EP1750659A1

EP1750659A1 - Wax mixture based on partial glycerides and pentaerythriol esters

Info

Publication number: EP1750659A1
Application number: EP05716400A
Authority: EP
Inventors: Caroline Goget; Ulrich Issberner; Rolf Kawa; Catherine Mitchell
Original assignee: Cognis IP Management GmbH
Current assignee: Cognis IP Management GmbH
Priority date: 2004-04-05
Filing date: 2005-03-26
Publication date: 2007-02-14
Also published as: US20080249192A1; JP2007531777A; WO2005097056A1

Abstract

The invention relates to water-free wax mixtures containing, as components, (a) at least one pentaerythriol, dipentaerythriol, tripentaerythriol ester or any particular mixture of said esters and as components (b) at least one partial glyceride, wherein the ratio from (a)- to- (b)- is from 1: 3 to 3: 1. The invention also optionally relates to self-emulsifying bases which contain the inventive wax mixture in addition to at least one emulsifier (c) which is selected from the group of anionic or non-ionic emulsifiers having an HLB value greater than 10. The invention further relates to the use of the wax mixtures or self-emulsifying bases in the cosmetic industry.

Description

Wax mixture based on partial glycerides and pentaerythritol esters

Field of the Invention

The invention relates to wax mixtures of partial glyecrides and esters of pentaerythritol or oligomers of pentaerythritol and self-emulsifying mixtures based on the wax mixtures. The invention also relates to compositions based on the self-emulsifying mixtures.

State of the art

Wax-based formulations have long been known to the person skilled in the art. These are among others used for cosmetic and pharmaceutical formulations, e.g. Suppositories, various cosmetic compositions in stick form or in creams and lotions, for coating papers and textiles, etc. Numerous wax-like substances and substance mixtures are available to the person skilled in the art. These include, for example, glycerides and fatty alcohols, which have a decisive impact on the sensor technology of the final formulations. Glycerides leave an often oily / greasy skin feeling. Fatty alcohols lead to a stronger white residue formation, which is perceived by users as very disadvantageous. In addition, fatty alcohols often lead to excessive viscosity increases during storage.

Waxes and wax combinations are also used, among other things, to favorably influence the consistency and viscosity of cosmetic formulations. The viscosity of cosmetic emulsions, in particular oil in water (O / W) emulsions, is generally adjusted using so-called hydrophilic waxes. This is understood to mean substances or mixtures of substances that have a melting point above 30 ° C and have free OH groups in the molecule that can interact with water (hydrate formation through hydrogen bonding) and thus through the formation of so-called lamellar phases make a significant contribution to the increase in viscosity in O / W emulsions. The viscosity not only influences the phase stability, but also has a clearly positive effect on essential sensory parameters, which include "cushion", "distribution" and "peaking". The cosmetic chemist uses waxes of this type to form emulsions with regard to sensors and viscosity The disadvantage is that lamellar phases are not resistant to aging and the viscosities depend on the time can fall or rise, which ultimately changes the sensor system. In DE 31 31 006 A1, a solution to the problem of achieving stable viscosities was shown with a precisely coordinated wax combination of partial glycerides, fatty alcohols, wax esters and triglycerides, but as the document describes, it always fails when the specified quantitative ratios vary slightly become.

The object of the present invention was to provide combinations of known hydrophilic waxes which, in a wide mixture ratio, ensure long-term stable viscosities of O / W emulsions, regardless of the structure of the emulsifiers used and the polarity of the emollients used.

Surprisingly, it has now been found that this can be achieved by specific wax mixtures based on esters of pentaerythritol or its oligomers in combination with partial glycerides.

Description of the invention

The invention therefore relates to an anhydrous wax mixture comprising as component (a) at least one ester of pentaerythritol, dipentaerythritol, tripentaerythritol or any mixture of these esters and as component (b) at least one partial glyceride, the weight ratio of (a) to (b ) from 1: 3 to 3: 1.

Anhydrous for the purposes of the invention are wax mixtures which contain less than 2% by weight of water, preferably less than 1% by weight of water, particularly preferably less than 0.5% by weight of water and in particular less than 0.1 Wt .-% water. The wax mixtures usually only contain residual amounts of water due to the raw material.

Surprisingly, it was found that O / W emulsions which contain the wax mixtures according to the invention not only show "stable" viscosity values over several weeks, but that the viscosities of the emulsions are significantly higher than viscosities obtained when using the same amount of a single wax component In addition, the viscosity build-up in emulsions based on the wax mixtures according to the invention is independent of the polarity of the oils used and also independent of the structure of the emulsifiers used.The wax mixtures according to the invention allow the cosmetic chemist, sensors and viscosity to coordinate exactly with each other, without running the risk that the temporal changes in viscosity also negatively affect the sensory properties.

Component (a) According to the invention, preferred are wax mixtures which are characterized in that component (a) is selected from the group of the C6-C22 fatty acid esters of pentaerythritol, dipentaerythritol, tripentaerythritol or any mixture of these esters, some of which Have a melting point of at least 30 ° C.

The esters can have a single type of fatty acid acyl group or a mixture of different fatty acid acyl groups, the fatty acids can be branched or unbranched and / or saturated or unsaturated. Preferably be used for esterification used with a high content of saturated unbranched fatty acids, especially those that come from vegetable raw material sources. C14-C24 fatty acids, in particular C14-C20 fatty acids, are preferred according to the invention. These include, for example, myristic, pentadecane, palmitic, margarine, stearic, nonadecane, arachine, behenic, lignoceric, cerotinic, melissic, erucic and elaeostearic acids as well as substituted fatty acids such as 12-hydroxystearic acid.

A further preferred embodiment of the wax mixture is characterized in that component (a) is selected from the group of the esters of pentaerythritol which have a proportion of (i) 5-35% by weight monoester, (ii) 20-50% by weight. -% diester and (iii) 25-50% by weight triester, and optionally tetraester. A content of (a) 10-25% by weight of monoester, (b) 25-40% by weight of diester and (c) 30-45% by weight of triester, and optionally tetraester is particularly preferred and is particularly preferred (a) 12-19% by weight monoester, (b) 25-35% by weight diester, (c) 30-40% by weight triester and (d) 6-11% by weight tetraester. A very particularly preferred embodiment of the wax mixture contains as ester component (a) esters of pentaerythritol, dipentaerythritol or tripentaerythritol which contain less than 0.3% by weight of C17 fatty acid acyl groups.

A further preferred embodiment of the wax mixture is characterized in that the ester component (a) is obtained by esterification with a fatty acid mixture containing 40-50% by weight of C16 fatty acid and 45-55% by weight of C18 fatty acid. The remaining amounts of the fatty acid mixture are shorter-chain (<C14) and longer-chain (> C18) fatty acids. Esters of pentaerythritol and dipentaerythritol with a C16 / C18 fatty acid weight ratio of approx. 0.7 - 0.9 are related to the superior sensory properties. According to the invention, an ester of pentaerythritol is preferred, which is obtained by reacting pentaerythritol with a fatty acid mixture containing 42-48% by weight of C16 fatty acid and 50-56% by weight of C18 fatty acid (remaining amounts: <C14 fatty acids and> C18 Fatty acids) is obtained and has the following ester distribution: 12-19% by weight monoester, (b) 25-35% by weight diester, (c) 30-40% by weight triester and (d) 6-11% by weight .-% tetraester. Usually, per mol pentaerythritol is 1.8 - 2.2 mol of the fatty acid mixture, preferably 1.9 - 2.1 mol, eiπgesetzt for the esterification ^~. ^"

For example, the production of C16 / C18 fatty acid pentaerythritol esters can be carried out by adding 1.8-2.2 mol, preferably 1.9-2.1 mol, of a fatty acid mixture containing 40-50% by weight of C16 fatty acid and 45-55% by weight per 1 mol of pentaerythritol. -% C18 fatty acid or a raw material mixture with a corresponding fatty acid distribution and (a) the esterification at temperatures in the range of

^~ Tδ C to 250 ° C under a protective gas atmosphere, and carried out without solvent, (b) the water formed is distilled off, (c) the reaction mixture obtained is stirred in a vacuum until an acid number of <1 and an OH number of 145-158 is reached , (d) unreacted pentaerythritol is filtered off and (e) if necessary, an aftertreatment is carried out with hydrogen peroxide. The methods for checking and adjusting the acid number and the OH number are well known to the person skilled in the art, so that there is no need to go into this here.

Component (b) A preferred embodiment of the wax mixture is characterized in that the partial glyceride (b) is selected from the group of esterification products from glycerol or oligoglycerol with fatty acids with a chain length of 12 to 24 carbon atoms or any mixture of these esterification products. According to the invention, oligoglycerols are understood to mean oligomers of glycerol with 2-12 glycerol units.

The fatty acids which can be used for the esterification include, for example, myristic, pentadecane, palmitic, margarine, stearic, nonadecane, arachine, behenic, lignoceric, cerotinic, melissic, erucic and elaeostearic acids and substituted fatty acids, such as B. 12-hydroxystearic acid, this list being exemplary and not restrictive. It is preferred according to the invention to use fatty acids / fatty acid mixtures which have a high proportion of unbranched, saturated fatty acids. The partial glyceride (b) is preferably a palmitic and / or stearic acid ester of glycerol with a monoglyceride content of 30 to 65% by weight and a diglyceride content of 25 to 45% by weight. With a monoglyceride content of at least 30% by weight, the viscosity build-up is ensured particularly well and the final cosmetic formulations are distinguished by improved long-term stability. Up to an upper limit of 65% by weight of monoglyceride, the risk of crystallization is also relatively low.

The partial glyceride (b) is preferably obtained by reacting glycerol with a fatty acid mixture of palmitic and stearic acid in a weight ratio of 1: 3 to 3: 1.

Among the inventively employable partial glycerides include, for example, by Cognis Germany GmbH & Co. KG marketed products Cutina ^® MD (30 - 45 wt .-% Monogylceridanteil - / -. Diglyeeridanteil-35 --- 45% by weight), Cutina ^® GMS ( 40-55% by weight monoglyceride / diglyceride 30-45% by weight) and Monomuls 60-35 (55-65% by weight monoglyceride / diglyceride 25-45% by weight).

Mixed esters and mixtures of mono-, di- and triglycerides are preferably suitable according to the invention because they show a lower tendency to crystallize and thus improve the performance of the wax mixture according to the invention. They are also much more compatible with oils of different polarities.

The wax mixtures according to the invention are usually processed in the formulation of cosmetic or pharmaceutical compositions with oil bodies, water and emulsifiers. From an application point of view, it is particularly advantageous to provide a self-emulsifying base based on the wax mixtures according to the invention which already contains the required amount of emulsifiers.

Self-emulsifying basis

Another object of the invention is therefore self-emulsifying bases containing a wax mixture according to one of claims 1 to 7 and additionally at least one emulsifier (c) selected from the group of anionic or nonionic emulsifiers with an HLB value greater than 10. Between the term emulsifier and According to the invention, surfactant is not differentiated. Emulsifiers (c)

As mentioned above, the structure of the emulsifiers is not particularly critical. Detailed lists of the HLB values of commercial emulsifiers are known to the person skilled in the art and can be found, for example, in Fiedler, Lexicon of auxiliaries for pharmacy, cosmetics and related areas, Volume 9, 1971, pages 265-270; Kirk-Othmer (3rd edition) volume 8, pages 909-918 and Janistyn (3rd edition) volume 1, page 470; and Volume 3, pages 68-78. The listed there anionic and nonionic Emulgatören ^"rnit an HLB greater than 10 should be of the present disclosure part. The emulsifiers can be used as active substance or in the form of aqueous solutions. Examples of anionic emulsifiers / surfactants that may be used erfindungsgemäß- are soaps , Alkyl benzene sulfonates, alkane sulfonates, _ olefin sulfonates, alkyl ether sulfonates, _ glycerol ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerin ether sulfates, fatty acid ether sulfates, hydroxymixed ether sulfates, monosulfate sulfate, monoglyate sulfate, sulfate amate sulfate, monoglyate sulfate, sulfate amate sulfate, monoglyate sulfate, and , Sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid aurides, N-acyl amino acids, such as acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, Pr otein fatty acid condensates (especially vegetable products based on wheat), alkyl phosphates and alkyl ether phosphates. If the anionic surfactants contain polyglycol ether chains, these can have a conventional, but preferably a narrow, homolog distribution.

The group of particularly suitable nonionic emulsifiers / surfactants with an HLB value> 10 includes corresponding compounds which are selected from:

(1) Adducts of ethylene oxide and / or propylene oxide with linear and branched fatty alcohols with 8 to 40 carbon atoms, with linear and branched fatty acids with 12 to 40 carbon atoms and with alkylphenols with 8 to 15 carbon atoms in the alkyl group.

(2) Ci2 / i8 fatty acid monoesters and diesters of adducts of ethylene oxide and / or propylene oxide with glycerol.

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

(4) Alkyl mono- and oligoglycosides with 8 to 22 carbon atoms in the alkyl radical and their ethoxylated analogues. (5) Addition products of ethylene oxide and / or propylene oxide with castor oil and / or hardened castor oil.

Individual examples (see Kirk-Othmer) for nonionic emulsifiers / surfactants with an HLB value of at least 10 are P0E- (5) sorbitan mono-oleate (POE = polyoxyethylene), POE (40) sorbitol hexaoleate, PEG 400 dilaurate, POE (5 ) Nonylphenol (ether), POE (20) sorbitan tristearate, POP / POE condensate, POE (6) nonylphenol (ether), POE (20) lanolin (ether and ester), POE (20) sorbitan trioleate, POE (8) stearic acid (monoester ), POE (50) sorbitol hexaoleate, POE (6) tridecyl alcohol (ether), PEG 400 monostearate ,. POE. (8) nonylphenol (ether), POE (10) stearyl alcohol (ether), POE (8) tridecyl alcohol (ether), POE (8) lauric acid (monoester), POE (10) cetyl alcohol (ether), acetylated POE (10 ) Lanolin, POE (20) glycerol monostearate, PEG 400 monolaurate, POE (16) lanolin alcohol (ether), POE (4) sorbitan monolaurate, POE (10) nonylphenol (ether), POE (15) long oil fatty acids (ester), POE (10 )

Oclylphe1ϊδr (ethe 7P- ^ 0 ^" monostearate, tertiary amines: POE fatty amines; POE (24) cholesterol, POE (14) nonylphenol (ether), POE (12) lauryl alcohol, POE (20) sorbitan monostearate, sucrose monolaurate, POE (20) sorbitan Monooleate, acetylated POE (9) lanolin, POE (20) stearyl alcohol, POE (20) oleyl alcohol (ether), PEG 1000 monooleate, POE (20) taigamine, POE (20) sorbitan monopalmitate, POE (20) cetyl alcohol (ether), POE (25) propylene glycol monostearate, POE (20) nonylphenol (ether), PEG (1000) monolaurate, POE (20) sorbitan monolaurate, POE (23) lauryl alcohol (ether), POE (40) stearic acid (monoester), POE (50) lanolin ( ether and ester), POE (25) soyasterol, POE (30) nonylphenol (ether), PEG 4000 distearate, POE (50) stearic acid (monoester), POE (70) dinonylphenol (ether), POE (20) castor oil (ether, ester), N-cetyl-N-ethyl-morpholinium ethyl sulfate, etc.

The self-emulsifying bases make it possible to produce viscosity-stable O / W emulsions particularly easily, since the ratio of the emulsifiers to the consistency waxes is already precisely coordinated.

It is particularly advantageous according to the invention to contain a self-emulsifying base comprising (a) 20-60% by weight of at least one ester of pentaerythritol, dipentaerythritol and / or tripentaerythritol according to one of Claims 2 to 5 (b) 20-60% by weight. at least one partial glyceride according to one of claims 6 to 8 and (c) 5-30% by weight, preferably 10-30% by weight of at least one additional emulsifier selected from the group of anionic or nonionic emulsifiers with an HLB value greater 10 use, the self-emulsifying mixture contains less than 20 wt .-% water.

The percentages by weight relate to the amount of active substance in the self-emulsifying composition. Preferably, a water content of less than 15 wt .-%, in particular of less than 1O is ^{^{^"wt.%".}} ^'"

^'A ^{^} b ^{^} oil ügte Ausführüήgs rrder or self-emulsifying base is characterized in that the anionic emulsifier is selected from among the alkali metal salts of C12-C24-acyl glutamates. the alkali metal and triethanolamine salts of the C12-G24 fatty acids and the alkali metal salts of the _.Ci2-C24 fatty alcohol sulfates / C1.2 - C24- _: fatty alcohol ether sulfates-.or_-the-C12 - C24 .-- fatty alcohol phosphates / C12- C24 fatty alcohol ether. Alkali metal salts of C16-C24 acylglutamates, alkali metal salts and triethanolamine salts of C16-C24 fatty acids and alkali metal salts of C16-C24 fatty alcohol (ether) sulfates or C16-C24 fatty alcohol (ether) phosphates are particularly preferred. Alkali metal salts of C16-C18 acylglutamates, alkali metal and triethanolamine salts of C16-C18 fatty acids and alkali metal salts of C16-C18 fatty alcohol (ether) sulfates or of C 16-C 18 fatty alcohol (ether) phosphates are very particularly preferred. According to the invention, particular preference is given to monosodium stearoyl glutamate, disodium stearoyl glutamate or triethanolamine, potassium and sodium stearate. Preferred acylglutamates are e.g. B. under the name Amisoft® from Ajinomoto in the trade. Amisoft® HS-21 P (disodium stearoyl glutamate) and Amisoft® HS-11 P (sodium stearoyl glutamate) can be used with preference.

Soaps which are preferably suitable according to the invention contain palmitic and stearic acid in a weight ratio of 1: 3 to 3: 1.

A further preferred embodiment of the self-emulsifying base is characterized in that the nonionic emulsifiers with an HLB value greater than 10 are selected from the group of the C12-C24 fatty alcohol ethoxylates and / or the C12-C24 alkyl oligoglycosides.

To the present invention, usable C12-C24 fatty alcohol ethoxylates include, for example ceteareth-12, ceteareth-20, ceteareth-30 by Cognis Germany GmbH & Co. KG under the name Eumulgin ^® B1, Eumulgin ^® B2 or Eumulgin ^® B3 in Are trade. The C12-C24-alk (en) yl oligoglycosides which can preferably be used according to the invention are known nonionic surfactants which follow the formula (I), R ¹ 0- [G] _p (I), in which R ^{1 is} a C12-C24-alk (en) yl residue, G stands for a sugar residue with 5 or 6 carbon atoms and p stands for numbers from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry. As representative of the extensive literature, reference is made here to EP 0301298 A1 and WO 90/03977 A.

The alk (en) yl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alk (en) yl oligoglycosides are thus alk (en) yl oligoglucosides. The index number _. ^ jn "of the general formula (I) indicates the degree of oligomerization (DP degree), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p in a given compound must always be an integer, and here in particular that Values p =

1 to 6, the value p for a certain alk (en) yl oligoglycoside is an analytically determined arithmetic parameter, which usually represents a fractional number. Alk (en) yl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, alk (en) yl oligoglycosides are preferred whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4. According to the invention, preference is given to using alkyl oligoglycosides in which the radical R ^{1 is derived} from primary, preferably unbranched, alcohols having 12 to 24 carbon atoms, in particular 16 to 24 and particularly preferably 16 to 18 carbon atoms. Technical mixtures of the alcohols can also be used. Particularly preferred alkyl oligoglucosides are called Plantacare® 1200, - 2000, - 810, - 818, Tego Care® CG 90, Emulgade® PL 68/50, Montanov® 14, - 202, - 68, - 82, - L, - S, W018, Oramix® BG 14, -CG 110, -NS 10 offered in the market.

Industrial applicability

The wax mixtures according to the invention and the self-emulsifying bases are used for the production of cosmetic and pharmaceutical compositions.

The invention therefore furthermore relates to cosmetic or pharmaceutical preparations containing 1 to 20% by weight of a wax mixture according to the invention or 1 to 20% by weight of a self-emulsifying base according to the invention. The use concentration is preferably 2-10% by weight. The application also relates to the use of a wax mixture according to one of claims 1 to 7 for increasing the viscosity of emulsions, in particular oil-in Water emulsions, and the use of a self-emulsifying mixture according to one of claims 8 to 11 for increasing the viscosity of emulsions, in particular oil-in-water emulsions. Another object of the application is the use of a wax mixture according to one of claims 1 to 7 or a self-emulsifying mixture according to one of claims 8 to 11 as a consistency agent in cosmetic or pharmaceutical emulsions. Depending on the concentration used, lotions or creams are created, which are characterized by this; that there is an average particle size of 1 μm to 20 μm, preferably 5 μm to 10 μm. The viscosities of such emulsions are between 2000 mPa-s and 500000 mPa-s, a range from 10000 mPa-s to 200000 mPa-s is preferred. The viscosity measurements were carried out with a Brookfield RVF at 23 ° C ^' Independent of the viscosity, the spindles 5 or 6 at 10 rpm (up to 60,000 mPa-s for lotions) or the spindle TE with Helipath (> 60,000 mPa-s for creams) were used.

oil components

The preparations according to the invention contain an aqueous and an oil phase, which can contain auxiliaries and additives. The proportion of the water phase is usually in the range from 20-90% by weight, based on the overall composition, and the proportion of the oil phase is 1-70% by weight, based on the total composition. The oil phase can be composed of an oil component or any mixture of oil components. The oil component (s) is / are preferably present in an amount of 1-25% by weight, in particular 1-20% by weight and very preferably 5-15% by weight, based on the total composition.

The following classes of compounds are suitable as oil bodies, for example: Guerbet alcohols based on fatty alcohols with 6 to 18, preferably 8 to 10 carbon atoms in question, esters of linear or branched, saturated or unsaturated C6-C22 fatty acids with linear or branched, saturated or unsaturated C6-C22 fatty alcohols, especially 2-ethylhexanol. Examples that may be mentioned are hexyl laurate, myristyl isostearate, myristyl oleate, cetyl isostearate, cetyl oleate, stearyl isostearate, stearyl oleate, isosteary I my ristat, isostearyl palmitate, isostearyl stearate, isostearyl isostearate, isostearylolostirate, oleyl isolate stolate, oleyl isolate stolate, oleyl isolate styrene Other suitable esters are, for example, esters of C18-C38-alkylhydroxycarboxylic acids with linear or branched, saturated or unsaturated C6-C22-fatty alcohols, esters of linear and / or branched, saturated or unsaturated fatty acids with polyhydric alcohols (such as propylene glycol, dimer diol or trimer triol) and / or Guerbet alcohols, triglycerides or triglyceride mixtures, liquid mono- / di- / triglyceride mixtures, Esters of C6-C22 fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, especially benzoic acid, esters of C2-Ci2-dicarboxylic acids with linear or branched, saturated or unsaturated alcohols with 1 to 22 carbon atoms or polyols with 2 to 10 carbon atoms and 2 to 6 Hydroxyl groups, vegetable oils, branched primary alcohols, substituted-cyclohexanes; linear dialkyl carbonates (e.g. Cetiol® CC), Guerbet carbonates based on fatty alcohols with 6 to 18, preferably 8 to 10 C atoms, esters of benzoic acid with linear and / or branched C6-C22 alcohols (e.g. Finsolv® TN) , linear or branched, symmetrical or asymmetrical dialkyl ethers having 6 to 22 carbon atoms per alkyl group, such as. B. Di-n-octyl ether (Cetiol® OE) or ring opening products of epoxidized fatty acid esters with polyols, Kohlenwas5jers e_-JwJe_P.araffin --_ oder- mineral oils, _-- oligo- or eolyalphaolefins. Dialkyl ethers, dialkyl carbonates, triglyceride mixtures and esters of C8-C24 fatty acids and C8-C24 fatty alcohols or a mixture of these substances are particularly suitable according to the invention as oil bodies. The dialkyl carbonates and dialkyl ethers can be symmetrical or asymmetrical, branched or unbranched, saturated or unsaturated and can be prepared by reactions which are well known from the prior art. Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones (cyclomethicone) and amino, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and / or alkyl-modified silicone compounds. Simethicones, which are. Mixtures of dimethicones with an average chain length of 200 to 300 dimethylsiloxane units and hydrogenated silicates.

According to the invention, hydrocarbons, preferably with a chain length of 8 to 40 carbon atoms, can also be used as oil bodies. They can be branched or unbranched, saturated or unsaturated. Among them, branched, saturated C8-C40 alkanes are preferred. Both pure substances and mixtures of substances can be used. Usually it is a matter of mixtures of substances of different isomeric compounds. Compositions which have alkanes with 10 to 30, preferably 12 to 20, and particularly preferably 16 to 20 carbon atoms are particularly suitable, and among these a mixture of alkanes which contains at least 10% by weight of branched alkanes, based on the total amount of Contains alkanes. They are preferably branched, saturated alkanes. Mixtures of alkanes which contain more than 1% by weight of 5,8-diethyldodecane and / or more than 1% by weight of didecene are particularly suitable. Other optional auxiliaries and additives, depending on the application, the cosmetic ^{formulations'} is a number of other auxiliaries and additives may include, for example, thickeners, superfatting agents, stabilizers, polymers, lecithins, phospholipids, biogenic agents, UV protection factors, antioxidants, deodorants; - film formers, - swelling agents; - insect repellents; Hydrotropes, solubilizers, preservatives, perfume oils, dyes etc., which are listed below as examples. The quantities-the respective additions riühteTTsicfTnach ^{'derbeäbsichtigteii} use.

Suitable thickening agents are, for example, Aerosil types (hydrophilic silicas), polysaccharides, in particular xanthan gum, guar guar, agar agar, .alginate and unavoidable, carboxymethyl cellulose and hydroxyethyl and hydroxypropyl cellulose, polyvinyl alcohol, Polyvinyl pyrrolidone and bentonites such as e.g. B. Bentone® Gel VS-5PC (Rheox).

Under UV light protection factors are to be understood, for example, liquid or crystalline organic substances (light protection filters) at room temperature which are able to absorb ultraviolet rays and absorb the energy in the form of longer-wave radiation, e.g. B. to release heat again. UV-B filters can be oil-soluble or water-soluble. Derivatives of benzoylmethane are particularly suitable as typical UV-A filters. The UV-A and UV-B filters can of course also be used in mixtures, for example combinations of the derivatives of benzoylmethane, e.g. B. 4-tert-butyl-4'-methoxydibenzoylmethane (Parsol ^® 1789) and 2-cyano-3,3-phenylcinnamic acid-2-ethyl-hexyl ester (octocrylene) and esters of cinnamic acid, preferably 4-methoxycinnamic acid-2-ethylhexyl ester and / or propyl 4-methoxycinnamate and / or isoamyl 4-methoxycinnamate. Such combinations are often used with water-soluble filters such. B. 2-phenylbenzimidazole-5-sulfonic acid and their alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts combined.

In addition to the soluble substances mentioned, insoluble light-protection pigments, namely finely dispersed metal oxides, are also suitable. Examples of suitable metal oxides are, in particular, zinc oxide and titanium dioxide. In addition to the two aforementioned groups of primary light stabilizers, it is also possible to use secondary light stabilizers of the antioxidant type which interrupt the photochemical reaction chain which is triggered when UV radiation penetrates the skin.

Examples of biogenic active substances are tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, (deoxy) ribonucleic acid and its fragmentation products, β-glucans, retinol, Bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts, such as. B. Prunus extract, Bambaranus extract and vitamin complexes to understand.

Deodorising actives counteract body odors, mask or eliminate them. Body odors arise from the action of skin bacteria on apocrine sweat, whereby - unpleasant smelling degradation products are formed. Accordingly, suitable deodorising agents include germ inhibitors, enzyme inhibitors, odor absorbers or odor maskers.

Suitable insect repellents are, for example, include N, N-diethyl-m-toluamide, 1, 2-diol or 3- (N-n-butyl-N-acetyl-amino) -propionic acid ethyl ester) which lent as Insect Repel- ^® 3535 is marketed by Merck KGaA, as well as butylacetylaminopropionate.

Dihydroxyacetone is suitable as a self-tanner. Arbutin, ferulic acid, kojic acid, coumaric acid and ascorbic acid (vitamin C) can be used as tyrosine inhibitors, which prevent the formation of melanin and are used in depigmenting agents.

Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid as well as the silver complexes known under the name Surfacine® and the other classes of substances listed in Appendix 6, Parts A and B of the Cosmetics Ordinance.

Perfume oils include mixtures of natural and synthetic fragrances. Natural fragrances are extracts of flowers, stems and leaves, fruits, fruit peels, roots, woods, herbs and grasses, needles and branches, resins and balms. Animal raw materials such as civet and castoreum and synthetic fragrance compounds of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are also suitable.

The dyes which can be used are those which are suitable and approved for cosmetic purposes. Examples are Kochillerot A (Cl 16255), Patent Blue V (C.1.42051), Indigotine (C.1.73015), Chlorophyllin (C.1.75810), Quinoline Yellow (CI47005), Titanium Dioxide (C.1.77891), Indanthrene Blue RS (Cl 69800) and Madder varnish (CI58000). These dyes are usually used in concentrations of 0.001 to 0.1% by weight, based on the mixture as a whole. The following examples ^" describe emulsions which were produced on the basis of the wax mixtures according to the invention and show the viscosity build-up and course in comparison to emulsions using the singular waxes and wax mixtures which do not correspond to the mixture ratio according to the invention.

Examples

The production (based on a 200g laboratory batch) takes place in the hot process. To do this, the oil phase is heated to 80 ° C. The water phase, also at 80 ° C, is slowly added to the oil phase with stirring. The emulsion is cooled to 40 ° C. with constant stirring. At 40 ° C, the pH is adjusted to 7, if necessary with citric acid or sodium hydroxide, and cooling to 30 ° C ^' homogenized for 2 minutes using a suitable rotor-stator system (e.g. Ultra Turrax T 50 from IKA). The viscosity (Brookfield RVF, spindle 5, 10 rpm, 23 ° C.) of the emulsions produced in this way was determined after preparation and after 4, 8 and 12 weeks (W) and compared in the tables below. The viscosity measurements were carried out at room temperature. The amounts given below relate to% by weight of the commercially available substance in the overall composition. The examples marked with “V” serve for comparison. It can clearly be seen that only the wax mixtures according to the invention have sufficient viscosity stability or phase stability in the monitoring period.

Test series 1

Determination of the viscosity build-up as a function of the ratio of the waxes used when using an emulsifier with an ionic structure; Emulsifier: sodium stearoyl glutamate (mono salt) - anionic; Emollient: Cococaprylate / Caprat - medium polar

Table 1

1) esters of pentaerythritol, obtained by reacting 1 mole of pentaerythritol with about 2 moles of a fatty acid mixture of 42-48 wt .-% C16 fatty acid ^~ and 50-56 wt .-% of C18 fatty acid (residual amounts: <C14 Fatty acids and> C18 fatty acids) is obtained and has the following ester distribution: 12-19% by weight monoester, (b) 25-35% by weight diester, (c) 30-40% by weight triester and ^~ (i.e. ) Contains 6-11% by weight tetraester and less than 0.3% by weight C17 fatty acid acyl groups. This ester was also used in all other experiments (see the following tables).

Test series 2

Determination of the viscosity build-up as a function of the ratio of the waxes used when using an emulsifier with an ionic structure; Emulsifier: sodium cetearyl sulfate - anionic Emollient: cococaprylate / caprate - medium polar

Table 2

Test series 3

Determination of the viscosity build-up as a function of the ratio of the waxes used when using an emulsifier with an ionic structure; Emulsifier: sodium stearate - anionic; Emollient: Cococaprylate / Caprat - medium polar Table 3

Test series 4

Determination of the viscosity build-up as a function of the polarity of the emollients used, using the example of the Cutina® GMS wax mixture: pentaerythrityl distearate ¹⁾ = 1: 1 when using an emulsifier with an ionic structure; Emulsifier: sodium stearoyl glutamate - anionic; Emollient: dicaprylyl ether - weakly polar; Soybean oil - highly polar

Table 4

Test series 5

Determination of the viscosity build-up as a function of the ratio of the waxes used when using an emulsifier with a nonionic structure; Emulsifier: Ceteareth-20 - non-ionic; Emollient: Cococaprylate / Caprat - medium polar Table 5

--YersuehsserJe-fi.

Determination of the viscosity build-up as a function of the ratio of the waxes used when using an emulsifier with a nonionic structure; Emulsifier: lauryl glucoside - non-ionic; Emollient: Cococaprylate / Caprat - medium polar

Table 6

Test series 7

Determination of the viscosity build-up as a function of the polarity of the emollients used, using the example of the Cutina® GMS wax mixture: pentaerythrityl distearate ¹⁾ = 1: 1 when using an emulsifier with a nonionic structure; Emulsifier: Ceteareth-20 - non-ionic; Emollient: dicaprylyl ether - weakly polar; Soybean oil - highly polar. Table 7

Claims

claims

1. An anhydrous wax mixture containing as component (a) at least one ester of pentaerythritol, dipentaerythritol, tripentaerythritol or any mixture of these esters and as component (b) at least one partial glyceride, the weight ratio of (a) to (b) being 1 : 3 to 3: 1.

2. "Wax mixture according to claim 1, characterized in that component (a) is selected from _. the group of the C6-C22 fatty acid esters of pentaerythritol, dipentaerythritol, tripentaerythritol or any mixture of these esters, which have a melting point of at least 30 ° C.

3. Wax mixture according to claim 1 or 2, characterized in that component (a) is selected from the group of esters of pentaerythritol which have a proportion of (i) 5-35% by weight monoester, (ii) 20-50 % By weight of diester and (iii) 25-50% by weight of triester and optionally tetraester.

4. Wax mixture according to at least one of claims 1 to 3, characterized in that the ester component (a) is obtained by esterification with a fatty acid mixture containing 40-50% by weight of C16 fatty acid and 45-55% by weight of C18 fatty acid ,

5. wax mixture according to at least one of claims 1 to 4, characterized in that the partial glyceride (b) is selected from the group of esterification products of glycerol or oligoglycerol with fatty acids having a chain length of 12 to 24 carbon atoms or any mixture of these esterification products.

6. wax mixture according to at least one of claims 1 to 5, characterized in that the partial glyceride (b) is a palmitic and / or stearic acid ester of glycerol which has a monoglyceride content of 30 to 65% by weight and a diglyceride content of 25 to 45 % By weight.

7. wax mixture according to claim 7, characterized in that the partial glyceride (b) is obtained by reacting glycerol with a fatty acid mixture of palmitic and stearic acid in a weight ratio of 1: 3 to 3: 1.

8. Self-emulsifying base containing a wax mixture according to one of claims 1 to 7 and additionally at least one emulsifier (c) selected from the group of anionic or nonionic emulsifiers with an HLB value of at least 10.

9. Self-emulsifying base according to claim 8 containing (d) 20-60% by weight of at least one ester of pentaerythritol, dipentaerythritol and / or tripentaerythritol according to one of claims 2 to 5 (e) 20-60% by weight at least a partial glyceride according to any one of claims 6 to 8 and (f) 10-30% by weight of at least one additional emulsifier selected from the group of anionic or nonionic emulsifiers with an HLB value of at least 10, the self-emulsifying mixture being less than 20 Wt .-% water contains.

10. Self-emulsifying base according to claim 8 or 9, characterized in that the anionic emulsifier is selected from the alkali metal salts of C12-C24 acylglutamates, from the alkali metal and triethanolamine salts of C12-C24 fatty acids and the alkali metal salts of C12-C24 fatty alcohol (ether) sulfate or the C12-C24 fatty alcohol (ether) phosphate.

11. Self-emulsifying base according to at least one of claims 9 to 11, characterized in that the nonionic emulsifiers with an HLB value of at least 10 are selected from the group of C12-C24 fatty alcohol ethoxylates and / or the C12-C24 alkyl (s ) oligoglycosides.

12. Cosmetic or pharmaceutical preparation containing 1-20% by weight of a wax mixture according to one of claims 1 to 7 or 1-20% by weight of a self-emulsifying base according to one of claims 8-11.

13. Use of a wax mixture according to one of claims 1 to 7 for increasing the viscosity of emulsions, in particular oil-in-water emulsions.

14. Use of a self-emulsifying mixture according to one of claims 8 to 11 for increasing the viscosity of emulsions, in particular oil-in-water emulsions.

15. Use of a wax mixture according to one of claims 1 to 7 or a self-emulsifying mixture according to one of claims 8 to 11 as a consistency agent in cosmetic or pharmaceutical emulsions.