Emulsifier for low-viscosity w/o emulsions, based on partially crosslinked polyglycerin esters of polyhydroxystearic acid.

The invention relates to polyglycerol partial esters of polyhydroxystearic acid and polyfunctional carboxylic acids, obtainable by esterification of a polyglycerol mixture with polyhydroxystearic acid with N = 1 to 10 units and either dimer fatty acids obtained by catalytic dimerization of unsaturated fatty acids with 12 to 22 carbon atoms and an average functionality of 2 to 3, or with aliphatic, linear or branched dicarboxylic acids with a chain length of 2 to 16 carbon atoms and additionally saturated or unsaturated, linear or branched fatty acids with 6 to 22 carbon atoms, the degree of esterification of the polyglycerol mixture being between 20 and 75%. The invention comprises their production and use as W / O emulsifiers in cosmetic or pharmaceutical preparations and as auxiliaries for the dispersion of inorganic micropigments in oil dispersions.

It is known to the person skilled in the art that water-in-oil emulsions are difficult to stabilize against coalescence of the water droplets and thus against water separation due to the dense packing of the water droplets, which is a consequence of the usually high proportion of disperse phase (> 65%) . Another consequence of the high packing density is a high viscosity of the emulsion per se. In order to achieve sufficient stability required by the cosmetic industry, stabilizing waxes and in some cases also highly viscous oils are used, both of which increase the viscosity of the (outer) oil phase, thus reducing the mobility of the water droplets and protecting them against coalescence. However, highly viscous oils and stabilizing waxes have a negative impact on the skin feeling, which is reflected in a heavy and sticky feeling. In principle, oil-in-water emulsions, which are known to have a lighter skin feel, can be used as an alternative, but water-in-oil emulsions have a significantly better care effect than oil-in-water emulsions.

A generally desirable goal is therefore to make water-in-oil emulsions as light as possible, ie low-viscosity as oil-in-water emulsions, without having to give up their special care effect. In particular, the task is to enable water-in-oil emulsions that are as viscous as possible, non-sticky and nevertheless stable. The emulsifier to be used plays a key role here.

For ecological reasons, there is considerable interest in W / O emulsifiers based on native raw materials, both among producers and consumers of emulsion preparations. For this reason, partial esters of polyalcohols, such as glycerol, polyglycerol, sorbitol or methylglycoside and fatty acids, such as oleic or isostearic acid, are used in a variety of ways.

However, this type of emulsifier is not suitable for stabilizing flowable emulsions (lotions) and creams with a high content of native triglycerides. The creams corresponding to the stability requirements of the market (temperature resistance from -15 to +45 ° C, sometimes from -25 to +50 ° C) contain, in addition to the mentioned W / O emulsifiers on lipid-like components, mainly paraffin oils and fatty acid esters of monoalkanols (MW <500 ); these have more favorable technological properties than the higher molecular weight triglycerides. For stabilization, however, relatively high concentrations of viscosity-increasing waxes (≥ 3%) are required, which have a negative effect on the application properties, since they produce an undesirable sticky-greasy feeling on the skin.

Co-emulsifiers, especially ethylene oxide adducts in combination with metal soaps, only extend the range of application to lotions containing paraffin oil.

The polyglycerol esters of dimeric and polymerized unsaturated C have significantly better emulsifying properties than the polyalcohol fatty acid partial esters₁₈Fatty acids. They are obtained from the mono- and diglycerides of vegetable oils, preferably soybean oil, by thermal treatment at about 300 ° C. for several hours or by transesterification of a thermally polymerized vegetable oil with polyglycerol.

The polyglycerol polyricinoleates formed from castor oil using an analogous process are also powerful W / O emulsifiers (DE-B-44 09 569).

Both classes of substances have not been able to establish themselves in cosmetic or pharmaceutical emulsion preparations because of their sensitivity to oxidation and the often greasy rancid odor. This is primarily due to the massive thermal load during production and the unsaturated character (iodine number approx. 100).

In contrast, the polyglycerol polyricinoleate chemically related, which can also be produced from vegetable raw materials, has a satisfactory sensory quality and has the basic ability to form creamy and in particular flowable W / O emulsions.

According to DE-A-40 12 693, esters of polycarboxylic acids with polyhydroxy compounds have been proposed. Condensation of the starting compounds gives products with excess carboxyl groups, which are then neutralized. The reaction products are suitable as O / W emulsifiers.

EP-B-0 835 862 describes partial polyglycerol esters obtainable by esterification of a polyglycerol mixture with a degree of esterification of polyglycerol between 30 and 75% and saturated or unsaturated, linear or branched fatty acids with 12 to 22 carbon atoms and dimer fatty acids with an average functionality of 2 to 2.4. Compared to polyglycerol polyhydroxystearate, these have the additional advantage of improved stability, in particular a higher freeze-thaw capacity of the W / O emulsions produced therewith. However, the emulsions are still relatively viscous and cause a slightly sticky feeling on the skin.

The improvement of the freeze-thaw load capacity is of considerable practical interest for the transportability and storability of the emulsion preparations. Due to prolonged storage at very low temperatures or extreme temperature fluctuations with longer transport routes, the insufficient stabilization of the emulsion can show through clear water deposits in the emulsion preparation or even lead to complete breakage of the emulsion.

The object of the invention was to develop an emulsifier which allows the formulation of low-viscosity emulsions which have a pleasant feeling on the skin and at the same time have an improved resistance to freeze-thaw.

It has now surprisingly been found that, in particular, low-viscosity, but at the same time particularly stable water-in-oil emulsions can be obtained if the emulsifiers used are polyglycerol partial esters of polyhydroxystearic acid which are additionally linked to dicarboxylic acids.

The invention therefore relates to partial polyglycerol esters of polyhydroxystearic acid and polyfunctional carboxylic acids, obtainable by esterification of a polyglycerol mixture with polyhydroxystearic acid with N = 1 to 10, preferably 2 to 8, in particular 2 to 5 units and dimer fatty acids which are obtained by catalytic dimerization of unsaturated fatty acids with 12 to 22 C atoms were obtained and have an average functionality of 2 to 3 and / or with aliphatic, linear or branched di- and / or tricarboxylic acids with a chain length of 2 to 16 carbon atoms and additionally saturated or unsaturated, linear or branched fatty acids with 6 to 22 carbon atoms, preferably 12 to 18 carbon atoms, the degree of esterification of the polyglycerol mixture is between 20 and 75%, preferably 40 to 70%.

Another object of the invention is the use of the polyglycerol partial esters according to the invention as W / O emulsifiers in cosmetic or pharmaceutical preparations.

Surprisingly, it has been shown that even highly polar vegetable oils can be introduced into stable emulsions, whereas conventional emulsifiers lead to emulsions which are particularly unstable at low temperatures. The condensation products based on the 12-hydroxystearic acid are liquid and are therefore suitable in addition to the classic "hot-hot" production also for the energy-saving "cold-cold" production of emulsions.

The polyhydroxystearic acids used in accordance with the invention are prepared, for example, by polycondensation of hydroxystearic acid, preferably 12-hydroxystearic acid, which is obtained by curing ricinoleic acid or technical castor oil fatty acid, using the known processes. There are esterification products of the general formula<chemistry id="chem0001" num="0001"><img file="EP1500427A2_D0001.tif" /></chemistry> With<dl id="dl0001" compact="compact"><dt>N =</dt><dd>1 to 10, preferably 2 to 8, in particular 2 to 5 fatty acid units formed, which have acid numbers between 187 and 20, preferably between 96 and 45.</dd></dl>

Polyglycerols are, in particular, those of the general formula<chemistry id="chem0002" num="0002"><img file="EP1500427A2_D0002.tif" /></chemistry> with an average degree of condensation n of 1 to 11, preferably 2 to 6, particularly preferably 3 to 6 and hydroxyl numbers of approx. 1,350 to approx. 800, preferably approx. 1,200 to approx. 900.

These are technical polyglycerol mixtures which, for. B. can be obtained by alkaline-catalyzed condensation of glycerol at elevated temperatures, from which fractions with the desired degree of condensation can optionally be obtained by distillation processes. Also suitable are polyglycerols which are used in other ways, e.g. B. from epichlorohydrin or glycidol.

The use of polyglycerols which have the following homolog distribution (GC method) has proven to be particularly advantageous; The preferred ranges are given in brackets:<ul id="ul0001" list-style="none" compact="compact"><li>Glycerin: 0 to 20 (&lt;5) wt%</li><li>Diglycerins: 0 to 60 (5 to 30)% by weight</li><li>Triglycerins: 0 to 60 (5 to 50)% by weight</li><li>Tetraglycerols: 0 to 30 (5 to 25)% by weight</li><li>Pentaglycerins: 0 to 30 (5 to 20)% by weight</li><li>Oligoglycerins: ad 100% by weight</li></ul>

As is known, the dimer fatty acids used are a mixture of acyclic and cyclic dicarboxylic acids which are obtained by a catalyzed dimerization of unsaturated fatty acids having 12 to 22 carbon atoms and have an average functionality of 2 to 3, preferably about 2. They can also contain to a lesser extent polymeric fatty acids (trimeric and higher functional). The acid numbers are in the range from 150 to 290, preferably 190 to 200.

Commercial products have an average <tables id="tabl0001" num="0001"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Monomer content of approx.</entry><entry namest="col2" nameend="col2" align="right">7 up to 15% by weight</entry></row><row><entry namest="col1" nameend="col1" align="left">Dimer levels of approx.</entry><entry namest="col2" nameend="col2" align="right">70 up to 77% by weight</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Polymer content of approx.</entry><entry namest="col2" nameend="col2" align="right">15 up to 16% by weight.</entry></row></tbody></tgroup></table></tables>

They can be adjusted to higher contents of the respective functionalities (mono, di, tri) and / or by hydrogenation to low proportions of unsaturated fatty acids (low iodine numbers) by the known separation processes.

Further information can be found in the product sheets of manufacturers such as Uniqema (Pripol®) and Arizona Chem. (Unidyme®, Century®).

For the production and use of dimer acids and their physical and chemical properties, reference is also made to the publication "The Dimer Acids: The chemical and physical properties, reactions and applications", Ed. EC Leonard; Humko Sheffield Chemical, 1975, Memphis, Tenn.

The use of relatively short-chain di- or tricarboxylic acids instead of dimer acids, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, is particularly suitable for the use according to the invention as emulsifiers. Also suitable are hydroxydi- or tricarboxylic acids, such as malic acid, tartaric acid, citric acid.

The alkanedicarboxylic acids having 4 to 14 carbon atoms are particularly preferred.

By using these acids, a significantly improved stabilization of the phase interfaces in W / O emulsions can be achieved.

Saturated fatty acids such as lauric acid, tridecanoic acid, myristic acid, palmitic acid, margaric acid, stearic acid, isostearic acid, arachic acid and behenic acid and mixtures thereof are particularly suitable as additional fatty acid components.

Naturally occurring mixtures are, for example, coconut fatty acids, the main constituent of which is lauric acid, and also saturated C₁₄- to C₁₈Fatty acids and optionally saturated C₈- to C₁₀-Fatty acids and unsaturated fatty acids contain, as well as tallow fatty acids, which are essentially a mixture of palmitic acid and stearic acid.

Suitable additional unsaturated fatty acid components are monoolefinically unsaturated acids, for example hexadecenoic acids, octadecenoic acids, such as oleic acid (cis-9-octadecenoic acid) or elaidic acid (trans-9-octadecenoic acid), eicosenoic acids and docosenoic acids, such as erucic acid (cis-13-docosenoic acid) or brassido trans-13-docosenoic acid), polyunsaturated fatty acids, for example octadecadienoic acids and octadecatrienoic acids, such as linoleic acid and linolenic acid, and mixtures thereof.

The liquid fatty acids such as oleic, ricinoleic, erucic and isostearic acid, which contain 18 to 22 carbon atoms, are particularly suitable. Their solidification points are below 35 ° C due to branching or a double bond in the hydrocarbon chain. Fatty acid mixtures which can also contain waxy components such as hardened ricinoleic acid can also be used. It is also possible to use lactones, such as butyrolactone or caprolactone, as the fatty acid component.

In the polyglycerol partial esters according to the invention, 20 to 75%, preferably 40 to 70%, of the hydroxyl groups of the polyglycerol are esterified.

In their production, variants A) and B) are preferred according to those in one<ul id="ul0002" list-style="none" compact="compact"><li>A) first stage polyglycerol up to a degree of esterification of 10 to 70%, preferably 25 to 40%, esterified with fatty acid and dicarboxylic acid and / or dimer acid and in a second stage with polyhydroxystearic acid to a total degree of esterification 20 to 75%, preferably 40 to 60% , esterified or in one</li><li>B) first stage polyglycerol up to a degree of esterification of 10 to 70%, preferably 25 to 40%, esterified with fatty acid and polyhydroxystearic acid and in one second stage with dicarboxylic acid and / or dimer acid to a total degree of esterification 20 to 75%, preferably 40 to 60%, esterified.</li></ul>

Other fatty acid order and one-pot procedures are also possible.

The molar ratio of polyhydroxystearic acid to diacid / dimer acid to fatty acid according to the invention is in the range from 0.25 to 4 mol to 0.1 to 2 mol to 0 to 10 mol, preferably in the range from 0.25 to 2 mol to 0.3 to 1 mol 0.5 to 3 mol, a suitable HLB value of about 3 to 8 being set by suitable selection of the hydrophilic and lipophilic molecular components in order to obtain properties which are favorable for the stabilization of W / O emulsions. This is achieved by the proportion of hydrophilic components being in the range 10 to 70%, preferably 20 to 40%.

The polyglycerol partial esters according to the invention can be prepared in a manner known per se by heating the reaction components and removing the water of reaction formed by distillation. Acidic or basic catalysts, such as sulfonic acids, phosphoric acid or phosphorous acid, Lewis acids, such as tin salts, alkali metal or alkaline earth metal oxides or hydroxides, alcoholates or salts, can also be used for the acceleration. However, the addition of a catalyst is not absolutely necessary. The progressing conversion can be monitored, for example, by means of the water of reaction separated off, by measuring the acid number or by infrared spectroscopy. In general, an acid number in the end product of &lt;20, preferably &lt;10 is aimed for. Products with an acid number &lt;5 are particularly preferred.

The polyglycerol esters according to the invention are suitable for stabilizing aqueous emulsions and dispersions.

Their use as emulsifiers for the production of cosmetic or pharmaceutical preparations is preferred. Possible cosmetic preparations which obtain an easily spreadable consistency through the use of oil-in-water or water-in-oil emulsifiers, because these emulsifier systems allow an oil or a fat to readily penetrate into an aqueous phase or allows an aqueous phase to be worked well into an oil or a fat, for example creams, such as care creams, baby creams or sunscreen creams, ointments, lotions or make-up. In pharmaceutical preparations, such as ointments or creams, oil-in-water or water-in-oil emulsifiers are required to apply active ingredients.

The following oil components can be used:<ul id="ul0003" list-style="dash" compact="compact"><li>Ester oils, such as octyl palmitate, octyl stearate, cetyl octanoate, caprylic / capric acid triglycerides, decyl oleate, cetearyl octanoate, isopropyl myristate, isopropyl palmitate, C_12-13-Alkyl benzoate, stearyl heptanoate, dibutyl adipates</li><li>Vegetable oils such as wheat germ oil, jojoba oil, olive oil, borage oil, avocado oil, peanut oil, almond oil, sunflower oil, walnut oil</li><li>higher alcohols, such as octyldodecanol (or Guerbet alcohols in general), oleyl alcohol, and</li><li>paraffin-like (hydrocarbon) oils, such as paraffin oil, isohexadecane, polydecene, petroleum jelly, paraffinum perliquidum, squalane.</li></ul>

Furthermore, the compositions and constituents known to the person skilled in the art in cosmetic and pharmaceutical applications, and also conventional auxiliaries and additives, such as stabilizers or preservatives, are also used for such cosmetic and pharmaceutical preparations.

The polyglycerol partial esters used according to the invention bring about a significantly increased storage stability of the cosmetic and pharmaceutical preparations prepared with them at low temperatures compared to the prior art, which is particularly important in the case of water-in-oil emulsions which are more difficult to stabilize than oil-in-water emulsions is.

Furthermore, lower concentrations and / or smaller amounts of consistency waxes in the preparations are generally required of the polyglycerol partial esters in order to achieve the same effect as with agents of the prior art. The water-in-oil emulsions produced with the polyglycerol partial esters according to the invention are also less viscous than similarly stable emulsions which are produced with emulsifiers from the prior art.

Synthesis examples:

Example 1:

In the first stage, polyglycerol (hydroxyl number (OH-Z) = 1,090) is esterified with fatty acid. 88.4 g (0.31 mol) of isostearic acid and 157.5 g (0.13 mol) of polyhydroxystearic acid with an acid number (SZ) of 47 are esterified with 100 g of polyglycerol in the first stage at 240 ° C. and under nitrogen. After a reaction time of 2 hours at this temperature, the acid number was &lt;10. In the second stage, the mixture is cooled to 130 ° C. and 22.5 g (0.11 mol) of sebacic acid are added. The mixture is heated again to 240 ° C. and stirred at this temperature for 3 hours. A viscous product with an acid number of &lt;5 is obtained.

Example 2:

91.1 g (0.32 mol) of isostearic acid and 141.7 g (0.12 mol) of polyhydroxystearic acid with an acid number (SZ) of 47 are mixed with 61.9 g of polyglycerol (OH-Z = 950) at 240 ° C. and esterified under nitrogen. After a reaction time of 2 hours at this temperature, the acid number was &lt;10. In the second stage, the mixture is cooled to 130 ° C. and 20.2 g (0.1 mol) of sebacic acid are added. The mixture is heated again to 240 ° C. and stirred at this temperature for 3 hours. A viscous product with an acid number of &lt;5 is obtained.

Example 3:

120.0 g (0.42 mol) of isostearic acid and 75.0 g (0.17 mol) of polyhydroxystearic acid with an acid number (SZ) of 47 are mixed with 75.0 g of polyglycerol (OH-Z = 950) at 240 ° C. and esterified under nitrogen. After a reaction time of 2 hours at this temperature, the acid number was &lt;10. In the second stage, the mixture is cooled to 130 ° C. and 20.2 g (0.1 mol) of sebacic acid are added. The mixture is heated again to 240 ° C. and stirred at this temperature for 3 hours. A viscous product with an acid number of &lt;5 is obtained.

Example 4:

111.8 g (0.39 mol) of isostearic acid and 110.4 g (0.09 mol) of polyhydroxystearic acid with an acid number (SZ) of 47 are mixed with 61.9 g of polyglycerol (OH-Z = 1,090) at 240 ° C. and esterified while passing nitrogen. After a reaction time of 2 hours at this temperature, the acid number was &lt;10. In the second stage, the mixture is cooled to 130 ° C. and 20.2 g (0.1 mol) of sebacic acid are added. The mixture is heated again to 240 ° C. and stirred at this temperature for 3 hours. A viscous product with an acid number of &lt;5 is obtained.

Example 5:

91.1 g (0.32 mol) of isostearic acid and 141.7 g (0.12 mol) of polyhydroxystearic acid with an acid number (SZ) of 45 are mixed with 61.9 g of polyglycerol (OH-Z = 1,090) in the first stage 240 ° C and esterified under nitrogen. After a reaction time of 2 hours at this temperature, the acid number was &lt;10. The mixture is then cooled to 180 ° C. and 57.5 g (0.1 mol) of dimer fatty acid (Empol 1,062) are added. The mixture is heated again to 240 ° C. and stirred at this temperature for 3 hours. A viscous product is obtained which is characterized by an acid number of &lt;5.

Example 6:

91.1 g (0.32 mol) of isostearic acid and 141.7 g (0.12 mol) of polyhydroxystearic acid with an acid number (SZ) of 45 are mixed with 61.9 g of polyglycerol (OH-Z = 1,090) in the first stage 240 ° C and esterified under nitrogen. After a reaction time of 2 hours at this temperature, the acid number was &lt;10. The mixture is then cooled to 130 ° C. and 14.6 g (0.1 mol) of adipic acid are added. The mixture is heated again to 240 ° C. and stirred at this temperature for 3 hours. A viscous product is obtained which is characterized by an acid number of &lt;5.

Example 7:

88.4 g (0.31 mol) of isostearic acid and 22.5 g (0.11 mol) of sebacic acid are esterified with 175.8 g of polyglycerol (OH-Z = 850) in the first stage at 240 ° C. while passing nitrogen through. After a reaction time of 2 hours at this temperature, the acid number was &lt;10. Then 157.5 g (0.13 mol) of polyhydroxystearic acid with an acid number (SZ) of 45 are added at 240 ° C. while passing nitrogen. The mixture is then stirred at 240 ° C. until the temperature is &lt;5.

Example 8:

91.1 g (0.32 mol) of isostearic acid and 20.2 g (0.1 mol) of sebacic acid are esterified with 61.9 g of polyglycerol (OH-Z = 1090) in the first stage at 240 ° C. while passing nitrogen through. After a reaction time of 2 hours at this temperature, the acid number was &lt;10. Then 141.7 g (0.12 mol) of polyhydroxystearic acid with an acid number (SZ) of 59 are added at 240 ° C. while passing nitrogen. The mixture is then stirred at 240 ° C. until the temperature is &lt;5.

Example 9:

215.6 g (0.2 mol) of polyhydroxystearic acid with an acid number (SZ) of 48, which had previously been esterified with an equivalent amount of isostearic acid, are esterified with 24 g of polyglycerol (OH-Z = 1,190) in a manner known per se. After a reaction time of 2 hours at this temperature, the acid number was &lt;10. The mixture is then cooled to 130 ° C. and 10.1 g (0.2 mol) of sebacic acid are added. The batch is heated again to 240 ° C. and stirred at this temperature for 8 hours until an acid number of &lt;5 is reached.

Example 10:

The polyglycerol ester is prepared in one step. 61 g polyglycerol (OH-Z = 1,090), 91.1 g (0.32 mol) isostearic acid, 20.2 g (0.1 mol) sebacic acid and 141.7 g (0.12 mol) polyhydroxystearic acid with an acid number ( SZ) of 59 are initially introduced and then heated to 240 ° C. while passing through nitrogen until the acid number is &lt;5.

Example 11:

91.1 g (0.32 mol) of isostearic acid, 10.1 g (0.05 mol) of sebacic acid and 6.7 g (0.05 mol) of malic acid are mixed in with 61.9 g of polyglycerol (OH-Z = 1,090) the first stage esterified at 240 ° C under nitrogen. After a reaction time of 2 hours at this temperature, the acid number was &lt;10. Then 141.7 g (0.12 mol) of polyhydroxystearic acid with an acid number (SZ) of 45 are added at 240 ° C. while passing nitrogen. The mixture is then stirred at 240 ° C. until the temperature is &lt;5.

Example 12:

91.1 g (0.32 mol) of isostearic acid and 20.2 g (0.1 mol) of sebacic acid are esterified with 61.9 g of polyglycerol (OH-Z = 850) in the first stage at 240 ° C. while passing nitrogen through. After a reaction time of 2 hours at this temperature, the acid number was &lt;10. Then 141.7 g (0.12 mol) of polyhydroxystearic acid with an acid number (SZ) of 45 are added at 240 ° C. while passing nitrogen. The mixture is then stirred at 240 ° C. until the temperature is &lt;5.

Example 13:

91.1 g (0.32 mol) of isostearic acid and 20.2 g (0.1 mol) of sebacic acid are esterified with 63 g of polyglycerol (OH-Z = 1190) in the first stage at 240 ° C. while passing nitrogen through. After a reaction time of 2 hours at this temperature, the acid number was &lt;10. Then 141.7 g (0.12 mol) of polyhydroxystearic acid with an acid number (SZ) of 45 are added at 240 ° C. while passing nitrogen. The mixture is then stirred at 240 ° C. until the temperature is &lt;5.

Example 14:

88.4 g (0.31 mol) of isostearic acid and 22.5 g (0.11 mol) of sebacic acid are esterified with 127.8 g of polyglycerol (OH-Z = 890) in the first stage at 240 ° C. while passing nitrogen through. After a reaction time of 2 hours at this temperature, the acid number was &lt;10. Then 157.5 g (0.12 mol) of polyhydroxystearic acid with an acid number (SZ) of 45 are added at 240 ° C. while passing nitrogen. The mixture is then stirred at 240 ° C. until the temperature is &lt;5.

Example 15:

88.4 g (0.31 mol) of isostearic acid and 22.5 g (0.11 mol) of sebacic acid are esterified with 175.8 g of polyglycerol (OH-Z = 850) in the first stage at 240 ° C. while passing nitrogen through. After a reaction time of 2 hours at this temperature, the acid number was &lt;10. Then 157.5 g (0.13 mol) of polyhydroxystearic acid with an acid number (SZ) of 45 are added at 240 ° C. while passing nitrogen. The mixture is then stirred at 240 ° C. until the temperature is &lt;5.

Example 16:

132.9 g (0.47 mol) of isostearic acid and 16.9 g (0.08 mol) of sebacic acid are esterified with 51.6 g of polyglycerol (OH-Z = 1,080) in the first stage at 240 ° C. while passing nitrogen through. After a reaction time of 2 hours at this temperature, the acid number was &lt;10. Then 237.7 g (0.2 mol) of polyhydroxystearic acid with an acid number (SZ) of 45 are added at 240 ° C. while passing nitrogen. The mixture is then stirred at 240 ° C. until the temperature is &lt;5.

Formulation examples:

Formulation example 1:

An emulsifier from the prior art based on polyglycerol partial esters of fatty acid and dimer acid (EP-B-0 835 862) is used as the emulsifier. <tables id="tabl0002" num="0002"><table frame="all"><tgroup cols="3" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center"><b>Formulation 1A (%)</b></entry><entry namest="col3" nameend="col3" align="center"><b>Formulation 1B (%)</b></entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left"><b>A</b>State-of-the-art emulsifier</entry><entry namest="col2" nameend="col2" align="center">2,50</entry><entry namest="col3" nameend="col3" align="center">2,50</entry></row><row><entry namest="col1" nameend="col1" align="left">Castor wax</entry><entry namest="col2" nameend="col2" align="center">0,25</entry><entry namest="col3" nameend="col3" align="center">0,25</entry></row><row><entry namest="col1" nameend="col1" align="left">Ceresin W 80</entry><entry namest="col2" nameend="col2" align="center">0,25</entry><entry namest="col3" nameend="col3" align="center">0,25</entry></row><row><entry namest="col1" nameend="col1" align="left">Paraffin oil</entry><entry namest="col2" nameend="col2" align="center">-</entry><entry namest="col3" nameend="col3" align="center">14,00</entry></row><row><entry namest="col1" nameend="col1" align="left">Octyl palmitate</entry><entry namest="col2" nameend="col2" align="center">11,00</entry><entry namest="col3" nameend="col3" align="center">8,00</entry></row><row><entry namest="col1" nameend="col1" align="left">C._8/10-Triglycerin</entry><entry namest="col2" nameend="col2" align="center">11,00</entry><entry namest="col3" nameend="col3" align="center">-</entry></row><row><entry namest="col1" nameend="col1" align="left"><b>B</b>Glycerin</entry><entry namest="col2" nameend="col2" align="center">3,35</entry><entry namest="col3" nameend="col3" align="center">3,35</entry></row><row><entry namest="col1" nameend="col1" align="left">Bronopol</entry><entry namest="col2" nameend="col2" align="center">0,05</entry><entry namest="col3" nameend="col3" align="center">0,05</entry></row><row><entry namest="col1" nameend="col1" align="left">MgSO₄ x 7H₂O</entry><entry namest="col2" nameend="col2" align="center">0,60</entry><entry namest="col3" nameend="col3" align="center">0,60</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">water</entry><entry namest="col2" nameend="col2" align="center">71,00</entry><entry namest="col3" nameend="col3" align="center">71,00</entry></row></tbody></tgroup></table></tables>

Manufacturing:

Stir B (20 ° C) into A (80 ° C), homogenize, repeat homogenization after 2 h cooling time.

Formulation example 2:

Another emulsifier from the prior art based on polyglycerol partial esters of polyhydroxystearic acid (DE-A-44 09 569) is used as the emulsifier. <tables id="tabl0003" num="0003"><table frame="all"><tgroup cols="3" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center"><b>Formulation 2A (%)</b></entry><entry namest="col3" nameend="col3" align="center"><b>Formulation 2B (%)</b></entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left"><b>A</b>State-of-the-art emulsifier</entry><entry namest="col2" nameend="col2" align="center">2,50</entry><entry namest="col3" nameend="col3" align="center">2,50</entry></row><row><entry namest="col1" nameend="col1" align="left">Castor wax</entry><entry namest="col2" nameend="col2" align="center">0,25</entry><entry namest="col3" nameend="col3" align="center">0,25</entry></row><row><entry namest="col1" nameend="col1" align="left">Ceresin W 80</entry><entry namest="col2" nameend="col2" align="center">0,25</entry><entry namest="col3" nameend="col3" align="center">0,25</entry></row><row><entry namest="col1" nameend="col1" align="left">Paraffin oil</entry><entry namest="col2" nameend="col2" align="center">-</entry><entry namest="col3" nameend="col3" align="center">14,00</entry></row><row><entry namest="col1" nameend="col1" align="left">Octyl palmitate</entry><entry namest="col2" nameend="col2" align="center">11,00</entry><entry namest="col3" nameend="col3" align="center">8,00</entry></row><row><entry namest="col1" nameend="col1" align="left">C._8/10-Triglycerin</entry><entry namest="col2" nameend="col2" align="center">11,00</entry><entry namest="col3" nameend="col3" align="center">-</entry></row><row><entry namest="col1" nameend="col1" align="left"><b>B</b>Glycerin</entry><entry namest="col2" nameend="col2" align="center">3,35</entry><entry namest="col3" nameend="col3" align="center">3,35</entry></row><row><entry namest="col1" nameend="col1" align="left">Bronopol</entry><entry namest="col2" nameend="col2" align="center">0,05</entry><entry namest="col3" nameend="col3" align="center">0,05</entry></row><row><entry namest="col1" nameend="col1" align="left">MgSO₄ x 7H₂O</entry><entry namest="col2" nameend="col2" align="center">0,60</entry><entry namest="col3" nameend="col3" align="center">0,60</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">water</entry><entry namest="col2" nameend="col2" align="center">71,00</entry><entry namest="col3" nameend="col3" align="center">71,00</entry></row></tbody></tgroup></table></tables>

Manufacturing:

Stir B (20 ° C) into A (80 ° C), homogenize, repeat homogenization after 2 h cooling time.

Formulation example 3:

An emulsifier according to embodiment 1 is used as the emulsifier. <tables id="tabl0004" num="0004"><table frame="all"><tgroup cols="3" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center"><b>Formulation 3A (%)</b></entry><entry namest="col3" nameend="col3" align="center"><b>Formulation 3B (%)</b></entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left"><b>A</b>Emulsifier according to example 1</entry><entry namest="col2" nameend="col2" align="center">2,50</entry><entry namest="col3" nameend="col3" align="center">2,50</entry></row><row><entry namest="col1" nameend="col1" align="left">Castor wax</entry><entry namest="col2" nameend="col2" align="center">0,25</entry><entry namest="col3" nameend="col3" align="center">0,25</entry></row><row><entry namest="col1" nameend="col1" align="left">Ceresin W 80</entry><entry namest="col2" nameend="col2" align="center">0,25</entry><entry namest="col3" nameend="col3" align="center">0,25</entry></row><row><entry namest="col1" nameend="col1" align="left">Paraffin oil</entry><entry namest="col2" nameend="col2" align="center">-</entry><entry namest="col3" nameend="col3" align="center">14,00</entry></row><row><entry namest="col1" nameend="col1" align="left">Octyl palmitate</entry><entry namest="col2" nameend="col2" align="center">11,00</entry><entry namest="col3" nameend="col3" align="center">8,00</entry></row><row><entry namest="col1" nameend="col1" align="left">C._8/10- triglycerin</entry><entry namest="col2" nameend="col2" align="center">11,00</entry><entry namest="col3" nameend="col3" align="center">-</entry></row><row><entry namest="col1" nameend="col1" align="left"><b>B</b>Glycerin</entry><entry namest="col2" nameend="col2" align="center">3,35</entry><entry namest="col3" nameend="col3" align="center">3,35</entry></row><row><entry namest="col1" nameend="col1" align="left">Bronopol</entry><entry namest="col2" nameend="col2" align="center">0,05</entry><entry namest="col3" nameend="col3" align="center">0,05</entry></row><row><entry namest="col1" nameend="col1" align="left">MgSO₄ x 7H₂O</entry><entry namest="col2" nameend="col2" align="center">0,60</entry><entry namest="col3" nameend="col3" align="center">0,60</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">water</entry><entry namest="col2" nameend="col2" align="center">71,00</entry><entry namest="col3" nameend="col3" align="center">71,00</entry></row></tbody></tgroup></table></tables>

Manufacturing:

Stir B (20 ° C) into A (80 ° C), homogenize, repeat homogenization after 2 h cooling time.

Formulation example 4:

An emulsifier according to embodiment 2 is used as the emulsifier. <tables id="tabl0005" num="0005"><table frame="all"><tgroup cols="3" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center"><b>Formulation 4A (%)</b></entry><entry namest="col3" nameend="col3" align="center"><b>Formulation 4B (%)</b></entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left"><b>A</b>Emulsifier according to example 2nd</entry><entry namest="col2" nameend="col2" align="center">2,50</entry><entry namest="col3" nameend="col3" align="center">2,50</entry></row><row><entry namest="col1" nameend="col1" align="left">Castor wax</entry><entry namest="col2" nameend="col2" align="center">0,25</entry><entry namest="col3" nameend="col3" align="center">0,25</entry></row><row><entry namest="col1" nameend="col1" align="left">Ceresin W 80</entry><entry namest="col2" nameend="col2" align="center">0,25</entry><entry namest="col3" nameend="col3" align="center">0,25</entry></row><row><entry namest="col1" nameend="col1" align="left">Paraffin oil</entry><entry namest="col2" nameend="col2" align="center">-</entry><entry namest="col3" nameend="col3" align="center">14,00</entry></row><row><entry namest="col1" nameend="col1" align="left">Octyl palmitate</entry><entry namest="col2" nameend="col2" align="center">11,00</entry><entry namest="col3" nameend="col3" align="center">8,00</entry></row><row><entry namest="col1" nameend="col1" align="left">C._8/10-Triglycerin</entry><entry namest="col2" nameend="col2" align="center">11,00</entry><entry namest="col3" nameend="col3" align="center">-</entry></row><row><entry namest="col1" nameend="col1" align="left"><b>B</b>Glycerin</entry><entry namest="col2" nameend="col2" align="center">3,35</entry><entry namest="col3" nameend="col3" align="center">3,35</entry></row><row><entry namest="col1" nameend="col1" align="left">Bronopol</entry><entry namest="col2" nameend="col2" align="center">0,05</entry><entry namest="col3" nameend="col3" align="center">0,05</entry></row><row><entry namest="col1" nameend="col1" align="left">MgSO₄ x 7H₂O</entry><entry namest="col2" nameend="col2" align="center">0,60</entry><entry namest="col3" nameend="col3" align="center">0,60</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">water</entry><entry namest="col2" nameend="col2" align="center">71,00</entry><entry namest="col3" nameend="col3" align="center">71,00</entry></row></tbody></tgroup></table></tables>

Manufacturing:

Stir B (20 ° C) into A (80 ° C), homogenize, repeat homogenization after 2 h cooling time.

Formulation example 5:

An emulsifier according to embodiment 3 is used as the emulsifier. <tables id="tabl0006" num="0006"><table frame="all"><tgroup cols="3" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center"><b>Formulation 5A%</b></entry><entry namest="col3" nameend="col3" align="center"><b>Wording 5B%</b></entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left"><b>A</b>Emulsifier according to example 3rd</entry><entry namest="col2" nameend="col2" align="center">2,50</entry><entry namest="col3" nameend="col3" align="center">2,50</entry></row><row><entry namest="col1" nameend="col1" align="left">Castor wax</entry><entry namest="col2" nameend="col2" align="center">0,25</entry><entry namest="col3" nameend="col3" align="center">0,25</entry></row><row><entry namest="col1" nameend="col1" align="left">Ceresin W 80</entry><entry namest="col2" nameend="col2" align="center">0,25</entry><entry namest="col3" nameend="col3" align="center">0,25</entry></row><row><entry namest="col1" nameend="col1" align="left">Paraffin oil</entry><entry namest="col2" nameend="col2" align="center">-</entry><entry namest="col3" nameend="col3" align="center">14,00</entry></row><row><entry namest="col1" nameend="col1" align="left">Octyl palmitate</entry><entry namest="col2" nameend="col2" align="center">11,00</entry><entry namest="col3" nameend="col3" align="center">8,00</entry></row><row><entry namest="col1" nameend="col1" align="left">C._8/10-Triglycerin</entry><entry namest="col2" nameend="col2" align="center">11,00</entry><entry namest="col3" nameend="col3" align="center">-</entry></row><row><entry namest="col1" nameend="col1" align="left"><b>B</b>Glycerin</entry><entry namest="col2" nameend="col2" align="center">3,35</entry><entry namest="col3" nameend="col3" align="center">3,35</entry></row><row><entry namest="col1" nameend="col1" align="left">Bronopol</entry><entry namest="col2" nameend="col2" align="center">0,05</entry><entry namest="col3" nameend="col3" align="center">0,05</entry></row><row><entry namest="col1" nameend="col1" align="left">MgSO₄ x 7H₂O</entry><entry namest="col2" nameend="col2" align="center">0,60</entry><entry namest="col3" nameend="col3" align="center">0,60</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">water</entry><entry namest="col2" nameend="col2" align="center">71,00</entry><entry namest="col3" nameend="col3" align="center">71,00</entry></row></tbody></tgroup></table></tables>

Manufacturing:

Stir B (20 ° C) into A (80 ° C), homogenize, repeat homogenization after 2 h cooling time.

Formulation example 6:

An emulsifier according to embodiment 4 is used as the emulsifier. <tables id="tabl0007" num="0007"><table frame="all"><tgroup cols="3" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center"><b>Formulation 6A (%)</b></entry><entry namest="col3" nameend="col3" align="center"><b>Formulation 6B (%)</b></entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left"><b>A</b>Emulsifier according to example 4th</entry><entry namest="col2" nameend="col2" align="center">2,50</entry><entry namest="col3" nameend="col3" align="center">2,50</entry></row><row><entry namest="col1" nameend="col1" align="left">Castor wax</entry><entry namest="col2" nameend="col2" align="center">0,25</entry><entry namest="col3" nameend="col3" align="center">0,25</entry></row><row><entry namest="col1" nameend="col1" align="left">Ceresin W 80</entry><entry namest="col2" nameend="col2" align="center">0,25</entry><entry namest="col3" nameend="col3" align="center">0,25</entry></row><row><entry namest="col1" nameend="col1" align="left">Paraffin oil</entry><entry namest="col2" nameend="col2" align="center">-</entry><entry namest="col3" nameend="col3" align="center">14,00</entry></row><row><entry namest="col1" nameend="col1" align="left">Octyl palmitate</entry><entry namest="col2" nameend="col2" align="center">11,00</entry><entry namest="col3" nameend="col3" align="center">8,00</entry></row><row><entry namest="col1" nameend="col1" align="left">C._8/10-Triglycerin</entry><entry namest="col2" nameend="col2" align="center">11,00</entry><entry namest="col3" nameend="col3" align="center">-</entry></row><row><entry namest="col1" nameend="col1" align="left"><b>B</b>Glycerin</entry><entry namest="col2" nameend="col2" align="center">3,35</entry><entry namest="col3" nameend="col3" align="center">3,35</entry></row><row><entry namest="col1" nameend="col1" align="left">Bronopol</entry><entry namest="col2" nameend="col2" align="center">0,05</entry><entry namest="col3" nameend="col3" align="center">0,05</entry></row><row><entry namest="col1" nameend="col1" align="left">MgSO₄ x 7H₂O</entry><entry namest="col2" nameend="col2" align="center">0,60</entry><entry namest="col3" nameend="col3" align="center">0,60</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">water</entry><entry namest="col2" nameend="col2" align="center">71,00</entry><entry namest="col3" nameend="col3" align="center">71,00</entry></row></tbody></tgroup></table></tables>

Manufacturing:

Stir B (20 ° C) into A (80 ° C), homogenize, repeat homogenization after 2 h cooling time.

While emulsions 3A, 3B, 4A, 4B, 5A, 5B, 6A and 6B produced with an emulsifier according to the invention have a low viscosity (Brookefield RVT Helipath Stand, Model D; VAC 230, spindle C), Emulsion 1A and 1B show produced with an emulsifier from the prior art based on polyglycerol partial esters of fatty acid and dimer acid (EP-B-0 835 862), an increased viscosity and thus a slightly sticky skin feel.

Emulsions 2A and 2B, produced with an emulsifier from the prior art based on polyglycerol partial esters of polyhydroxystearic acid (DE-A-44 09 569), show a medium viscosity but clear water separation after low-temperature storage (12 h at -15 ° C or . -25 ° C), which makes it difficult to transport the emulsions.

The results are summarized in the following table: <tables id="tabl0008" num="0008"><table frame="all"><tgroup cols="3" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center"><b>Viscosity [Pas]</b></entry><entry namest="col3" nameend="col3" align="center"><b>stability</b></entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left"><b>Emulsion 1A</b></entry><entry namest="col2" nameend="col2" align="center">28</entry><entry namest="col3" nameend="col3" align="center">stable</entry></row><row><entry namest="col1" nameend="col1" align="left"><b>Emulsion 1B</b></entry><entry namest="col2" nameend="col2" align="center">23</entry><entry namest="col3" nameend="col3" align="center">stable</entry></row><row><entry namest="col1" nameend="col1" align="left"><b>Emulsion 2A</b></entry><entry namest="col2" nameend="col2" align="center">19</entry><entry namest="col3" nameend="col3" align="center">Water separation at -15 ° C</entry></row><row><entry namest="col1" nameend="col1" align="left"><b>Emulsion 2B</b></entry><entry namest="col2" nameend="col2" align="center">15</entry><entry namest="col3" nameend="col3" align="center">Water separation at -25 ° C</entry></row><row><entry namest="col1" nameend="col1" align="left"><b>Emulsion 3A</b></entry><entry namest="col2" nameend="col2" align="center">13</entry><entry namest="col3" nameend="col3" align="center">stable</entry></row><row><entry namest="col1" nameend="col1" align="left"><b>Emulsion 3B</b></entry><entry namest="col2" nameend="col2" align="center">8</entry><entry namest="col3" nameend="col3" align="center">stable</entry></row><row><entry namest="col1" nameend="col1" align="left"><b>Emulsion 4A</b></entry><entry namest="col2" nameend="col2" align="center">13</entry><entry namest="col3" nameend="col3" align="center">stable</entry></row><row><entry namest="col1" nameend="col1" align="left"><b>Emulsion 4B</b></entry><entry namest="col2" nameend="col2" align="center">10</entry><entry namest="col3" nameend="col3" align="center">stable</entry></row><row><entry namest="col1" nameend="col1" align="left"><b>Emulsion 5A</b></entry><entry namest="col2" nameend="col2" align="center">12</entry><entry namest="col3" nameend="col3" align="center">stable</entry></row><row><entry namest="col1" nameend="col1" align="left"><b>Emulsion 5B</b></entry><entry namest="col2" nameend="col2" align="center">10</entry><entry namest="col3" nameend="col3" align="center">stable</entry></row><row><entry namest="col1" nameend="col1" align="left"><b>Emulsion 6A</b></entry><entry namest="col2" nameend="col2" align="center">11</entry><entry namest="col3" nameend="col3" align="center">stable</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left"><b>Emulsion 6B</b></entry><entry namest="col2" nameend="col2" align="center">9</entry><entry namest="col3" nameend="col3" align="center">stable</entry></row></tbody></tgroup></table></tables>