucamides of the same chain length and / or polyglycerol poly-12-hydroxystearates.

Suitable thickeners are, for example, Aerosil types (hydrophilic silicas), Polysac charide, 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), poly acrylamides, polyvinyl alcohol and polyvinyl pyrrolidone, surfactants such as ethoxylated fatty acid reglycerides, 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. e.g. B. amodimethicones, copolymers of adipic acid and dimethyla minohydroxypropyldiethylenetriamine (Cartaretine® / Sandoz), copolymers of acrylic acid with dimethyl diallylammonium chloride (Merquat® 550 / Chemviron), polyaminopolyamides, e.g. B. described in the FR 2252840 A and its crosslinked water-soluble polymers, cationic chitin derivatives as in for example, quaternized chitosan, optionally microcrystalline, condensation products 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 Celanese, quaternized ammonium salt polymers, such as. B. Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 der Miranol company.

Examples of anionic, zwitterionic, amphoteric and nonionic polymers are Vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / iso bornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and their esters, un mixed and crosslinked with polyols, acrylic acids, acrylamidopropyltrimethylammonium chloride / Acrylate copolymers, octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymers, vinylpyrrolidone / Dimethylaminoethyl methacrylate / vinylcaprolactam terpolymers and, if appropriate, derivatized Cellulose ethers and silicones in question.

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

Typical examples of fats are glycerides. Natural waxes, such as, for example, B. candelilla wax, carnauba wax, japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, montan wax, beeswax, shellac wax, walnut, lanolin (wool wax), pretzel fat, ceresin, ozokerite (earth wax), petrolatum, paraffin waxes chemically modified waxes (hard waxes), such as. B. Montanester waxes, Sasol waxes, hydrogenated jojoba waxes and synthetic waxes, such as. B. polyalkylene waxes and polyethylene glycol waxes in question. 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. Lecithins are therefore often referred to in the art as phosphatidylcholines (PC) and follow the general formula

where R typically for linear aliphatic hydrocarbon radicals with 15 to 17 carbon atoms men and up to 4 cis double bonds. The cephalins are examples of natural lecithins called, which are also called phosphatidic acids and derivatives of 1,2-diacyl-sn-glycerol-3- represent phosphoric acids. In contrast, phospholipids are usually understood to be mono- and preferably diesters of phosphoric acid with glycerin (glycerol phosphates), which are generally related to the fet ten can be expected. In addition, sphingosines or sphingolipids are also suitable.

Metal salts of fatty acids, such as. B. magnesium, aluminum and / or Zinc stearate or ricinoleate can be used.

Examples of biogenic active ingredients are tocopherol, tocopherol acetate, tocopherol palmitate, Ascorbic acid, deoxyribonucleic acid, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acid ren, amino acids, ceramides, pseudoceramides, essential oils, plant extracts and vitamin complexes to understand.

Cosmetic deodorants (deodorants) counteract, mask or mask body odors eliminate them. Body odors arise from the action of skin bacteria on apocrine Sweat, producing unpleasant smelling breakdown products. Accordingly included Deodorants active ingredients that act as germ inhibitors, enzyme inhibitors, or odor absorbers Odor maskers act.

In principle, all substances effective against gram-positive bacteria are anti-germ agents suitable, such as B. 4-hydroxybenzoic acid and its salts and esters, N- (4-chlorophenyl) -N '- (3,4 dichlor phenyl) 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- Chlorophenoxy) -1,2-propanediol, 3-iodo-2-propynyl butyl carbamate, chlorhexidine, 3,4,4'-trichlorocarbonilide (TTC), antibacterial fragrances, thymol, thyme oil, eugenol, clove oil, menthol, mint oil, farnesol, Phenoxyethanol, glycerol monolaurate (GML), diglycerol monocaprinate (DMC), salicylic acid N-alkylamides such as B. salicylic acid-n-octylamide or salicylic acid-n-decylamide.

Esterase inhibitors, for example, are suitable as enzyme inhibitors. This is before preferably around trialkyl citrates such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and ins  special triethyl citrate (Hydagen® CAT, Henkel KGaA, Düsseldorf / FRG). The substances inhibit the Enzyme activity and thereby reduce odor. Other substances that act as esterase inhibitors sterol sulfates or phosphates, such as lanosterol, cholesterol, Campesterin, 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, adipine acid monoethyl ester, adipic acid diethyl ester, malonic acid and malonic acid diethyl ester, hydroxycarb on acids and their esters such as citric acid, malic acid, tartaric acid or tartaric acid diethyl ester, and zinc glycinate.

Suitable as odor absorbers are substances which absorb odor-forming compounds and are widely used can hold on. They lower the partial pressure of the individual components and thus reduce them also their speed of propagation. It is important that perfumes remain unaffected sen. Odor absorbers are not effective against bacteria. For example, they contain as The main ingredient is a complex zinc salt of ricinoleic acid or a special, largely odorless Fragrances known to the person skilled in the art as "fixators", such as, for. B. extracts of labdanum or Styrax or certain abietic acid derivatives. Fragrance agents or par act as odor maskers for, in addition to their function as odor maskers, the deodorants their respective Give fragrance. Perfume oils include, for example, mixtures of natural and synthetic table 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 bal seeds. Animal raw materials, such as civet and castoreum, are also suitable. Typical synthetic fragrance compounds are products of the ester, ether, aldehyde, Ketones, alcohols and hydrocarbons. Fragrance compounds of the ester type are e.g. B. Ben cyanoacetate, 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, to the aldehydes z. B. the linear alkanals with 8 to 18 carbon atoms, citral, Citronellal, Citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, too the ketones e.g. B. the Jonone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, Isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol, belong to the hydrocarbons mainly the terpenes and balms. However, mixtures of different scents are preferred substances that together create an appealing fragrance. Essential oils also low Rer volatility, which are mostly used as aroma components, are suitable as perfume oils, for. B. 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, labdanum oil and lavandin oil. Bergamot oil, Dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, α-hexylcinnamaldehyde, geraniol, benzyl acetone, cyclamenaldehyde, linalool, boisambrene forte, ambroxan, indole, hedione, sandelice, citro nenoil, mandarin oil, orange oil, allylamyl glycolate, cyclover valley, lavandin oil, muscatel sage oil, β- Damascone, geranium oil bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP,  Evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilate, irotyl and Floramat used alone or 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 giver,
• - auxiliaries such. B. thickeners or complexing agents and / or
• - non-aqueous solvents such as As ethanol, propylene glycol and / or glycerin.

Salts of aluminum and zirconium are particularly suitable as astringent antiperspirant active ingredients or zinc. Such suitable antiperspirant active ingredients are e.g. B. aluminum chloride, Aluminum chlorohydrate, aluminum dichlorohydrate, aluminum sesquichlorohydrate and their complex compound dung z. B. with propylene glycol-1,2. Aluminum hydroxyallantoinate, aluminum chloride tartrate, aluminum Zirconium trichlorohydrate, aluminum zirconium tetrachlorohydrate, aluminum zirconium pentachlo crude hydrate and their complex compounds z. B. with amino acids such as glycine.

In addition, conventional oil-soluble and water-soluble auxiliaries can be present in smaller amounts in antiperspirants. Such oil-soluble aids can e.g. B. be:

• - anti-inflammatory, skin-protecting or fragrant essential oils,
• - synthetic skin-protecting agents and / or
• - oil-soluble perfume oils.

Usual water-soluble additives are e.g. B. preservatives, water-soluble fragrances, pH value Adjusting means, e.g. B. buffer mixtures, water-soluble thickeners, e.g. B. water-soluble natural or synthetic polymers such as B. xanthan gum, hydroxyethyl cellulose, polyvinyl pyrrolidone or high molecular weight polyethylene oxides.

As anti-dandruff agents, Octopirox® (1-hydroxy-4-methyl-6- (2,4,4-trimythylpentyl) -2- (1H) -pyri don-monoethanolamine salt), Baypival, piroctone olamine, Ketoconazol®, (4-acetyl-1 - {- 4- [2- (2.4-dichlor phenyl) r-2- (1H-imidazol-1-ylmethyl) -1,3-dioxylan-c-4-ylmethoxyphenyl} piperazine, selenium disulfide, Sulfur colloidal, sulfur polyethylene glycol sorbitan monooleate, sulfur ricinole polyethoxylate,  Sulfur tar distillates, salicylic acid (or in combination with hexachlorophene), undexylenic acid Monoethanolamide sulfosuccinate Na salt, Lamepon® UD (protein undecylenic acid condensate, Zinc pyrethione, aluminum pyrition and magnesium pyrithione / dipyrithione magnesium sulfate are used become.

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

Montmorillonite, clay minerals, pemulene and alkyl can be used as swelling agents for aqueous phases modified carbopol types (Goodrich) are used. Other suitable polymers or swelling agents can the overview by R. Lochhead in Cosm. Toil. 108, 95 (1993).

Under UV light protection factors are to be understood, for example, liquid or crystalline organic substances (light protection filters) at room temperature, which are able to absorb ultraviolet rays and absorb the energy in the form of longer-wave radiation, e.g. B. to give off heat like that. UVB filters can be oil-soluble or water-soluble. As oil-soluble substances such. B. To name:

• - 3-benzylidene camphor or 3-benzylidene norcampher and its derivatives, e.g. B. 3- (4-Methylbenzy liden) camphor as described in EP 0693471 B1;
• - 4-aminobenzoic acid derivatives, preferably 4- (dimethylamino) benzoic acid 2-ethylhexyl ester, 4- 2-octyl (dimethylamino) benzoate and amyl 4- (dimethylamino) benzoate;
• - Esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, 4-methoxycinnamate pro pylester, 4-methoxycinnamic acid isamyl ester, 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (octo crylene);
• - 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-me thoxy-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 octyl tria zone as described in EP 0818450 A1 or dioctyl butamido triazone (Uvasorb® HEB);
• Propane-1,3-diones, such as e.g. B. 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, such as. B. 4- (2-Oxo-3-bornylidenemethyl) benzene sulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and its 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, 4-tert-butyl-4'-methoxydibenzoyl methane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione and enamine compounds, as described in DE 197 12 033 A1 (BASF). The UV-A and UV-B filters can of course can also be used in mixtures. In addition to the soluble substances mentioned come for this Purpose also insoluble light protection pigments, namely finely dispersed metal oxides or salts in question. 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 as well as their mixtures. As salts Silicates (talc), barium sulfate or zinc stearate can be used. The oxides and salts are in the form of pigments for skin-care and skin-protecting emulsions and decorative cosmetics used. The particles should preferably have an average diameter of less than 100 nm have between 5 and 50 nm and in particular between 15 and 30 nm. You can ... a have a spherical shape, but it is also possible to use particles which have a have an ellipsoidal shape or a shape other than the spherical shape. The Pig elements can also be surface treated, i. H. are hydrophilized or hydrophobized. Typical Examples are coated titanium dioxide, such as. B. Titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Silicones and, in particular, trials are the main hydrophobic coating agents koxyoctylsilane or Simethicone in question. So-called sunscreens are preferred Micro or nanopigments used. 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) remove.

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 are 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-carnosine and their derivatives (e.g. anserine), carotenoids, carotenes (e.g. α-carotene, β-carotene, lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and its derivatives (e.g. dihydroliponic acid), Auro thioglucose, propylthiouracil and other thiols (e.g. thioredoxin, glutathione, 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. buthioninsulfoxim , Homocysteine sulfoximine, Butionin sulfone, Penta-, Hexa-, Heptathioninsulfoxim in) in very low tolerable doses (e.g. B. pmol to µmol / kg), further (metal) chelators (e.g. α-hydroxy fatty acids, palmitic acid, phytic acid, lac toferrin), α-hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid, bile acid , Biliary 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 its derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and derivatives (e.g. ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and derivatives (vitamin A palmitate) and coniferyl benzoate of benzoin, rutinic acid and its derivatives, α-Glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine, butylated hydroxytoluene, butylated hydroxyanisole, nordihydroguajak resin acid, nordihydroguajaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, man nose and its derivatives, superoxide dismutase, zinc vate (e.g. ZnO, ZnSO ₄ ), selenium and its derivatives (e.g. B. selenium-methionine), stilbenes and their derivatives (e.g. stilbene oxide, trans-style benoxid) and the derivatives suitable according to the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these active substances.

To improve the flow behavior, hydrotropes such as ethanol, isopropyl alcohol or polyols can also be used. 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, 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;  
• - Dialcohol amines, such as diethanolamine or 2-amino-1,3-propanediol.

Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, para benzene, pentanediol or sorbic acid as well as those in Appendix 6, Parts A and B of the Cosmetics Regulation led further substance classes. As insect repellents there are N, N-diethyl-m-toluamide, 1,2- Pentanediol or ethyl butylacetylaminopropionate in question, dihydroxy is suitable as a self-tanner acetone. As tyrosine inhibitors that prevent the formation of melanin and use in depigmas Finding agents come, for example, arbutin, kojic acid, coumaric acid and ascorbic acid (Vitamin C) in question.

Perfume oils include mixtures of natural and synthetic fragrances. Natural Fragrance substances are extracts of flowers (lily, lavender, rose, 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), woods (pine, sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, Lemongrass, sage, thyme), needles and twigs (spruce, fir, pine, mountain pine), resins and bal seeds (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Furthermore animal raw come substances in question, such as civet and castoreum. Typical synthetic fragrance compounds gen are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Fragrance compounds of the ester type are e.g. B. benzyl acetate, phenoxyethyl isobutyrate, p-tert-Bu tylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, Benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzylsa licylate. The ethers include, for example, benzyl ethyl ether, the aldehydes z. B. the linear Alka nals with 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones z. B. the Jonone, α-isomethylionon and Me thylcedryl ketone, to the alcohols anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, pheny ethyl alcohol and terpineol, the hydrocarbons mainly include terpenes and bal same. However, preference is given to using mixtures of different fragrances that work together generate an appealing fragrance. Also essential oils of lower volatility, mostly as an aro Mac components are used as perfume oils, e.g. B. sage oil, chamomile oil, clove oil, Lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanu mole, labolanum oil and lavandin oil. Bergamot oil, dihydromyrcenol, lilial, lyral, Citronellol, phenylethyl alcohol, α-hexyl cinnamaldehyde, geraniol, benzylacetone, cyclamenaldehyde, Lina lool, boisambrene forte, ambroxan, indole, hedione, sandelice, lemon oil, mandarin oil, orange oil, Allylamyl glycolate, cyclover valley, lavandin oil, muscatel sage oil, β-damascone, geranium oil bourbon, Cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, Evernyl, Iraldein gamma, phenylacetic acid acid, geranyl acetate, benzyl acetate, rose oxide, romillate, irotyl and floramate alone or in mixtures gene, used.  

As dyes, the substances suitable and approved for cosmetic purposes can be used be used, such as the dye in the publication "Cosmetic Colorants" 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.

The total proportion of auxiliaries and additives can be 1 to 50, preferably 5 to 40% by weight on the middle - amount. The agents can be produced by customary cold or hot processes gene; the phase inversion temperature method is preferably used.

Examples (I) Preparation of β, β-diglycerol lauryl monoester according to steps (a) to (e) (a) Conversion to 1,3,4,6-tetra-O-acetyl-2,5-anhydro-D-mannitol (1)

4 g (18.5 mmol) of glucosamine hydrochloride were stirred in water for 20 hours at room temperature. The solution was cooled to 0 ° C and 3 equivalents of sodium nitrite were added in one portion. With stirring and cooling (<2 ° C) 3 equivalents of conc. Acetic acid is added to form nitrous acid in situ. After stirring at 0 ° C. for 2 hours, the solution was warmed to room temperature and excess nitrous acid was expelled in a gentle stream of argon. The solution was evaporated to dryness and the crude 2,5-anhydro-D-mannose was reduced with 4 equivalents of sodium borohydride in water (10 ml / g, added in portions at 0 ° C.) at room temperature for 1 hour. Excess borohydride was decomposed with Amberlite® IR-120 ion exchange resin (H ⁺ form). The resin was filtered off and the solvent of the filtrate was removed in vacuo. Crude 2,5-anhydro-mannitol was peracetylated with acetic anhydride / pyridine mixture overnight at room temperature. After methanolysis, evaporation and coevaporation of the solvent mixture with toluene, the product was purified by column chromatography (silica gel column, 6: 4 petroleum ether / ethyl acetate as eluent). Yield: 4.92 g (14.8 mmol) 1 as a colorless oil, 80% with respect to glucosamine hydrochloride.

(b) Conversion to 2,5-anhydro-D-mannitol (2)

4.92 g (1) were deacetylated in methanol with 1 molar, methanolic sodium methoxide solution overnight at room temperature. The solution was then neutralized with Amberlite® IR-120 ion exchange resin (H ⁺ form), the resin was filtered off and the solvent was removed in vacuo. The syrupy product was seeded for crystallization and then recrystallized from anhydrous ethanol. Yield: 2.18 g (13.3 mmol) 2 as colorless crystals (mp. 100-102 ° C), 90% with regard to starting material.

(c) Conversion to 1,5-diacetoxy-2,4-diacetoxymethyl-3-oxapentane (3)

150 mg (0.914 mmol) (2) were mixed with a 0.1 molar aqueous sodium periodate solution (5 equivalents in 50 ml water). The mixture was stirred at room temperature for 2 hours and the solvent was then evaporated. The dry residue was then taken up again in water and a solution of the crude dialdehyde in 7.6 ml of water was reduced with 6 equivalents of sodium borohydride. After stirring for 16 hours at room temperature, the excess borohydride was decomposed with Amberlite® IR-120 ion exchange resin (H ⁺ form). The resin was filtered off and the filtrate was concentrated in vacuo. The crude sec, sec dimer thus obtained was peracetylated with acetic acid anhydride / pyridine mixture overnight at room temperature. After subsequent methanolysis, the solvent mixture was removed in vacuo and the residue was extracted with dichloromethane. The organic phase was washed with saturated aqueous sodium thiosulfate solution (to remove traces of iodine) and water and then dried over MgSO ₄ . After filtration and removal of the solvent in vacuo, the crude product was purified by column chromatography (silica gel column, 6: 4 petroleum ether / ethyl acetate as eluent). Yield quantitatively, ie 305 mg (0.91 mmol) (3), as a pale yellow oil.

(d) conversion to the di-2-glycerol ether ("sec, sec- or β, β-diglycerin") or 2,4-bishydroxymes thyl-3-oxapentane-1,5-diol (4)

305 mg (0.91 mmol) (3) were deacetylated with 1 molar sodium methoxide solution in methanol overnight at room temperature. The solution was then neutralized with Amberlite IR-120 ion exchange resin (H ⁺ form), the resin was filtered off and the solvent was removed in vacuo. The di-2-glycerol ether thus obtained was purified by column chromatography on silica gel (mobile phase: ethyl acetate / methanol / water - 80/15/5). Yield quantitative; ie 152 mg (0.91 mmol) di-2-glycerol ether (4), as a colorless, hygroscopic solid (mp. 76-78 ° C).

(e) Preparation of the polyglycerol ester 1-lauroyloxy-2,4-bishydroxymethyl-3-oxapentan-5-ol (5) Method A (enzymatic esterification)

100 mg (0.60 mmol) of di-2-glycerol ether 4 together with 510 mg (1.81 mmol) of trifluoroethyl laurate dissolved in anhydrous pyridine (1 ml / 0.2 mmol) and warmed to 45-50 ° C under a nitrogen atmosphere. Novozym 435 lipase (763 mg / mmol) was added and the suspension at 45-50 ° C for 90 Mi grooves stirred. The lipase was then filtered off and the mixture was concentrated in vacuo. The crude ester was purified by column chromatography (silica gel) (mobile phase ethyl acetate). Yield 86 mg (0.25 mmol) 5, as a colorless wax (mp. <50 ° C.), 41% with regard to starting material.

Method B (chemical esterification)

1 g (6.02 mmol) di-2-glycerol ether 4 was dissolved in anhydrous DMF (10 ml / g) and with 0.2 equiva lenten NaH. A solution of 2.18 g (7.22 mmol) of N-lauroyl-thiazolidin-2-thione in 10 ml was Serf-free DMF was added dropwise to the yellowish solution with stirring. The mixture was stirred at room temperature for 20 hours until decolorization. Then came the release withdrawn medium in vacuo and the crude product purified by column chromatography (silica gel)  (Mobile phase ethyl acetate). Yield 754 mg (0.22 mmol) 5, as a colorless wax (mp. <50 ° C.), 36% regarding educt.

(II) Preparation of linear (all-α-triglycerol lauryl monoester according to steps (A) to (F) (A) 1,2-epoxy-6,7-O-isopropylidene-4-oxaheptane (1)

12.43 ml (0.1 mol) of Solketal (isopropylidene glycerol) and 1.6 g (5 mmol) of tetrabutylammonium bromide were added to a 50% aqueous solution of NaOH (1.6 g / 0.04 mol), followed by 90 ml n-hexane. Then 15.64 ml (0.2 mol) of epichlorohydrin were added and the resulting mixture was stirred vigorously at 50 ° C. for 2 hours. The reaction mixture was then diluted with 100 ml of diethyl ether and water and the aqueous phase extracted with diethyl ether. The combined organic extracts were washed with Brine solution, dried over MgSO ₄ and then spun in on a rotary evaporator. 12.78 g (68%) of product 1 were obtained as a colorless oil after vacuum distillation (148-152 ° C / 18 mbar).

(B) 6-Hydroxy-1,2: 10,11-di-O-isopropylidene-4,8-dioxaundecane (2)

13.21 ml (0.106 mol) of Solketal, 865 mg (2.65 mmol) of tetrabutylammonium bromide (TBAB) and 15 ml of n-hexane were added to a 50% aqueous solution of NaOH (10.6 g / 0.265 mol). 10 g (53 mmol) of compound 1 were then added and the resulting mixture was stirred vigorously at 60 ° C. for 5 hours. The mixture was then diluted with 50 ml of diethyl ether and 100 ml of water and the aqueous phase was extracted with diethyl ether. The combined organic extracts were washed with Brine solution, dried over MgSO ₄ and then spun in on a rotary evaporator. 10.1 g (59%) of product 2 were obtained from the residue after vacuum distillation (168-170 ° C./2 mbar) as a colorless oil.

(C) 6-O-benzyl-1,2: 10,11-di-O-isopropylidene-4,8-dioxaundecane (4)

3 g (9.36 mmol) of product 2 was added dropwise to a suspension of NaH (748 mg / 18.7 mmol) in dry THF (40 ml). After the reaction, the mixture was stirred at room temperature for 45 minutes and 1.7 ml (14 mmol) of benzyl bromide and 150 mg (0.47 mmol) of TBAB were added. After stirring at room temperature for 90 minutes, the mixture was diluted with diethyl ether, washed with water until neutral (pH 7), then washed with brine solution, dried over MgSO ₄ and concentrated in vacuo. The crude product was purified by column chromatography (mobile phase petroleum ether / ethyl acetate 8: 2). Yield: 3.1 g (81%) 4, as a colorless oil.

(D) 6-O-benzyl-1,2: 10,11-tetrahydroxy-4,8-dioxaundecane (5)

To remove the isopropylidene groups, 3.1 g (7.6 mmol) 4 in boiling methanol were added Dowex® 50Wx8 ion exchange resin stirred. Yield 1.95 g (78%) 5 as a colorless oil.

(E) 6-O-benzyl-1,2: 10,11-trihydroxy-1-O-lauroyl-4,8-dioxaundecane (6)

3.7 g (11.2 mmol) of product 5 was slowly added to a suspension of 134 mg (3.36 mmol) of NaBH ₄ in 25 ml of dry THF. 4.05 g (13.4 mmol) of N-lauroyl-thiazolidine-2-thione, dissolved in 40 ml of dry THF, was then added dropwise under nitrogen. After the addition had ended, the yellow mixture was stirred until it had completely decolorized, then saturated aqueous NH ₄ Cl solution was added and the mixture was extracted with diethyl ether. The combined organic phases were washed with brine solution, dried over MgSO ₄ and concentrated in vacuo. The crude product was purified by column chromatography (eluent methylene chloride / acetone 8: 2). Yield: 2.59 g (45%) 6, as a colorless oil.

(F) 2,6: 10,11-tetrahydroxy-1-lauroyl-4,8-dioxaundecane (7)

250 mg (10%) Pd / C was added to a solution of 2.5 g (4.88 mmol) 6 in 60 ml methanol and the mixture was stirred for 90 minutes under a hydrogen atmosphere. The reaction mixture was filtered through Celite, concentrated in vacuo and purified by column chromatography (mobile phase methy lenchloride / methanol 9: 1). 1.85 g (90%) of the desired ester 7 were obtained as a white solid receive.

III. Use of the polyglycerol monoesters

Examples 1 to 4 according to the invention and comparative examples V1 to V4 were in each case as 25% by weight solutions in ultrapure water to their relative irritation potential [Q] after the reaction time method (W. Steiling et al., "The HET-CAM, a reliable in vitro test for the prediction of eye irriation" in: Alternatives to Animal Testing, pp. 364-368, eds. S.G. Lisansky, R. Macmillan, J. Dupuis, Colipa, CPL Press 1996). 300 µl of the samples were used on at least 6 fertilized chicken eggs tested with well-developed blood vessels of the chorion-allantoic membrane.

The relative stimulus potential [Q] was classified as follows: ≦ 0.8 slightly irritating / <0.8 - <1.2 moderately irritating / ≧ 1.2 - <2.0 irritating (R 36) / ≧ 2.0 strongly irritating (R 41).  

Table 1

Testing the polyglycerol esters in the HET-CAM test

The stability of emulsifiers 1 to 4 and V1 to V4 was observed over a period of 4 weeks at 20 and 40 ° C rated. Stable, homogeneous emulsions are rated with (+) and two-phase, segregated systems get a (-). Furthermore, the relative skin feeling of 5 test subjects rated (++ = very good; + = good). The results were summarized in Table 2.

Table 2

Emulsions (quantities in% by weight)

Claims (9)

1. Primary monofatty acid esters of self-condensation products of glycerol of the formulas (I) to (VI) and mixtures thereof
in which R ^{1 is} a linear and / or branched alkyl and / or alkenyl radical having 1 to 22 carbon atoms and a and b independently of one another for numbers from 0 to 8, q and p independently of one another for numbers from 0 to 8, with the proviso that only q or p can be 0 and n and m are independently numbers from 1 to 8 and r and s and t and u are independently numbers from 0 to 8. 2. Composition according to claim 1, characterized in that R ^{1 represents} a linear and / or branched alkyl and / or alkenyl radical having 6 to 18 carbon atoms. 3. Composition according to claims 1 and / or 2, characterized in that primary polyglycine rinmonofatty acid esters of the formula (I) in which a and b independently of one another represent 0 or 1 stand. 4. Agent according to at least one of claims 1 to 3, characterized in that primary Polyglycerol monofatty acid esters of the formula (II) and / or (III) in which n and m are independent stand for numbers from 1 to 4. 5. Composition according to at least one of claims 1 to 4, characterized in that primary Polyglycerol monofatty acid esters of the formula (IV) in which p for numbers from 1 to 4 and q for 0 or 1 stand. 6. Composition according to at least one of claims 1 to 5, characterized in that primary Polyglycerol monofatty acid ester of the formula (V), in which r and s independently of one another Numbers from 0 to 4 are available. 7. Composition according to at least one of claims 1 to 6, characterized in that primary Polyglycerol monofatty acid ester of the formula (VI) in which t and u are independently of one another Numbers from 0 to 4 are available. 8. Use of esters according to at least one of claims 1 to 7 for the preparation of surfactants. 9. Use according to claim 8 for the production of cosmetic and / or pharmaceutical For formulations, food preparations and washing and cleaning agents.