DE3346642C2 - Spreadable preparation with high adhesion to the skin - Google Patents

Abstract

Spreadable preparations made from a component of an oily consistency and preferably an active ingredient contained therein are proposed which, due to the content of new ester mixtures, consisting of reaction products of partial esters of polyols of aliphatic monocarboxylic acids and optionally of aliphatic dicarboxylic acids with γ-glycidyl-oxypropyl-trialkoxysilanes, have high adhesiveness of the skin, are difficult to wash off from the skin and cause the skin to be difficult to wet.

Description

2. Preparation according to claim 1, characterized in that in the reaction products as further Reaction component dicarboxylic acids or their anhydrides or halides in amounts of 0.01 to 50 mol% is contained per mole of OH groups in the polyols.

3. Use of the preparation according to any one of claims 1 to 2 as a pharmaceutical or cosmetic Preparation for skin treatment.

4. Use according to claim 3 as a skin protection agent or sunscreen or radiation protection agent.

5. Use according to claim 3 as a spray preparation.

The invention relates to spreadable preparations for use as pharmaceutical and cosmetic Middle.

The preparation contains a component with an oily consistency and possibly an active ingredient or active ingredient content in the component of oily consistency as well as a new viscous gel-like ester mixture, which

ι new previously unknown properties of the preparation

causes.

In the context of the invention, spreadable means the ability to use human or animal skin both the surface of the skin and the mucous membranes near the surface and the mucous membranes inside the body to cover and spread on this to form an even film. Accordingly concerns the invention preparation forms of all suitable consistencies of low-viscosity preparations, especially low viscosity oils up to creams. Ointments, emulsions and especially Gels, which can range from flowable oils to stiff and solid gels.

For a long time there has been a need for preparations which can be applied to the skin and which have better adhesion on the skin, are difficult to remove from the skin and therefore have a longer duration of action have or allow a longer protective effect of the skin.

However, preparations of this type were not available; rather, they are the known preparations frequently, at least several times a day, to reapply.

An essential part of the new spreadable preparations is a new viscous gel-like ester mixture, that from a reaction product of fatty acid polyol partial esters with hydroxyl numbers from 5 to 150 with / -Glycidyl-oxipropyl-trialkoxisilanen consists The remainder of a dicarboxylic acid, in particular an aliphatic dicarboxylic acid, in which case the dicarboxylic acid component is preferred a part of said partial ester of hydroxyl numbers 5 to 150 forms

The other components of the spreadable preparation only need the condition of tolerance To be fulfilled in the context of pharmaceutical or cosmetic preparations and of an oily consistency to be.

The oily preparation can also contain pharmaceutical or cosmetic active ingredients in dissolved or distributed form, and they can be added separately or are already part of the component with an oily consistency.
In certain cases, however, the preparations have no pharmaceutical or cosmetic active ingredients added or contained in the oily component, since the viscous gel-like ester mixtures already have certain novel pharmaceutical and cosmetic effects.

It has namely been found that the viscous gel-like ester mixtures mentioned, soft below in detail are described, an extremely good adhesion to the skin, the mucous membranes and human and animal Have body tissue of all kinds. This particularly good adhesion has the particular effect that the preparations are difficult to remove from the skin. The treated skin area becomes difficult to wet and shows has a mild or even strong shine in numerous preparations. By normal washing with soap or Detergents, the preparations are initially not removable, however, the removal of the gel, depending on the Hooked the viscous gel-like ester mixture and its type, by repeated washing with z. B. the usual soap possible. Gels and other preparations can be produced from the ester mixtures, which can only be removed by washing 5 to 6 times or even 10 times, so that the removal by washing with soap in the usual way is used as a test for the adhesiveness.

On the other hand, the viscous gel-like ester mixtures and thus the spreadable preparations are after Can be completely absorbed through the skin for a longer period of time without any side effects, with any active ingredients present or the component of oily resistance according to their own penetration ability to an earlier one Time to be absorbed by the skin.

The new viscous gel-like ester mixtures still have the remarkable property, especially to be stable gel formers, so that proportions of the viscous gel-like ester mixtures to adjust the viscosity the component of an oily consistency to any value from a light consistency to a stiff one Gel is possible. Thanks to the three-dimensional network

tion with the silane component in the reaction product of the ester mixtures creates a three-dimensional one Framework structure which, even with small additions, gives rise to gels with the viscosity that has been set retained for very long periods of time and which, in particular, even at significantly higher temperatures z. B. Tropical conditions maintain the viscosity once set. Partly the drip points are the viscous gel-like ester mixtures higher than 300 ° C. Furthermore, these are viscous gel-like ester mixtures excellent emulsifiers, both for the production of W / O and for the production of O / W emulsions and thus enable the production of ointments, creams, lotions and the like viscous gel-like ester mixtures have a good spreading effect on the skin, causing an attacked or Frequent washing of damaged skin retains its own fats or has a lipid-replenishing effect from z. B. nourishing skin creams occurs.

In particular, the subject matter of the invention is a spreadable preparation with high adhesion the skin, consisting of

a) 5 to 80% by weight of a gel-like ester mixture, consisting of reaction products of fatty acid polyol partial esters or mixtures thereof with hydroxyl numbers from 5 to 150 with 2 to 45% by weight, based on the ester mixtures, of ^ -glycidyl-oxypropyl-trialkoxysilanes with alkyl groups of 1 to 3 carbon atoms or mixtures thereof and

b) 95 to 20% by weight of a component with an oily consistency or a W / O or O / W emulsion from this and water as well as possibly

c) 0.01 to 20% by weight of an active ingredient or its liquid or, if appropriate, solid preparation.

As already said, the only thing that matters is the spreadability of the preparation and a content of the viscous gel-like Ester mixtures necessary prerequisite for the preparation according to the invention, while the contents of the viscous gel-like ester mixture can also have proportions below 5% by weight or above 80% by weight and the other components are subject to change as long as a spreadable preparation for use in pharmaceutical and cosmetic preparations.

The fatty acid polyol partial esters preferably have a hydroxyl number of 10 to 80.

The amount of ^ -Glycidyl-oxypropyl-trialkoxysilane in the reaction product is preferably 4 to 30% by weight.

As far as additional dicarboxylic acids, their anhydrides or halides as reaction components of the reaction products are contained, their amount is 0.01 to 50 mol%, preferably 0.01 to 30 mol% each MoI OH groups of the polyols.

Another subject is the use of the preparations as a pharmaceutical or cosmetic preparation, especially for skin treatment.

Another particular subject of the invention are sun protection or UV protection preparations under Use of the particularly good adhesion to the skin and the resistance when washing the skin with soap in the usual way. These sunscreens with contents of known light protection substances are likewise for sun protection for sporting activities, for example for hikers and skiers in high mountains, Sun protection during the summer vacation time as well as for commercial purposes, for example for the UV radiation protection of electric welders or for therapeutic treatment under the action of UV rays suitable for skin protection. The particular advantage is that the particularly good adhesion of the containing ester preparations, the parts of the skin treated by the sunscreens come into contact with Water, for example during a beach holiday, are not wettable and so the usual very frequent

ίο Using the sunscreen due to the simpler Application can be replaced at longer intervals.

The preparations are also of particular value as skin protection agents, for example in the commercial sector for protection against aggressive aqueous media and equally for skin protection in the domestic sector as a component of detergents containing surfactants in the household.
Gel preparations, particularly clear gels, are preferred in many cases as sunscreens and skin protection agents.

Examples of further preparations are massage oils of arbitrarily adjustable consistency with levels of skin-active ingredients such. B. eucalyptus oil or extract oils from Hyperikum perforatum or the like, oily treatment agents of the nasal mucous membrane made of paraffin in particular subliquidum and possibly contents of eucalyptus oil, ephedrine or other active ingredients, lip pomades based on paraffin both for use in strong sunlight and then existing contents of light protection agents such as also for the care of the lips to protect against cracking. Preparations for dentistry with the advantage of good adhesion to the oral mucosa and teeth when the mouth is rinsed with water are also provided. Liquid or pasty preparations with or without active ingredients are suitable for rectal application.
According to what has been said, the further component of an oily consistency is of any type, provided that it is pharmaceutically or cosmetic harmless and suitability.

Fatty oils of natural and synthetic origin, those derived synthetically from glycerides, are suitable produced neutral oils, paraffinum subliquidum and generally esters from polyhydric alcohols with 2 to 4 carbon atoms and saturated or unsaturated, straight-chain or branched-chain monocarboxylic acids having 1 to 30 carbon atoms.

So-called neutral oils are preferred, i. H. non-rancid triglycerides of the saturated straight-chain Fatty acids with 6 to 14, in particular 8 to 12 carbon atoms, and corresponding triglycerides, in which, in addition to the saturated fatty acids mentioned, are aliphatic dicarboxylic acids with 2 to 6 carbon atoms are included.

It is to be understood that the oily consistency component may or may not have very small proportions can even be omitted if the viscous gel-like ester mixture contains only very small proportions of silanes as a reaction component, in which case the active ingredient is then a Herbal active ingredient-containing press oil is.

The new viscous gel-like ester mixtures and their preparation are described below.

In Examples 1 to 3 and in Example 8b, the examples relate to spreadable preparations. The remaining Examples relate to the preparation of the viscous gel-like ester mixtures.

The viscous gel-like ester mixtures consist of reaction products of fatty acid polyol partial esters or mixtures thereof with hydroxyl numbers of 5 to 150, preferably 10 to 80, with 2 to 45% by weight, preferably 4 to 30% by weight, based on the ester mixtures, of / -Glycidyloxypropyl-trialkoxysilanes with Alkyl groups of 1 to 3 carbon atoms or mixtures thereof and from reaction products, which are further Reaction component dicarboxylic acids or their anhydrides or halides in amounts of 0.01 to 50 Mol%, preferably 0.01 to 50 mol%, preferably 0.01 to 30 mol%, per mole of OH groups in the polyols may contain.

With increasing hydroxyl numbers from 5 to 150 the converted partial esters become with corresponding increasing Contained from 2 to 45% by weight / -glycidyl-oxipropyl-trialkoxisilanes Obtained ester mixtures of increasing viscosity.

If dicarboxylic acids are included as a reaction component, their increasing content causes a less increase in viscosity, but above all low cloud points.

The viscosities of the ester mixtures are therefore determined by the choice of the components and the components used Proportions variable and reproducible.

The term fatty acid polyol partial ester refers to the substance class of fatty acid esters containing hydroxyl groups from di- to hexafunctional alcohols and their ether polyols. Polyhydric alcohols, d. H. Polyols are for example propanediol, glycerol, trimethylolpropane, pentaerythritol or sorbitol. The spectrum the acids esterifiable to partial esters include saturated, unsaturated, straight-chain and branched-chain, aliphatic and cycloaliphatic monocarboxylic acids with 2 to 22 carbon atoms or mixtures thereof and, if necessary, additionally esterifiable saturated, unsaturated, aliphatic and / or aromatic dicarboxylic acids, preferably aliphatic dicarboxylic acids with 2 to 20, especially 2 to 8 carbon atoms. The ones for the cosmetic sector Possible viscous gel-like ester mixtures particularly contain polyols such as 1,2-propanediol, Mono-, di- and triethylene glycols or glycerol and especially fatty acids of aliphatic, straight-chain or branched, especially saturated, type with 6 to 18 carbon atoms. In addition, especially in the partial esterification dicarboxylic acids such as succinic acid, adipic or sebacic acid are included.

Optionally trimethylolpropane or pentaerythritol can be used be included.

The fatty acid polyol partial esters to be converted always contain free hydroxyl groups of the ones used Polyols, the amount of which is expressed by the hydroxyl number (OH number, measured in mg KOH per g ester).

The converted silanes go through reaction of the epoxy group of the glycidyl radical with these hydroxyl groups the partial ester a bond.

In the case of partial esters with contents of dicarboxylic acids, these also have the hydroxyl numbers in the mentioned area. The acid number (AN) is then preferably 0 or very small. So much for the way the reaction is carried out the second carboxyl group of the dicarboxylic acids is not bound, may possibly be a small or higher acid number, in addition to the hydroxyl number, occur.

In contrast, neutral esters or full esters of the polyols with the acids mentioned have hydroxyl numbers and acid numbers of 0 or very small values.

To the extent that esters are formed by reaction of partial esters with a molar excess of dicarboxylic acids these will have OHN 0 and an acid number due to free carboxyl groups.

Such partial esters with defined hydroxyl group contents can be prepared by known catalytic Esterification of the polyol components with a reduced amount compared to the stoichiometric amount Amount of fatty acid or by reaction of full esters of fatty acids or esters of fatty acids and Dicarboxylic acid of a transesterification according to EP 00 14 308 with polyols in the manner of a transesterification in the presence by alkali or acids.

The organo-organosilanes required are known and are commercially available. Are preferred ^ -Glycidyl-oxipropyl-trimethoxisilane, / -Glycidyl-oxipropyl-tripropoxisilane or their mixtures. As such, silanes with an epoxy group in a residue are more arbitrary Type and one to three alkoxy groups of any type and an additional number of inert residues can be used, however, such silanes are difficult to access.

The viscous gel-like ester mixtures are generally neutral esters with little or no hydroxyl and acid numbers.

For special purposes, the production conditions and quantities of the components can be selected Partial esters with an SZ of 5 up to 150 or esters containing carboxyl groups with SZ up to 150 are obtained will.

The ester mixtures are characterized by the following special advantages:

1. There are odorless, uniform, viscous, gel-like ester mixtures of transparency and pleasant Skin feeling.

2. The stability of the viscous gel-like ester mixtures is excellent because of the formation of a gel structure takes place by linking via main valences.

3. The viscous gel-like ester mixtures obtained show no tendency to oily when used in pharmaceutical preparations or for adding additives to technical formulations. Self Solid-liquid phase changes are reversible.

4. They are largely soluble in mineral oils of the paraffinic and aromatic type and in ester oils or dispersible and can be used to adjust their viscosity.

5. Viscous gel-like ester mixtures with dropping points of above 300 ^° C. can be produced.

6. The evaporation losses at elevated temperatures are due to the incorporation of the silane compound minimized.

7. The viscous gel-like ester mixtures have excellent structure-forming properties in creams and lotions on.

8. The viscosity or gel properties of the ester mixtures obtained can be as desired, depending on the installation the organo-organo-oxy-silane can be adjusted to the fatty acid-polyol-partial ester.

The silane radicals are preferably completely condensed by splitting off alcohol to form Si — O — Si siloxane groups, but the alkoxy groups can also be partially or, in exceptional cases, completely retained.
The production of the viscous gel-like ester mixtures can in the most general case be done by reacting the silane component with polyol ester, which preferably has hydroxyl groups corresponding to the hy-

Have hydroxyl numbers 5 to 150 and have monocarboxylic acid residues and optionally dicarboxylic acid residues or optionally with polyol esters which have carboxyl groups in appropriate amounts with acid numbers from 5 to 150 due to the content of dicarboxylic acids. Also the implementation of partial esters with a stoichiometric A deficit of the silane component is possible.

The partial esters can be prepared in any way before the reaction, as can esters with contents of carboxyl groups, known esterification catalysts, especially titanium esters, being used.

The reaction with the silanes is preferably carried out in the presence of catalysts, e.g. B. Lewis acids better known Kind, toluenesulfonic acid or AICh or SnCL4.

The same catalysts are suitable for the siloxane-type condensation. Suitable catalysts are given in Ullmann Volume 21 p. 515. As far as alkoxy groups are to be retained, no or only part of the alcohol is split off or the temperature is low, e.g. B. 120 to 140 ⁰ C held. Reduced pressure of 2 to 1000 mbar, particularly 100 to 200 mbar, is expedient.

Fatty acid polyol partial esters that are difficult to access, as well as esters with carboxyl group contents can directly before the reaction with the silane, z. B. from neutral esters or from the components below known conditions of transesterification or esterification are produced, with production in the same Vessel is possible.

If a dicarboxylic acid component is included, this can be achieved by adding the dicarboxylic acid or their derivatives, especially the anhydride mixtures, anhydrides or halides, especially chlorides will.

Viscous gel-like ester mixtures are produced by using fatty acid polyol partial esters or mixtures thereof with hydroxyl numbers of 5 to 150, preferably 10 to 80 with 2 to 45% by weight, preferably 4 to 30% by weight, based on the Estergemische of y- glycidyl oxipropyl-trialkoxysilanes having alkyl groups of 1 to 3 carbon atoms at 20-210 ⁰ C, preferably 60 to 120 ° C, and reacting the free alkoxy groups of the silanes at 100 to 240 ⁰ C, preferably 160 to 200 ⁰ C, with steam passing through at steam temperatures of 100 to 240 ⁰ C, preferably 150 to 170 ⁰ C, condensed completely or partially siloxane-like to viscous gel-like ester mixtures or fatty acid polyol partial esters with hydroxyl numbers from 5 to 150 by reaction of fatty acid polyol esters forms by reaction with polyols and then reacts with 2 to 45% by weight of ^ -glycidyl-oxipropyl-trialkoxysilanes and condenses in a corresponding siloxane-like manner

You can also use dicarboxylic acids or their anhydrides or halides in amounts of 0.01 to 50 mol% of the OH groups of the polyols with fatty acid polyol partial esters to those of hydroxyl numbers from 5 to 150 before the reaction with ^ -Glycidyl-oxipropyl-trialkoxysilanes realize.

In the examples, OHN is the hydroxyl number and AN is the acid number.

example 1

The sun protection gel la and the viscous sun protection oil 1 b are produced in a stirred tank by combining and stirring at 40 ^{° C. until the components are homogeneously distributed}

example

\ a

viscous
Ester mixture
after

Example 4
Most neutral 1 *)

50 parts by weight 10 parts by weight

50 parts by weight

90 parts by weight
5 parts by weight

Neo-Heliopan **) 5 parts by weight

*) Light protection substance from Haarmann and Reimer, Holzminden.

**) Mixed acid triglyceride from 2.1 mol of saturated fatty acids with chain length Cg to Qo and 0.45 mol of succinic acid.
■ 15

Both products have a pleasant feeling on the skin. Product IZ? creates a visible, product 1 a has a strong shine. The skin cannot be wetted.

Product la is subjected to a washing test by usual washing exposed to the skin with soap: Even after the 3rd

Laundry runs off the skin; only after the 5th

For the most part, laundry is the product.

Wash almost completely removed.

For comparison, a gel is made from the neutral ester I and an organically modified montmorillonite (Bentone (R), NL-Industries, Inc., Highstown, N.J., USA) in one to produce the same viscosity stirred in sufficient quantity. This gel is removed by washing with soap for the first time.

Example 2

By mixing 20 parts of the product according to Example 5 with 80 parts of neutral oil II (triglyceride der saturated fatty acids mean chain length Cs to Cio) and 10 parts of eucalyptus oil, a viscous oil for instillation in the nose for colds is made. Other active ingredients such. B. Ephedrine can be added.

The product is evenly distributed over the nasal mucous membrane in small amounts. Only after several Hours is required to be reapplied.

Example 3

By mixing 20 parts of the product according to Example 5 with 80 parts of neutral oil II and 5 parts of a Mixture of equal proportions of lemon balm oil, mountain pine oil and Johanneskant oil (01. Hyperici) is a Massage oil produced that can be easily and evenly distributed and after just a short rubbing in, none releases oily components on clothing

Example 4

A mixture of 150 g of triethylene glycol, 426 g of isostearic acid and 0.1 g of tetrabutyl titanate is heated to 240 ° C at 760 mbar while stirring in a 1 liter ground-joint flask equipped with a stirrer, water separator, thermometer and gas inlet tube, whereupon at the same temperature the pressure is reduced to 100 within 6 hours. The partial ester thus formed has an acid number below 1 and a hydroxyl number of 52. After cooling to 100 ⁰ C 150 g / -Glycidyloxipropyl-trimethoxysilane and 1 g of AlCl 3 are added as catalyst and stirred. At 180 ° C and 100 mbar, the steam is then introduced through the present at a steam temperature of 130 ° C

Reaction mixture. The steam is passed through until there is no more methanol is split off. In the process, methanol and water are continuously removed as vapors. Takes place in parallel the viscosity increase of the silane-modified ester mixture to a clear, transparent oleogel.

SZ: less than 2

Viscosity at 2O ⁰ C = 47 500 mPa · s

OHZ: 40

Example 5

At the reaction temperature described in Example 4, a mixture of 80 g of 1,2-propanediol, 450 g of oleic acid and 0.1 g of tetrabutyl titanate is esterified under the reaction conditions described to give a partial ester with an acid number of 0.6 and a hydroxyl number of 55. At 80 ° C. and 1000 mbar, 136 g of glycidyl-oxipropyl-triethoxysilane are added on in the presence of 0.5 g of SnCU. Subsequently, at 14O ⁰ C and 40 mbar introduced steam at 120 ⁰ C in the reaction mixture. The introduction of water vapor takes place until the ethanol has been completely split off. A viscous gel-like ester mixture with a spreadable and transparent consistency is obtained.

Viscosity at 20 ^° C. = 37,600 mPas

OHZ: 39

Example 6

In a 1 liter ground-joint flask equipped with a stirrer, water separator, thermometer and gas inlet tube, 500 g of a triglyceride mixture of saturated vegetable fatty acid with an average chain length of 8 to 10 carbon atoms and adipic acid, with 0.55 moles of adipic acid and 1.9 Moles of said vegetable fatty acid per mole of glycerin were esterified, and 6 g of glycerin and 0.1 g of tetrabutyl titanate were heated for 4 hours ^{with simultaneous passage of inert gas at 240 ° C. with stirring.} The achieved by transesterification hydroxyl number of the reaction mixture is 26. This reaction mixture, condensed as succinic acid fatty acid partial glyceride present, is added with 52 g of y-glycidyl-oxypropyl-trimethoxysilane and 1 g of AlCl3 and stirred for 0.5 hours at 100 ° C and 1000 mbar . Subsequently, at 180 ⁰ C and passed 80 mbar with stirring hot 160 ⁰ C water vapor through the silane-modified fatty acid partial esters. Fission methanol and water vapor are removed as vapors. The viscosity of the silane-modified fatty acid partial ester increases as the amount of methanol increases. a clear, transparent gel results after the elimination of the methanol has ended

SZ: 0.7

Saponification number: 394

OHZ: 22

Viscosity at 20 ^° C.: 10 800 mPas

Drop point higher than 300 ° C

Example 7

According to Example 6, 500 g of a triglyceride are used from saturated coconut oil fatty acids with 8 to 18 carbon atoms and a hydroxyl number of 9 and 12 g of glycerine in the presence of 0.1 g of tetrabutyl titanate to a fatty acid partial glyceride with a hydroxyl number of 49 interesterified The further reaction with 139 g / -glycidyl-oxypropyl-tripropoxysilane and 2 g SnCU takes place at

120 ° C and 1000 mbar. This is followed by at 200 ° C and 50 mbar steam introduction with steam temperatures of 170 ° C over a reaction period of 6 Hours the breakdown into a highly viscous oleogel.

SZ: 0.8

OHZ: 35

Viscosity at 52 ° C: 83,000 Pa · s

Melting point: 39.5 ⁰ C

Example 8a

As in Example 4, a mixture of 114 g of trimethylolpropane and 555 g of isostearic acid is esterified in the presence of 0.2 g of tetrabutyl titanate to give a partial ester with a hydroxyl number of 59. The addition of 156 g of ^ -glycidyl-oxypropyl-trimethoxysilane takes place in the presence of 2 g of AlCl ₃ at 100 ° C. and 1000 mbar. The silane-modified partial ester is filtered to remove the catalyst and then ^{gelled with passage of steam at steam temperatures of 160 to 180 °} C. and 80 mbar. Within a reaction time of 4 hours, methanol and water are removed as vapors.

SZ: 1.4
OHZ: 48
Viscosity at 20 ° C: 82,00OmPas

Example 8b

The solubility and viscosity of the silamodified trimethylolpropane isostearate gel produced according to Example 8a is examined in a mixture with trimethylolpropane triisostearate. The respective proportions of viscous Gel-like ester mixture and ester component are weighed out in a beaker and kept at 20 to 25 ° C stirred. Overall, viscous to gel-like clear solutions or gel systems result.

M]
Weight percent Weight percent Viscosity at Oleogel Ester 30 ° C [mPa · s] 45 '0 100 135 20th 80 840 40 60 4,380 50 50 10 500 60 40 18,000 50 80 20th 47 500 100 0 82,000

Oleogels with a similar gradation of viscosity are made by mixing the substances of the examples 1 to 5a with fatty oils, preferably non-rancid reesterification oils made from glycerine and saturated oils straight-chain monocarboxylic acids of chain length Cg to Ci 2 and with vegetable press oils containing active ingredients or extract oils obtained.

Example 9

In accordance with Example 4, 82 g of pentaerythritol and 613 g of isostearic acid are esterified in the presence of 0.1 g of tetrabuyl titanate to give a pentaerythritol partial ester with a hydroxyl number of 20. At 100 ⁰ C in the presence of 1 g AlCl 3, the addition takes place of 55 g of γ- glycidyl-oxypropyl-trimethoxysilane. Underwater

The introduction of steam at steam temperatures of 160 to 180 ° C. and 80 mbar condenses the reaction mixture within 6 hours to a clear, viscous gel-like ester mixture with elimination of methanol.

OHZ: 14 Viscosity at 30 ° C: 4 80OmPas

Example 10

According to Example 4, 82 g of pentaerythritol and 562 g of isostearic acid are obtained in the presence of 0.1 g of tetrabutyl titanate 2U esterified with a pentaerythritol partial ester with a hydroxyl number of 40. At 100 ° C the Addition of 102 g of ^ -glycidyl-oxypropyl-trimethoxysilane in the presence of 1 g of AICI3. With the introduction of steam with steam temperatures of 160 to 180 ° C and 80 mbar, the reaction mixture condenses within of 7 hours to a clear viscous oleogel with elimination of methanol.

OHZ: 32 Viscosity at 30 ° C: 36,00OmPas

Example 11

According to Example 4, 82 g of pentaerythritol and 511 g of isostearic acid are obtained in the presence of 0.1 g of tetrabutyl titanate esterified to a pentaerythritol partial ester with a hydroxyl number of 60. At 100 ° C the Addition of 141 g of ^ -glycidyl-oxypropyl-trimethoxysilane in the presence of 1 g of AICI3. With the introduction of steam with steam temperatures of 160 to 180 ° C and 80 mbar, the reaction mixture condenses within 8 hours to a clear, highly viscous oleogel with elimination of methanol.

OHT: 55 Viscosity at 30 ° C: 98,000 Pa-s

40

45

50

55

60

Claims (1)

Patent claims: 1. Spreadable preparation with high adhesion to the skin, consisting of a) 5 to 80% by weight of a gel-like ester mixture consisting of reaction products of fatty acid polyol partial esters or their mixtures with hydroxyl numbers from 5 to 150 with 2 to 45% by weight, based on the ester mixtures, of ^ -glycidyl-oxypropyl-trialkoxysilanes with alkyl groups of 1 to 3 carbon atoms or mixtures thereof and b) 95 to 20% by weight of a component with an oily consistency or a W / O or O / W emulsion from this and water as well as possibly c) 0.01 to 20% by weight of an active ingredient or its liquid or, if appropriate, solid preparation.