WO2010017651A1

WO2010017651A1 - Peg-free emulsifiers

Info

Publication number: WO2010017651A1
Application number: PCT/CH2009/000270
Authority: WO
Inventors: Ivo Nägeli; Alexander Wagner
Original assignee: Dr. W. Kolb Ag
Priority date: 2008-08-15
Filing date: 2009-08-13
Publication date: 2010-02-18
Also published as: EP2313455A1

Abstract

The invention relates to an emulsifier comprising a hydrophilic polyester, the terminal position of which is covalently extended by a hydrophobic part, such as fatty alcohol, long-chained 1,2-alkyl epoxy, polycyclic alcohol. Furthermore, a method for producing such an emulsifier is described, and also various uses of such a surfactant, particularly as an emulsifier in the cosmetics sector.

Description

DESCRIPTION

TITLE

TECHNICAL FIELD The present invention relates to biodegradable polyethylene glycol (PEG) -free emulsifiers or more generally surface-active substances, in particular based on naturally available starting materials and in particular for use in the cosmetic sector. Furthermore, it relates to processes for the preparation of such emulsifiers and uses as emulsifiers but also as surface-active substances.

STATE OF THE ART

Especially for cosmetic applications there is a steadily growing demand for natural products from renewable sources. This is one of the reasons why one tries, the successful PEG-containing emulsifiers z. T. replace with suitable alternatives. Instead of PEG, monomers are often selected as the hydrophilic part of the emulsifier. For example, EP0437460B1 and GB950667 describe synthetic routes for the preparation of emulsifiers based on sugars and glycerol.

Suitable hydrophilic polymers, which could form the hydrophilic part of an emulsifier in analogy to the polymer PEG, are not found in nature, but from other fields are (synthetic) hydrophilic polyethers and polyesters based on natural building blocks (polyols or polyols and ( Hydroxy) dicarboxylic acids). EP0835862A1 describes, for example, emulsifiers whose hydrophilic part is formed by polyglycerol, while WO2006 / 084613 discloses hydrophilic polyesters which have been esterified on free (pendant) hydroxyl groups (optionally also on terminal hydroxyl groups) by nitrogen-containing carboxylic acids or fatty acids. These graft copolymers find use as gas hydrate inhibitors.

From WO 2006/043048 specific systems are known in connection with emulsifiers, in which a polyester is coupled directly to a fatty acid such as lauric acid. Problematic with the descriptions in this document Lauric acid is coupled. The problem with the systems described in this document, in which the polyesters are based on polyols, is the fact that it is difficult or even frequently impossible to prevent the fatty acid not only terminally but also still in the course of the production process further hydroxyl groups of the polyester is attached.

From US 3511797 are in connection with polishes emulsifiers based on polyesters consisting of aromatic dicarboxylic acids, such as. As the isophthalic acid, and propylene or ethylene glycol known. In other words, they contain building-like or structurally identical monomers of PEG and are not free of aromatic substances, which makes them unsuitable in particular for cosmetic applications.

PRESENTATION OF THE INVENTION

Accordingly, the object of the invention is to provide an improved emulsifier (or, more generally, an improved surfactant), in particular, but not exclusively, for cosmetic applications. Furthermore, the object to be achieved is to produce such an emulsifier and to indicate uses of such an emulsifier.

The solution to this problem is achieved in that a surface-active substance or preferably an emulsifier is provided from a hydrophilic polyester, which is terminally covalently extended by a hydrophobic part. The hydrophobic part is preferably selected from the group of fatty alcohols, long-chain 1, 2-Alkylepoxide, and polycyclic alcohols, these preferably of natural origin, in particular cholesterol, tocopherol. Also possible are mixtures or combinations of such systems and derivatives of such systems. The term long-chain 1, 2-Alkylepoxide (also called 1, 2 alkylene oxide) are understood to mean systems in which the alkyl chain has 12-22 carbon atoms, preferably 16-18 carbon atoms.

In general, in connection with this application, the term "long-chain" in the case of alkyl groups, unless stated otherwise, is understood to mean that the alkyl chain is 12-22 Having carbon atoms, preferably 16-18 carbon atoms. The alkyl chain is linear or branched, preferably linear. The alkyl chain is preferably completely saturated, but it may also be partially unsaturated. Also possible are mixtures of such systems with different chain lengths. The term fatty alcohols, which is to be understood broadly in the context of this application, also means systems in which the fatty alcohol is not directly attached to the polyester element, but via hydroxyl groups of intervening structural elements such as sugar building blocks in the sense of alkyl polyglycosides, phosphate glyceryl spacers, phosphonate glyceryl spacers, tartrate glyceryl spacers, tartrate sorbitanyl spacers, tartrate sorbityl spacers, tartrate methylglucosyl spacers. or instead of tartrate corresponding diester of other dicarboxylic acids, such as. As malic acid or oxalic acid.

Also to be understood by the term fatty alcohols are systems in which a fatty acid has an ester bond via an intervening structural element which has an alcohol function for attachment to the polyester. For example, systems such as fatty acid sorbitan esters, fatty acid glyceryl esters or fatty acid methylglucosyl esters, which are attached to the polyester via hydroxyl groups of the sorbitan or the glyceryl or methylglucosyl unit. The term thus also includes such fatty acid derivatives with terminal hydroxyl function. The emulsifier is PEG-free and preferably free of aromatic constituents.

As well as fatty alcohol and / or long-chain 1,2-alkyl epoxide or derivatives thereof, polyhydric alcohols of natural origin, such as, for example, cholesterol, tocopherol, typically terpene-based alcohols of natural origin, are generally suitable as hydrophobic parts. Fatty alcohol and long-chain 1, 2-alkyl epoxides or their derivatives, but also the said polycyclic alcohols, can be used substituted or unsubstituted.

The preferred hydrophobic parts are fatty alcohol and / or long-chain 1,2-alkyl epoxide or their derivatives. The core of the invention is therefore to provide an emulsifier as a substitute for polyethylene glycol systems available by the chain of polyethylene glycol is replaced by a polyester, said polyester must have the corresponding hydrophilicity, then in combination or after Connection of fatty alcohol and / or long-chain 1, 2-alkyl-epoxide or their derivatives to show the desired emulsifying effect. Typically, the fatty alcohol and / or long-chain 1, 2-alkyl-epoxide is free of nitrogen.

Fatty alcohols have limited reactivity under certain conditions. This can be compensated by no fatty alcohol or not exclusively fatty alcohol is used, but as an alternative, a long-chain 1,2-alkyl epoxide is used.

Under certain circumstances, the fact that the polyester constituent has (and must have) a hydrophilic character is also not unproblematic, in which case the second constituent to be bonded to this constituent must have a hydrophobic character. Accordingly, the reaction can be problematic due to the poor miscibility of the reactants. This can be overcome by using not a simple fatty alcohol as starting material, but such a hydrophobic building block via an intermediate element, which in turn has hydrophilic character, and accordingly already has a certain hydrophilicity as starting material in combination with the fatty alcohol or fatty acid. Systems which are advantageous in this respect are the already mentioned above systems such as alkylpolyglycosides (in which the alkyl group usually has 12-18 carbon atoms, and in which 1-5 sugar building blocks, preferably 2-3 sugar building blocks are present), long-chain alkyl-glyceryl Phosphates or long-chain alkyl glyceryl phosphonates, long-chain alkyl glyceryl tartrates, long-chain alkyl sorbitanyl tartrates or long-chain alkyl sorbityl tartrates, long-chain alkyl methylglucosyl tartrates or the diesters of other diacids, such , As the malic acid or oxalic acid, or else systems such as fatty acid sorbitan esters, Fettsäuremethylglucoseester or Fettsäureglycerylester. The long-chain alkyl groups of these systems correspond to the fatty alcohol components. A polyester is preferably to be understood as meaning a hydrophilic polyester. hen, which prior to esterification or transesterification, or more generally expressed the attachment of fatty alcohol or its derivatives, in water at a temperature of 25 ° C has a solubility of more than 1 g per liter, preferably of more than 10 g per liter , In order for a polyester to have these properties, the specific combinations of dicarboxylic acids or their derivatives and diols described below are preferably used for the preparation.

According to one embodiment, the emulsifier is preferably characterized in that the hydrophilic polyester as starting material has a molar mass in the range of 500-50,000 g / mol, preferably in the range of 1,000-10,000 g / mol, particularly preferably in the range of 1,500-5,000 g / mol having.

Typically, in the case of the emulsifier, fatty alcohol or its derivatives and the already described fatty acid derivatives having terminal hydroxyl function and / or the long-chain 1,2-alkyl epoxide are exclusively terminally attached and not grafted to the polyester. According to a preferred embodiment of the invention, a dicarboxylic acid, preferably of natural origin, is reacted with a substituted or unsubstituted diol, preferably of natural origin, for the preparation of the polyester.

The dicarboxylic acid may be derivatized or non-derivatized, branched or unbranched. Furthermore, it may be unsubstituted or substituted with substituents selected from the group -OH, -OR, -COOH, COOR, -NH ₂ , -NHR, -NR ₂ , or combinations thereof, wherein R is preferably selected from among Group -CH ₃ , -CH ₂ CH ₃ .

The diol can in turn be branched or unbranched. Further, it may be unsubstituted or substituted with substituents selected from the group -OH, -OR, -COOH, COOR, -NH ₂ , -NHR, -NR ₂ , or combinations thereof, wherein R is preferably selected from the group -CH ₃ , -CH ₂ CH ₃ .

In particular, with regard to the hydrophilic properties of the polyester, it is preferred according to a further embodiment, when the dicarboxylic acid is a hydroxy or polyhydroxy dicarboxylic acid. This may preferably be selected from the group tartaric acid, malic acid or combinations or substituted and / or derivatized forms thereof.

Also with respect to the hydrophilic properties of the polyester, it is preferred that the diol is a polyol, preferably selected from the group consisting of glycerol, diglycerol, triglycerol, polyglycerol, sorbitol, isosorbide, or combinations or substituted forms thereof.

With regard to the hydrophilic properties of the polyester, it should be emphasized that not only the properties of the dicarboxylic acids alone or of the diols alone are to be used, but that the combination of a suitable dicarboxylic acid with a correspondingly adapted suitable diol must be selected such that the required actually adjust the hydrophilic properties of the polyester. Which combinations of the monomers are suitable can be easily determined by measuring the required solubility of the polyester alone mentioned above.

A further preferred embodiment of the invention is characterized in that the fatty alcohol and / or the long-chain 1, 2-alkyl-epoxide is branched or unbranched, saturated or unsaturated, and that it 6-24, preferably 10-18, particularly preferably 16 or Has 18 carbon atoms. It is particularly preferred, in particular also for ensuring the exclusively terminal attachment to the polyester, that it is not a fatty acid but a fatty alcohol or its derivatives or a fatty acid ester with terminal hydroxy groups, particularly preferably a fatty alcohol having 16 or 18 carbon atoms , A system of a polyester which is very particularly preferred in this context is based on tartaric acid and glycerol and / or sorbitol.

Furthermore, the present invention relates to a process for producing an emulsifier as described above. The method is particularly characterized in that diacid or corresponding diester and diol together with fatty alcohol and / or long-chain 1,2-alkyl epoxide or derivatives thereof in a single step, optionally in the presence of a catalyst and / or an enzyme (in particular upon reaction of a fatty acid and / or a polyol having at least 4 hydroxy groups), are reacted together. Under catalysts are here and below to understand both those that are used for esterification or transesterification reactions, as well as phase transfer catalysts such. B. crown ethers respectively inverse phase transfer catalysts such. As cyclodextrins or Kalixarene. An alternative method for producing such an emulsifier is characterized in that, in a first step, diacid or corresponding diester and diol, if appropriate in the presence of a catalyst and / or an enzyme, are polymerized or oligomerized to give the polyester, and in a second subsequent step the polyester is brought exclusively in the presence of fatty alcohol and / or 1,2-alkyl epoxide or derivatives thereof exclusively or essentially exclusively terminal, wherein in turn a catalyst and / or an enzyme can be used.

In addition, the present invention relates to the use of an emulsifier, as described above, as an emulsifier, in particular for cosmetic products. In addition to the use as an emulsifier in cosmetic products, however, other possible uses for surface-active substances are possible, such. In the context of personal care products, detergents, pharmaceuticals, food products, paints, inks, varnishes and paper chemicals.

Likewise, the present invention relates to a cosmetic product, hygiene product, cleaning agent, pharmaceutical product, food product, paints, ink or varnish, a paper or a paper coating with such a surface-active substance.

Preferred further embodiments of the invention are described in the dependent claims. BRIEF EXPLANATION OF THE FIGURES

The invention will be explained in more detail with reference to embodiments in conjunction with the drawings. The two Figures 1 and 2 show microscopic images of different magnification of an oil / water emulsion with an emulsifier according to the invention. WAYS OF IMPLEMENTING THE INVENTION

The invention relates to biodegradable PEG-free emulsifiers whose hydrophilic part consists of a polyester (building blocks: polyols and (hydroxy) dicarboxylic acids), while the hydrophobic part is covalently exclusively or substantially exclusively at the terminal end (the terminal) Ends) of the polyester is bound. This regioselectivity (in the case of hydrophilic polyesters based on hydroxydicarboxylic acids) can be achieved either by reacting the polyester with a fatty alcohol whose derivatives or fatty acid esters with terminal hydroxy groups are obtained under suitable catalysis, for. B. lipase B (reactions at the terminal acid / ester or alcohol group (possibly the terminal acid / ester or alcohol groups)). Typically, based on the average molar mass of the polyester, the molar ratio of hydrophobe to polyester is selected in the range of 0.5: 1 - 2: 1. In contrast to WO2006 / 084613, the invention is a molecule with (at least for the most part) a linear structure which has a more hydrophilic character. Accordingly, other applications, such. B. the use of the invention as an emulsifier for cosmetic O / W formulations.

In a preferred embodiment, the hydrophilic polyester is composed of natural building blocks and comprises the polyols glycerol, diglycerol, triglycerol, polyglycerol, sorbitol, isosorbide and the (hydroxy) dicarboxylic acids tartaric acid, malic acid, malonic acid, malonic acid, succinic acid, glutaric acid and Adipic acid, while, depending on the desired HLB value of the emulsifier, fatty alcohols (branched and unbranched, saturated and unsaturated) of C6 to C24, in a preferred embodiment of ClO to Cl 8 find use.

The combinations of polyol and diacid are to be chosen so that the corresponding polyester has hydrophilic properties. To avoid (high) cross-linking, high hydroxyl polyols such as sorbitol must be subjected to selective catalysis, such as enzymatic catalysis (lipase B), where the reaction temperature should not exceed 80 ° C to obtain a high molecular weight In the case of "low hydroxyl polyols", the esterification or transesterification reactions take place according to the known state of the art. You can uncatalyzed or be carried out under acidic or alkaline catalysis in a melt, wherein the reaction temperatures between 100 and 250 ° C, preferably between 120 and 150 ⁰ C. Suitable catalysts are, for example hydrochloric acid, sulfonic acids, phosphoric acid, sodium hydroxide, potassium hydroxide, sodium, potassium, Lewis acids such. B. BF ₃ .

The esterification reactions may be carried out at atmospheric pressure or at reduced pressure. The reaction generally takes 5 - 10 h, in the case of enzyme catalysis up to 48 h.

Examples Example 1, Preparation of a Lauryl Poly (glyceryl tartrate)

In a 500 ml four-necked flask equipped with KPG stirrer, thermometer and distillation bridge 660 g of L-tartaric acid, 526.5 g of glycerol (molar ratio of starting materials: 1: 1.3) and 2.81 g Natriumhydroxidplätzchen submitted and heated by means of oil bath to about 130 ° C. It is applied a reduced pressure of about 250 mbar, which is continuously lowered in the course of the reaction. After about 8 hours of reaction time about 80 ml of water are distilled off, the reaction is stopped. This gives about 860 g of colorless, viscous product. The acid number is about 90 mg KOH / g. GPC measurements give a molar mass of the hydrophilic polyester predominantly in the range from 500 g / mol to 2500 g / mol. 100 g of poly (glyceryl tartrate), 12.3 g of lauryl alcohol and 2.67 g of p-toluenesulfonic acid monohydrate are introduced into a 250 ml four-necked flask with KPG stirrer, thermometer and distillation bridge and heated to about 130 ° C. in an oil bath. It is applied a reduced pressure of about 250 mbar, which is continuously lowered in the course of the reaction. After 3 h reaction time about 2 ml of water are distilled off, the single-phase reaction mixture is highly viscous. The product obtained is a very hard, slightly yellowish solid which has surface-active properties in aqueous solution.

Example 2, Preparation of a cetyl poly (sorbic acid adipate)

The synthesis of the hydrophilic polyester requires enzymatic catalysis and occurs essentially according to the literature (AS Kulshrestha et al., Chapter 23 in Polymer Biocatalysis and Biomaterials, Eds .: HN Cheng, RA Gross (2005)). 5 g of sorbitol, 4 g of adipic acid (molar ratio 1: 1) are added to a 100 ml three-necked flask with thermometer and distillation bridge and melted by heating in an oil bath to about 130 ° C. The oil bath temperature is then lowered to 75 to 80 ⁰ C and 1 g of Novozym 435, bound to support material lipase B added. Novozym 435 is previously dried for 24 hours at 25 ° C and about 50 mbar. After 2 h, a pressure of about 50 mbar is applied, after a total of 48 h, the reaction is stopped. The enzyme is filtered off and the reaction mixture is taken up in methanol. The product is whitish and viscous, it contains educts in addition to the linear hydrophilic polyester.

In a three-necked flask with thermometer and distillation bridge, 2 g of product and 1 g of cetyl alcohol are heated in an oil bath to about 120 ° C and applied a reduced pressure of about 50 mbar. After 5 h, the reaction is stopped. In addition to unreacted fatty alcohol, a light brown product is formed which has surface-active properties in aqueous solution.

Proof of emulsifying properties

77.9 g of a 4% aqueous lauryl poly (glyceryl tartrate) solution are prepared and neutralized to pH 7 by dropwise addition of 10% sodium hydroxide solution. Subsequently, 20 g of avocado oil are added and homogenized by means of a rotor-stator system (Ultra-Turrax). FIGS. 1 and 2 show micrographs of the OAV emulsion; they illustrate the emulsifying properties of the substance class disclosed in this invention using the example of lauryl poly (glyceryl tartrate).

EXAMPLE 3 Transesterification of Diethyl Tartrate with Lauryl Alcohol and Glycerol In a 500 ml three-necked flask with KPG stirrer, thermometer and water separator, 165.10 g (0.80 mol) diethyl tartrate, 38.20 g (0.20 mol) lauryl alcohol, 73.67 g glycerol (0.80 mol) ( molar ratio of the reactants 4: 1: 4) and 1.61 g of sodium ethanolate and heated to 12O ⁰ C by means of an oil bath. It is initially worked under a N ₂ atmosphere, after ₂ hours applied a reduced pressure of about 800 mbar, which was lowered after a further hour to about 300 mbar. After 24 hours was cooled the reaction mixture to 20 ° C. A colorless, viscous product is obtained.

EXAMPLE 4 Transesterification of Diethyl Tartrate with Stearyl Polyglycoside and Glycerol 123.71 g (0.60 mol) diethyl tartrate, 89.22 g (0.15 mol) stearyl polyglycoside, 55.25 g glycerol (0.60 mol) (molar ratio) are placed in a 500 ml three-necked flask with KPG stirrer, thermometer and water separator the educts 4: 1: 4) and 8.05 g Natriu- presented methoxide and heated to 140 ° C by oil bath. After 72 h at 300 mbar and 140 ° C, the reaction mixture is cooled to 20 ° C. A brownish viscous solid is obtained. Example 5, Reaction of poly (glyceryl tartrate) with 1,2-cetyl epoxide

In a 500 ml four-necked flask equipped with KPG stirrer, thermometer and distillation bridge 660 g of L-tartaric acid, 526.5 g of glycerol (molar ratio of starting materials: 1: 1.3) and 2.81 g Natriumhydroxidplätzchen submitted and heated to 130 ° C by oil bath. It is applied a reduced pressure of about 250 mbar, which is continuously lowered in the course of the reaction. After 8 h reaction time about 80 ml of water are distilled off, the reaction is stopped. This gives 860 g of colorless, viscous product, polyglyceryl tartrate. The acid number is 90 mg KOH / g. GPC measurements give a molar mass of the hydrophilic polyester predominantly in the range from 500 g / mol to 2500 g / mol. The following cosmetic formulations were prepared with the aid of the synthesized emulsifiers. They showed good stability.

Formulation 1: cream

Phase Share in%

A water (water) to 100

EDTA 0.1

Glycerol 2.0

Xanthan (xanthan gum) 0.3

B emulsifier from Example 1 4.0

Cetearyl alcohol (cetearyl alcohol) 3.5

Shea butter 2.0

Saturated Coco Glycerides (Hydrogenated Coco Glycerides) 0.5

Prunus Amygdalus (Sweet Almond) OeI (Sweet Almond) OiI 3.0

Octyl Dodecanol 4.0 Persea Gratissima 2.0

Isopropyl myristate (isopropyl myristate) 4.0

Dimethicone (Dimethicone) 1.0

Isohexadecane (isohexadecane) 2.0

BHT (butylhydroxytoluene) 0.1

Phenoxyethanol 0.9

Propylparaben 0.3

C tocopheryl acetate (tocopheryl acetate) 0.2

D Water (Water) 10

Sodium hyaluronate 0.1

E Perfume (q.s.)

F sodium hydroxide (sodium hydroxide) q.s.

Formulation 2: Lotion

Phase Share in%

A water (water) to 100

EDTA 0.1

Propylene Glycol 3.5

Xanthan (xanthan gum) 0.2

B Emulsifier from Example 2 4.0

Cetyl Alcohol (Cetyl Alcohol) 0.8

Shea butter 0.5

Squalane 1.0

Octyl Dodecanol 4.0

Caprat / Caprinate triglycerides (Caprylic / Capric triglyceride) 1.5

Isopropyl Palmitate (Isopropyl Palmitate) 4.0

Dimethicone (Dimethicone) 2.0

Isohexadecane (isohexadecane) 3.5

Ethyl Hexyl Cocoate (Ethyl Hexyl Cocoate) 1.0

BHT 0.1

Phenoxyethanol 0.9

Propylparaben 0.3

C tocopheryl acetate (tocopheryl acetate) 0.2

D Hydrolysed Milk Protein 2.0

E Perfume (q.s.)

F sodium hydroxide (sodium hydroxide) q.s.

Claims

1. A surfactant of a hydrophilic polyester, which is terminally covalently extended by a hydrophobic moiety selected from the group: fatty alcohol, long-chain 1, 2-Alkylepoxid, polycyclic alcohol, or combinations or mixtures thereof.

2. Surface-active substance according to claim 1, characterized in that the hydrophobic part is a fatty alcohol selected from the group: alkylpolyglycosides, long-chain alkyl-glyceryl-phosphates or alkyl-glyceryl

Phosphonates, long-chain alkyl glyceryl tartrates, long-chain alkyl sorbitanyl tartrates or alkyl sorbityl tartrates, long-chain alkyl-methylglucosyl tartrates or the diesters of other diacids, in particular malic acid or oxalic acid, fatty acid sorbitan esters, fatty acid glyceryl esters, fatty acid methylglu - coseester is.

3. Surface-active substance according to claim 1, characterized in that it is an emulsifier.

4. Emulsifier according to one of the preceding claims, characterized in that the hydrophilic polyester prior to esterification or transesterification in water at a temperature of 25 ° C has a solubility of more than 1 g per liter, preferably more than 10 g per liter.

5. Emulsifier according to one of the preceding claims, characterized in that the hydrophobic part, particularly preferably the fatty alcohol and / or the 1, 2-Alkylepoxid is free of nitrogen.

6. Emulsifier according to one of the preceding claims, characterized in that the hydrophilic polyester has a molecular weight in the range of 500 - 50,000 g / mol, preferably in the range of 1000 - 10000 g / mol, particularly preferably in the range of 1500 - 5000 g / mol wherein it is preferably free of aromatic constituents.

7. Emulsifier according to one of the preceding claims, characterized in that the fatty alcohol or the polycyclic alcohol, the latter is preferably selected from the group cholesterol and / or tocopherol, exclusively terminally attached to the polyester.

8. Emulsifier according to one of the preceding claims, characterized in that for the preparation of the polyester, a dicarboxylic acid, preferably of natural origin, with a substituted or unsubstituted diol, preferably of natural-borrowed origin, is reacted, preferably the dicarboxylic acid derivatized or not derivatized is, branched or unbranched, and / or unsubstituted or substituted with substituents selected from the group -OH, -OR, -COOH, COOR, -NH ₂ , -NHR, -NR ₂ , or combinations thereof, wherein R is selected from the group -CH ₃ , -CH ₂ CH ₃ , and / or wherein preferably the diol is branched or unbranched, and / or unsubstituted or substituted with substituents selected from the group -OH, -OR, - COOH, COOR, -NH ₂ , -NHR, -NR ₂ , or combinations thereof, wherein R is selected from the group -CH ₃ , -CH ₂ CH ₃ .

9. An emulsifier according to claim 8, characterized in that the dicarboxylic acid or its diester is unsubstituted or a hydroxy- or polyhydroxydicarboxylic acid, preferably selected from the group of tartaric acid, malic acid, oxalic acid, malonic acid, succinic acid, glutaric acid and adipic acid or combinations or substituted Forms of it, and / or that the diol is a polyol, preferably selected from the group glycerol, diglycerin, triglycerol, polyglycerol, sorbitol, isosorbide or combinations or substituted forms thereof.

10. Emulsifier according to one of the preceding claims, characterized in that the fatty alcohol and / or the 1, 2-Alkylepoxid is branched or unbranched, saturated or unsaturated, and that he 6-24, preferably 10-18, particularly preferably 16 or 18 Having carbon atoms.

11. Emulsifier according to one of the preceding claims, characterized in that it is a fatty alcohol, particularly preferably a fatty alcohol having 16 or 18 carbon atoms.

12. Emulsifier according to claim 11, characterized in that the polyester is based on tartaric acid and glycerol and / or sorbitol.

13. A process for preparing an emulsifier according to any one of the preceding claims, characterized in that diacid, or diester and diol together with the hydrophobic part, in particular the fatty alcohol and / or the 1, 2-Alkylepoxid or their derivatives, in a single step, optionally in the presence of a catalyst and / or an enzyme, are reacted together.

14. A process for the preparation of an emulsifier according to any one of the preceding claims 1-11, characterized in that in a first step diacid or diester and diol, optionally polymerized or oligomerized in the presence of a catalyst and / or an enzyme to the polyester, and in one second subsequent step of the polyester in the presence of the hydrophobic part, in particular of fatty alcohol and / or 1,2-Alkylepoxid, or derivatives thereof, optionally in the presence of a catalyst, exclusively or substantially exclusively terminal is reacted.

15. Use of a surface-active substance according to one of the preceding claims 1-11 for hygiene products, cleaning agents, food products, paints, inks, lacquers, papermaking, but especially as an emulsifier for cosmetic products.

16. Cosmetic product, hygiene product, cleaning agent, pharmaceutical product, food product, paint, ink or lacquer, for paper or paper coating with surface-active substances according to one of claims 1-11.