WO1996026710A1 - Cosmetic and/or pharmaceutical preparations - Google Patents

Abstract

The invention concerns novel cosmetic and pharmaceutical preparations containing technical dimeric diol/trimeric triol mixtures with on average 24-66 carbon atoms. The polyols can be used as oils and are characterised by a low spreading capability.

Description

 Cosmetic and / or pharmaceutical preparations

Field of the Invention

The invention relates to cosmetic and / or pharmaceutical preparations containing selected polyols and the use of the polyols as oil bodies.

Stand d * yr 1V »r-hτι <V

For the production of cosmetic or pharmaceutical agents, for example creams, lotions or ointments, oil-soluble bases are needed, the task of which is to transport polar ingredients, such as, for example, active ingredients or moisture, through the lipid barrier of the skin. A variety of natural and synthetic oils are suitable for this purpose, for example almond or avocado oil or ester oils based on short-chain triglycerides. At the same time, the oil components in the agents mentioned also have a nourishing effect which is directly related to the skin oiling. Products are desired by the consumer which impart a non-sticky feeling of skin smoothness and suppleness that occurs as quickly as possible and lasts longer. The subjective sensation on the skin can be correlated and objectified with the physico-chemical parameter of the spreading of the oil bodies on the skin, as described by U. Zeidler in fats, soaps, paints. 82, 403 (1985). Accordingly, cosmetic oil bodies can be divided into low-spreading (below 300 mm ² / 10min), medium-spreading (approx. 300 to 1000 mm ² / 10min) and high-spreading oils (above 1000 mm ² / 10min).

Emulsions for the formulation of extensive care and Massageöl- are oil bodies with high greasiness, ie with a low Speit capacity of less than 100 mm ^2/10 minutes erforder¬ Lich. These include vegetable oils, (33 ² mm / 10 min), such as peanut oil (62 mm ^2/10 min) or castor oil. However, substances of this type are difficult to emulsify due to their high molecular weight, particularly in W / O emulsions [cf. Ansmann et al. in Soap-Oil-Fat-Waxes 117, 158 (1991)]. When using castor oil, concentrations above 15% by weight, for example, no longer lead to the formation of an emulsion. A further disadvantage is the susceptibility to oxidation of the oil bodies mentioned at the outset and the fact that they are practically insoluble in polar media such as, for example, ethanol.

The complex object of the present invention was therefore to provide cosmetic and / or pharmaceutical preparations with an oil body content that have a low Zeidler spreading value of <100 mm / 10 min, can be easily in W / Have O-emulsions incorporated, little susceptible to oxidation and moreover are still satisfactorily soluble in polar media such as ethanol.

Description of the invention

The invention relates to cosmetic and pharmaceutical preparations containing technical dimer diol / trimer triol mixtures with an average of 24 to 66, preferably 36 to 54 carbon atoms.

Surprisingly, it was found that technical mixtures of dimer diols and trimer triols are high-fat and low-spreading (spreading value approx. 50 mm / 10 min), can be incorporated into cosmetic emulsions without problems and are very resistant to autoxidation. The invention also includes the knowledge that the polyols have excellent alcohol / water solubility. For example, 25 g of water are added to 100 g of a 5% strength by weight ethanolic solution of a technical D-lmerdiol / trimer triol mixture without the solution becoming cloudy or phase separation occurring.

Dimer diol / trimer triol mixtures

Dimer diol / trimer triols are technical mixtures which are obtained by oligomerizing unsaturated fatty acids having 12 to 22, preferably 16 to 18 carbon atoms or their methyl esters and subsequent high-pressure hydrogenation. The oligomerization of unsaturated fatty acids is a known electrocyclic reaction, about which in review articles, for example by A. Behr in Fat Sei. Technol. 93, 340 (1991), G.Spiteller in Fat Sei.Technol. .94 _* 41 (1992) or P.Daute et al. in Fat Sei.Technol. J95_, 91 (1993) is reported. In oligomerization, on average two to three fatty acids come together and form dimers or trimers, which predominantly have cycloaliphatic structures. In addition to the fraction of the dimers and trimers, a so-called monomer fraction is obtained in which there are unreacted starting materials and branched monomers which have arisen in the course of the reaction by isomerization. There is of course also a fraction of higher oligomers, which, however, is generally not of major importance. The oligomerization can be carried out thermally or in the presence of noble metal catalysts. The reaction is preferably carried out in the presence of clays such as montomorillonite [cf. Greases, soaps, paints. 72, 667 (1970)]. The regulation of the content of dimers and trimers and the extent of the monomer fraction can be controlled by the reaction conditions.

As already mentioned, technical unsaturated fatty acids with 12 to 22 and preferably 16 to 18 carbon atoms are suitable as starting materials for the oligomerization. Typical examples are palmoleic acid, oleic acid, elaidic acid, petroselinyl acid, linoleic acid, linolenic acid, conjugated fatty acid, elaeostearic acid, ricinoleic acid, gadoleic acid, erucic acid and their technical mixtures with saturated fatty acids. Typical examples of suitable technical mixtures are uncured split fatty acids from natural triglyc ride with iodine numbers in the range from 40 to 140, such as palm fatty acid, tallow fatty acid, rapeseed oil fatty acid, sunflower fatty acid and the like. Split fatty acids with a high oleic acid content are preferred.

In addition to the fatty acids, their esters, preferably methyl esters, can also be dimerized. It is also possible to oligomerize the acid and convert it to the methyl ester before the hydrogenation. The acid or ester group is hydrogenated to the alcohol group in a manner known per se in the presence of heterogeneous cupfer / chromium or cupfer / zinc catalysts at temperatures in the range from 200 to 300 ° C. and pressures of about 250 to 350 bar .

Dimer diol / trimer diol mixtures, which are particularly preferred for the purposes of the invention, are obtained by oligomerizing technical oleic acid and subsequent high-pressure hydrogenation and have a dimer diol content of 33 to 99% by weight and a trimer triol content of 1 to 67% by weight. % on. The monomer content can be 1 to 15% by weight and, if necessary, reduced by distillation.

Cosmetic and / or pharmaceutical preparations

Cosmetic or pharmaceutical preparations are primarily to be understood as skin care products which can contain the technical dimer diol / trimer triol mixtures in amounts of 1 to 35 and preferably 5 to 25% by weight, based on the composition. Furthermore, the agents according to the invention, such as creams and lotions, can contain additional oil bodies, emulsifiers, fats and waxes, stabilizers and superfatting agents, thickeners, biogenic agents, film formers, preservatives, colorants and fragrances exhibit.

Ester von linearen Cιo^-C18~^Fβtt8*^urθn ∞^ verzweigten Alkoholen, insbesondere 2-Ethylhexanol, Ester von linearen und/oder verzweigten Fettsäuren mit zweiwertigen Alkoholen und/oder Guer-betalkoholen, Triglyceride auf Basis C -Cιo~^Fe<ttsäuren, pflanzliche öle, verzweigte primäre Alkohole, substituierte Cyclohexane, Guerbetcarbonate und/oder Dialkylether in Be¬ tracht.As a further lkörper example, Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C6-C20 ^{fatty acids} with linear Cg-C20 ~ lk ^Fetta ° h ° l ^s. _' Esters of branched C - Ci3 carboxylic acids with linear

Esters of linear ^-C 18 ~ ^Fβtt8 * ^urθn ∞ ^ branched alcohols, especially 2-ethylhexanol, esters of linear and / or branched fatty acids with dihydric alcohols and / or Guerbet alcohols, triglycerides based on C -Cιo ~ ^{Fe <t} tsÄure , vegetable oils, branched primary alcohols, substituted cyclohexanes, Guerbet carbonates and / or dialkyl ethers.

Suitable emulsifiers are both known W / O and 0 / W emulsifiers, such as, for example, hardened and ethoxylated castor oil, polyglycerol fatty acid esters or polyglycerol poly ricinoleates or hydroxystearates, and also fatty alcohol sulfates, soaps, fatty alcohol ethoxylates, alkyl oligoglucosides and the like.

Typical examples of fats are glycerides, waxes which may be used include beeswax, paraffin wax or microwaxes, if appropriate in combination with hydrophilic waxes, for example cetylstearyl alcohol. Metal salts of fatty acids such as magnesium, aluminum and / or zinc stearate can be used as stabilizers.

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

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 diesters of fatty acids, polyacrylates, polyvinyl alcohol and polyvinyl pyrrolidone.

Biogenic active substances are understood to mean, for example, plant extracts and vitamin complexes.

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

Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid. Suitable pearlizing agents are, for example, glycol distearic acid esters such as ethylene glycol distearate, but also fatty acid monoglycol esters.

The dyes which can be used are the substances which are suitable and approved for cosmetic purposes, as compiled, for example, in the publication "Cosmetic Dyes" of the Dye Controls of the German Research Foundation, published by 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 and the non-aqueous proportion (“active substance content”) 20 to 80, preferably 30 to 70% by weight, based on the composition. The preparation of the agents can be carried out in a manner known per se, i.e. for example by hot, cold, hot-hot / cold or PIT emulsification. This is a purely mechanical process, there is no chemical reaction.

Industrial applicability

The technical dimer diol / trimer triol mixtures are notable for their high fatness and low spreading capacity. They can be easily incorporated into emulsions and are surprisingly readily soluble in polar media. Another object of the invention therefore relates to their use as oil bodies or superfatting agents for the production of cosmetic and / or pharmaceutical preparations in which they are present in concentrations of 1 to 35, preferably 5 to 25% by weight on the means - may be included.

The following examples are intended to explain the subject matter of the invention in more detail without restricting it.

Examples

I. rHπ-γ-ag-y z e oil body

The characteristic data and composition of the technical dihydro / diols used as oil bodies are summarized in Table 1:

Table 1 Key figures for technical dimer diols

Sovermol Sovermol Sovermol 650 NS POL 900 POL 930

Acid number <1 <1 <1 hydroxyl number 180-200 180-210 190-210 Viscosity (mPa * s) 5000 3000 6000

Monomer content (% by weight) 13 <2 4 Dimer content (% by weight) 68> 96 45 Trimer content (% by weight) 19 <2 51

The three technical dimer diol / trimer triol mixtures mentioned above are hand-made products from Henkel KGaA, Düsseldorf / FRG. The following emulsions were produced with their use (see Table 2, percentages as% by weight): Table 2 Emulsions according to the invention and comparative example

Component τ II III rv

%%%%

Lanette ( ^R ) 0 1 1 1 1

Dehymuls ( ^R ) FCE 2 2 2 2

Lameform ( ^R ) TGI 4 4 4 4

Micro wax 7 7 7 7

Sovermol ( ^R ) 650 NS 21 - - -

Sovermol ( ^R ) POL 900 - 21 - -

Sovermol ( ^R ) POL 930 - - 21 -

Castor oil - - - 21

Glycerin 5 5 5 5

Magnesium sulfate 1 1 1 1

Water ad 1 () 0% by weight -%

Legend: Lanette ( ^R ) 0 ■ Cetearyl Alcohol; Dehymuls ( ^R ) FCE * dicocoyl pentaerythritol distearyl citrate

Lameform ( ^R ) TGI = polyglyceryl-3-diisostearate.

Emulsions I to III are according to the invention, emulsion IV is used for comparison. While highly viscous creams with a rich care effect were obtained in the first three cases, in the case of the comparative example it was not possible to produce a stable emulsion.

Claims

-, 2 -patent claims 1. Cosmetic and pharmaceutical preparations containing technical dimer diol / trimer triol mixtures with an average of 24 to 66 carbon atoms. 2. Preparations according to claim 1, characterized in that they contain technical dimer diol / trimer triol mixtures which are obtained by oligomerizing unsaturated fatty acids having 12 to 22 carbon atoms or their methyl esters and subsequent high-pressure hydrogenation. 3. Preparations according to claims 1 and 2, characterized ge indicates that they contain technical dimer diol / trimer triol mixtures which are obtained by oligomerization of technical oleic acid and subsequent high pressure hydrogenation. 4. Preparations according to claims 1 to 3, characterized ge indicates that they contain technical dimer diol / trimer triol mixtures which have a dimer diol content of 33 to 99 wt .-% and a trimer triol content of 1 to 67 wt .-%. 5. Preparations according to claims 1 to 4, characterized ge indicates that they contain the technical dimer diol / trimer triol mixtures in amounts of 1 to 35 wt .-% - based on the composition. 6. Use of technical dimer diol / trimer triol mixtures as an oil body or superfatting agent for the production of cosmetic and / or pharmaceutical preparations.