WO1999000400A1

WO1999000400A1 - Alkyl and/or alkenyl oligoglycoside silicon ethers

Info

Publication number: WO1999000400A1
Application number: PCT/EP1998/003622
Authority: WO
Inventors: Oliver Rhode
Original assignee: Cognis Deutschland Gmbh
Priority date: 1997-06-25
Filing date: 1998-06-16
Publication date: 1999-01-07
Also published as: AU8215798A; DE19727030A1

Abstract

New alkyl and/or alkenyl oligoglycoside silicon ethers are obtained by reacting alkyl and/or alkenyl oligoglycosides of formula (I): R1O-[G]¿p¿, in which R1 stands for an alkyl and/or alkenyl radical with 4 to 22 carbon atoms, G for a sugar radical with 5 or 6 carbon atoms and p equals 1 to 10, with epoxy silicon ethers of formula (II), in which R2 stands for alkyl radicals with 1 to 4 carbon atoms, q equals 0 or 1 and n and m are independently equal to 1 to 5, in the presence of basic catalysts. These substances are useful as surfactants, in particular as emulsifiers, but also as fatty substances and polysiloxane substitutes, for preparing surfactant products, in particular cosmetic compositions.

Description

Alkyl and / or alkenyl oligoglycoside silicone ethers

Field of the Invention

The invention relates to alkyl and / or alkenyl oligoglycoside ethers which are obtained by ring opening of epoxy silicone ethers with glycosides, a process for their preparation and their use for the preparation of surface-active agents.

State of the art

Alkyl oligoglucosides are nonionic surfactants with excellent foaming properties. However, the emulsifying power of these surfactants leaves something to be desired, which is why many attempts have been made in the past to change the hydrophilicity or lipophilicity of this class of compounds by derivatization, i.e. adapt to the desired requirements. In this context, condensation products of alkyl oligoglucosides with ethylene oxide or oligoglycerols are known.

In the documents JP-A1 Hei 07/041414, JP-A1 Hei 07/041415, JP-A1 Hei 07/041416, and JP-A1 Hei 07/041417 (Shiseido) and the patent US 5,550,219 (Siltech), sugar-modified silicones and described their use in cosmetics. Anionic, cationic and nonionic alkyl glucoside silicone ethers are known from the publications WO 94/29322, WO 94/29323 and WO 94/29324 (Bayer). European patent EP-B1 0612759 (Wacker) also relates to a process for the preparation of special alkyl glucoside silicone ethers, in which mono- or oligosaccharides are first reacted with unsaturated alcohols and the resulting alkenyl glycosides are then condensed with an Si-bonded hydrogen-containing organosilicon compound. These surfactant silicone compounds show a significantly improved emulsifying capacity, but are not entirely satisfactory in terms of stabilizing emulsions at higher temperatures. Another disadvantage is their complex production, since allyl glucosides have to be used for their production and there are high occupational safety requirements for the acetalization of glucose with allyl alcohol. The object of the present invention was therefore to provide new glycosidic silicone compounds which have improved application properties and in particular are easier to produce.

Description of the invention

The invention relates to alkyl and / or alkenyl oligoglycoside silicone ethers which are obtained by using alkyl and / or alkenyl oliglycosides of the formula (I),

¹ 0- [G] _p (I)

in which R ^{1 represents} an alkyl and / or alkenyl radical with 4 to 22 carbon atoms, G for a sugar radical with 5 or 6 carbon atoms and p for numbers from 1 to 10, in the presence of basic catalysts with epoxysilicone ethers of the formula (II) ,

in which R ^{2 stands} for alkyl radicals with 1 to 4 carbon atoms, q for 0 or 1 and n and m independently of one another for numbers from 1 to 5.

Surprisingly, it was found that the new glycosidic silicone compounds not only have excellent emulsifying properties, but also reliably stabilize emulsions even after prolonged storage at elevated temperatures. They also have lipophilic properties, which is why they are also suitable as polar oil bodies, especially as substitutes for conventional silicone oils of the polysiloxane type. Another advantage is their extremely simple manufacture.

The invention further relates to a process for the preparation of alkyl and / or alkenyl oligogiycosidesiiiconether, in which alkyl and / or alkenyl oliglycosides of the formula (I),

R ¹ 0- [G] _p (I)

Alkyl and / or alkenyl olefin glycosides

Alkyl and alkenyl oligoglycosides are known nonionic surfactants which follow the formula (I)

R ¹ 0- [G] _P (I)

in which R ^{1 is} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry. As representative of the extensive literature, reference is made here to the documents EP-A1 0301298 and WO 90/03977.

The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (I) indicates the degree of oligomerization (DP), i.e. H. the distribution of mono- and oligoglycosides is on and stands for a number between 1 and 10. While p must always be an integer in a given compound and here can take on the values p = 1 to 6, the value p is for a certain alkyl oligo - glycoside is an analytically calculated value that usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4.

The alkyl or alkenyl radical R ¹ can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capro alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucosides of chain length Cs are preferred C10 (DP = 1 to 3), which arises as a preliminary step in the separation of technical Cβ-Ciβ-coconut fatty alcohol by distillation and can be contaminated with a proportion of less than 6% by weight of Ci2-alcohol as well as alkyl oligoglucosides based on technical Cg / n-oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ¹ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palm oleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and the technical mixtures described above, which can be obtained as well as their technical mixtures. Alkyl oligoglucosides based on hydrogenated Ci2 / i4 coconut alcohol with a DP of 1 to 3 are preferred.

Epoxy silicone ether

Epoxysilicon ethers of the type mentioned are known substances which can be prepared by the customary methods of preparative chemistry. They are available, for example, under the brand name Silan-Z-6040 from Dow Corning. Epoxysilicon ethers of the formula (II) are preferably used in which R ^{2 is} methyl, p is 1 and n and m is 1 or 3. The glycosides and the silicone ethers are usually used in a molar ratio of 1: 0.95 to 1: 1, 2, preferably 1: 1 to 1.1.

Catalysts

The selection of the basic catalyst is not critical per se. Basically, alkali and / or alkaline earth metal hydroxides, oxides, carbonates, bicarbonates, C 1 -C 4 -alcoholates and ammonia, alkylamines and / or alkanolamines can be used. Typical examples are sodium hydroxide, potassium hydroxide, magnesium oxide, sodium carbonate, sodium hydrogen carbonate, sodium methylate, methylamine, ethanolamine and the like. The catalysts are usually used in amounts of 0.1 to 10, preferably 1 to 5,% by weight, based on the glycosides.

Opening procedure

The opening of the epoxy ring of the silicone ether through the primary hydroxyl group of the glycoside can be carried out in a manner known per se. For example, the ring opening of epoxides with glucosides is described in principle in DE-A1 4223581 (Henkel). The reaction is preferably carried out at temperatures in the range from 60 to 100.degree. In principle, lower temperatures are possible if the glucoside is liquid under these conditions and a lower reaction speed is acceptable. Temperatures above 100 ° C can lead to decomposition of the sugar body and are therefore less advantageous.

Industrial applicability

The new glycosidic silicone ethers reduce the interfacial tension and promote the emulsification of otherwise immiscible phases. They are also suitable as substitutes for polysiloxane oils, i.e. as a polar oil body. Another object of the invention therefore relates to their use as surfactants for the production of surface-active agents and as emulsifiers or oil bodies for the production of cosmetic and / or pharmaceutical preparations in which they are used in amounts of 1 to 90, preferably 5 to 75 and in particular 10 to 25 % By weight, based on the composition, may be present.

In a special embodiment of the invention, the new glycosidic silicones are used together with alkyl oligoglucosides and optionally pearlescent waxes to produce foam-strong, storage-stable silicone shampoos with excellent conditioning and conditioning properties as well as brilliant pearlescence.

Surfactants

For the purposes of the use according to the invention, the new glycosidic silicone ethers can be used together with further anionic, nonionic, cationic and / or amphoteric or zwitterionic surfactants. Typical examples of anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfofatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxymixed ether etherates, sulfate (sulfate) amate sulfate ethersulfate, mono - sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and salts thereof, fatty acid taurides, N-acylamino acids such as acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (in particular vegetable products based on wheat) and alkyl (ether ) phosphate. 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 glucoronic acid amide (in particular, glucoronic acid amide) vegetable oils, glucoronic acid amide, glucoronic acid amide, and / or glucoronic acid amide (glucoronic acid amide), in particular, glucoronic acid amide, glucoronic acid amide, (V), glucoronic acid amide, (v) Products on wheat basis), 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 and ester quats, 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, Surfactants and mineral oil additives ", Thieme Verlag, Stuttgart, 1978, pp. 123-217.

Cosmetic and / or pharmaceutical preparations

Preparations which are produced using the new glycosidic silicone ethers, such as, for example, hair shampoos, hair lotions, foam baths, creams, lotions or ointments, can furthermore contain, as further auxiliaries and additives, oil bodies, emulsifiers, superfatting agents, pearlescent waxes, stabilizers, consistency agents, thickeners, cation polymers, Contain silicone compounds, biogenic agents, anti-dandruff agents, film formers, preservatives, hydrotropes, solubilizers, UV light protection filters, insect repellents, self-tanners, perfume oils, dyes and the like.

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 C6-C22 fatty alcohols, esters of branched C6-Ci3 carboxylic acids with linear C6-C22- Fatty alcohols, esters of linear C6-C22 fatty acids with branched alcohols, especially 2-ethylhexanol, esters of linear and / or branched fatty acids with polyhydric alcohols (such as propylene glycol, dimerediol or trimer triol) and / or Guerbet alcohols, triglycerides based on Cθ -Cio fatty acids, liquid mono- / di- / triglyceride mixtures based on C6-Ci8 fatty acids, esters of C6-C22 fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, especially benzoic acid, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear C6-C22 fatty alcohol carbonates, Guerbet carbonates, esters of benzoic acid with linear and / or branched C6-C22 alcohols (e.g. Finsolv® TN), dialkyl ethers, ring opening products of epoxidized fatty acid esters with polyols, silicone oils and / or aliphatic or naphthenic hydrocarbons.

Examples of suitable emulsifiers are nonionic surfactants from at least one of the following groups: (1) Adducts 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 and with alkylphenols with 8 to 15 C atoms in the Alkyl group;

(2) Ci2 / i8 fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol;

(3) glycerol monoesters and diesters and sorbitan monoesters and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and their ethylene oxide addition products;

(4) alkyl mono- and oligoglycosides with 8 to 22 carbon atoms in the alkyl radical and their ethoxylated analogs;

(5) adducts of 15 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil;

(6) polyol and especially polyglycerol esters such as e.g. Polyglycerol polyricinoleate or polyglycerol poly-12-hydroxystearate. Mixtures of compounds from several of these classes of substances are also suitable;

(7) adducts of 2 to 15 moles of ethylene oxide with castor oil and / or hardened castor oil;

(8) partial esters based on linear, branched, unsaturated or saturated C6 / 22 fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerin, polyglycerin, pentaerythritol, dipentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. methyl glucoside, butyl glucoside - glucoside) and polyglucosides (eg cellulose);

(9) trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates;

(10) wool wax alcohols;

(11) polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;

(12) mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE-PS 1165574 and / or mixed esters of fatty acids with 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol and

(13) Polyalkylene glycols.

The adducts of ethylene oxide and / or of propylene oxide with fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or with castor oil are known, commercially available products. These are mixtures of homologs, the middle of which Degree of alkoxylation corresponds to the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out. Ci2 / i8 fatty acid monoesters and diesters of adducts of ethylene oxide with glycerol are known from DE-PS 20 24 051 as refatting agents for cosmetic preparations.

Cδ / 18-alkyl mono- and oligoglycosides, their preparation and their use as surface-active substances are known from the literature. They are produced in particular by reacting glucose or oligosaccharides with primary alcohols with 8 to 18 carbon atoms. Regarding the glycoside residue, both monoglycosides in which a cyclic sugar residue is giycosidically bound to the fatty alcohol is, 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 value which is based on a homolog distribution customary for such technical products.

Zwitterionic surfactants can also be used as emulsifiers. Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as the N-alkyl-N, N-dimethylammonium glycinate, for example coconut alkyldimethylammonium glycinate, N-acylamino propyl-N, N-dimethylammonium glycinate, for example coconut acylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxyl -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 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 -SO3H 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 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and Ci2 / i8-acylsarcosine. In addition to the ampholytic emulsifiers, quaternary emulsifiers are also suitable, those of the esterquat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, being particularly preferred.

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.

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; as well as their mixtures.

Mainly fatty alcohols with 12 to 22 and preferably 16 to 18 carbon atoms and also partial glycerides come into consideration as consistency agents. A combination of these substances with alkyl oligoglucosides and / or fatty acid N-methylglucamides of the same chain length and / or polyglycerol poly-12-hydroxystearates is preferred. Suitable thickeners are, for example, polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, and also higher molecular weight polyethylene glycol mono- and di-esters of fatty acids, polyacrylates, (for example Carbopole® from Goodrich or Synthalene® from Sigma), polyacrylamides, 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 as well as electrolytes such as sodium chloride and ammonium chloride.

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

Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones and amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine- and / or alkyl-modified silicone compounds, which can be both liquid and resinous at room temperature. Typical examples of fats are glycerides, beeswax, camamauba wax, candelilla wax, montan wax, paraffin wax or microwaxes, if appropriate in combination with hydrophilic waxes, for example cetylstearyl alcohol or partial glycerides. Metal salts of fatty acids such as magnesium, aluminum and / or zinc stearate can be used as stabilizers. Examples of biogenic active ingredients are tocopherol, tocopherol acetate and tocopherol. pherol palmitate, ascorbic acid, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts and vitamin complexes. Climbazole, octopirox and zinc pyrethione can be used as antidandruff agents. Common film formers are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinylpyrrolidone, vinyl-pyrrolidone-vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives, collagen, hyaluronic acid or its salts and similar compounds. Montmohlonite, clay minerals, pemulene and alkyl-modified carbopol types (Goodrich) can serve as swelling agents for aqueous phases.

UV light protection filters are organic substances that are able to absorb ultraviolet rays and the absorbed energy in the form of longer-wave radiation, e.g. To give off heat again. Typical examples are 4-aminobenzoic acid and its esters and derivatives (e.g. 2-ethylhexyl p-dimethylaminobenzoate or p-dimethylaminobenzoic acid octyl ester), methoxy cinnamic acid and its derivatives (e.g. 4-methoxy cinnamic acid 2-ethylhexyl ester), benzophenones (e.g. oxybenzone, 2-hydroxy-4-methoxybenzophenone), dibenzoylmethane, salicylate ester, 2-phenylbenzimidazole-5-sulfonic acid, 1- (4-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1, 3-dione, 3- (4'-methyl) benzylideboron-nan-2-one, methylbenzylidene camphor and the like. Finely dispersed metal oxides or salts are also suitable for this purpose, such as, for example, titanium dioxide, zinc oxide, iron oxide, aluminum oxide, cerium oxide, zirconium oxide, silicates (talc) and barium sulfate. 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 shape which differs from the spherical shape in some other way. 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 superoxide dismutase, tocopherols (vitamin E) and ascorbic acid (vitamin C).

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

• glycerin;

Alkylene glycols, such as, for example, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and polyethylene glycols with an average molecular weight of 100 to 1,000 daltons;

Technical oligoglycerol mixtures with a degree of self-condensation of 1.5 to 10, such as technical diglycerol mixtures with a diglycerol content of 40 to 50% by weight; • Methyl compounds, such as in particular trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;

• Lower alkyl glucosides, in particular 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.

Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid. N, N-diethyl-m-touluamide, 1, 2-pentanediol or Insect repellent 3535 are suitable as insect repellents, and dihydroxyacetone is suitable as a self-tanner.

Perfume oils include extracts from flowers (lavender, roses, jasmine, neroli), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, coriander, caraway seeds, juniper), fruit peels (bergamot, lemon, oranges), roots (Macis, Angelica, Celery, Cardamom, Costus, Iris, Calmus), woods (sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, lemon grass, sage, thyme), needles and branches (spruce , Fir, pine, mountain pine), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials such as musk, civet and castoreum are also suitable. Ambroxan, eugenol, isoeugenol, citronellal, hydroxycitronellal, geraniol, citronellol, geranyl acetate, citral, ionone and methylionone are suitable as synthetic or semi-synthetic perfume oils.

The dyes which can be used are those substances which are suitable and approved for cosmetic purposes, as compiled, for example, in the publication "Cosmetic Dyes" by the Dye Commission of the German Research Foundation, 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 50, preferably 5 to 40% by weight, based on the composition. The agents can be produced by customary cold or hot processes; the phase inversion temperature method is preferably used.

n Examples

Example 1. 389 g (1 mol) of octylglucoside (DP = 1.6) were placed in a 1 liter three-necked flask equipped with a stirrer, dropping funnel and reflux condenser, melted and 0.2 g (corresponding to 0.5 mol% based on the glucoside) sodium hydroxide. As soon as the melt was stirrable, 260 g (1.1 mol) of [3- (2,3-epoxypropoxy) propyl] trimethoxysilane were added dropwise at a rate such that the temperature in the reaction vessel did not rise above 180.degree. After the addition had ended, stirring was continued for a further 1 h and the reaction product was then processed with water to form a paste with a solids content of 40% by weight.

Example 2. 413 g (1 mol) of dodecylglucoside (DP = 1, 4) were placed in a 1 liter three-necked flask equipped with a stirrer, dropping funnel and reflux condenser, melted and mixed with 0.2 g (corresponding to 0.5 mol% based on the glucoside) sodium hydroxide. As soon as the melt was stirrable, 260 g (1.1 mol) of [3- (2,3-epoxypropoxy) propyl] trimethoxysilane were added dropwise at a rate such that the temperature in the reaction vessel did not rise above 180.degree. After the addition had ended, stirring was continued for a further 1 h and the reaction product was then processed with water to form a paste with a solids content of 35% by weight.

Application examples 3 to 11, comparative example V1. Pearlescent waxes were melted, mixed with the silicone compounds, the other surfactant ingredients and made up to 100 g with water. After homogenization, the shampoo formulations were stored at 40 ° C. for 1 week. The viscosity of the products was determined using the Brookfield method (23 ° C., spindle 5, 10 rpm), the fine particle size of the pearlescent crystals was visually assessed under a microscope on a scale from 1 = very fine crystals to 5 = coarse crystals. The pearlescence was also assessed on a scale from 1 = brilliant to 5 = dull; the turbidity was determined visually and rated as (+) = cloudy or (-) = free of turbidity. The results are summarized in Table 1 (percentages as% by weight

Table 1 Pearlescent shampoos

^* ) Dehyquart® F 75 (Henkel KGaA, Dusseldorf / FRG)

Claims

claims

1. alkyl and / or alkenyl oligoglycoside silicone ethers, obtainable by preparing alkyl and / or alkenyl oliglycosides of the formula (I),

R ¹ 0- [G] _P (I)

2. Process for the preparation of alkyl and / or alkenyl oligoglycoside silicone ethers, in which alkyl and / or alkenyl oliglycosides of the formula (I),

R ¹ 0- [G] _P (I)

3. The method according to claim 2, characterized in that one uses silicone ethers of the formula (II) in which R ^{2 is} methyl and n and m are 1.

4. Process according to claims 2 and 3, characterized in that glycosides and the silicone ethers are used in a molar ratio of 1: 0.95 to 1: 1, 2.

5. Process according to claims 2 to 4, characterized in that basic catalysts are used which are selected from the group formed by alkali and / or alkaline earth metal hydroxides, oxides, carbonates, bicarbonates, -C-C ₄ alcoholates and ammonia, alkylamines and / or alkanolamines.

6. Process according to claims 2 to 5, characterized in that the catalysts are used in amounts of 0.1 to 10% by weight, based on the glycosides.

7. The method according to claims 2 to 6, characterized in that one carries out the reaction at temperatures in the range of 60 to 100 ° C.

8. Use of alkyl and / or alkenyl oligoglycoside silicone ether according to claim 1 as surfactants for the preparation of surface-active agents.

9. Use of alkyl and / or alkenyl oligoglycoside silicone ether according to claim 1 as emulsifiers for the production of cosmetic and / or pharmaceutical preparations.

10. Use of alkyl and / or alkenyl oligoglycoside silicone ethers according to claim 1 as an oil body for the production of cosmetic and / or pharmaceutical preparations