DE19947550A1 - High water content stable and reproducible water-oil-water multiple emulsions containing an oil phase dispersed in a continuous external aqueous phase useful for cosmetic and dermatological compositions - Google Patents

Abstract

Multiple emulsions of water-oil-water type comprising a continuous external aqueous phase, an oil phase dispersed in it, and a second (internal) aqueous phase dispersed in this oil phase containing (wt.%): (a) at least 85% water or water soluble substances, (b) at least one surfactant, (c) one or more lipid components where the ratio of (b) to (c) is 0.15-0.25. New multiple water-oil-water (W/O/W) emulsions comprise a continuous external aqueous phase, an oil phase dispersed in it, and a second (internal) aqueous phase dispersed in this oil phase containing (wt.%): (a) at least 85% water or water soluble substances, relative to the total weight of the composition and a maximum content of lipids, emulsifiers, and lipophilic substances of 15%, (b) at least one surfactant, selected from substances of formula (I); and (c) one or more lipid components, comprising the lipid phase of the emulsion; the ratio of (b) to (c) is 0.15-0.25. A, A' = an organic residue selected from optionally unsaturated alkyl and acyl groups, and hydroxyacyl groups of 10-30C, or hydroxyacyl groups bonded via ester functions according to scheme(i): R' = 1-20C alkyl; R'' = 1-20C alkylene; b = 0-200; a = 1-100 (especially 5-40); X = a single bond or -CH(OR3)-; R1, R2 = H or Me; R3 = H or optionally unsaturated 1-20C alkyl or acyl. An Independent claim is included for preparation of the W/O/W emulsions.

Description

The present invention relates to stable multiple emulsions of the W / O / W type with ho hem water content, process for their preparation and their use for cosmetics and medical purposes.

The present invention relates to cosmetic and dermatological preparations, in particular those of the water-in-oil type, processes for their preparation and their Use for cosmetic and medical purposes.

As the largest human organ, the human skin performs numerous vital functions. With an average surface area of around 2 m ² in adults, it has an outstanding role as a protective and sensory organ. The task of this organ is to convey and ward off mechanical, thermal, actinic, chemical and biological stimuli. It also plays an important role as a regulatory and target organ in human metabolism.

Cosmetic skin care means primarily the natural function the skin as a barrier against environmental influences (e.g. dirt, chemicals, microorganisms nisms) and against the loss of the body's own substances (e.g. water, natural Fats, electrolytes) to strengthen or restore their horny layer when on to support damage that has occurred in its natural regenerative capacity.

If the barrier properties of the skin are disturbed, increased absorption can occur toxic or allergenic substances or to infest microorganisms and as a result toxic or allergic skin reactions.  

The aim of skin care is also to reduce the fat and fat caused by daily washing Compensate for skin water loss. This is especially important when the natural regeneration capacity is not sufficient. In addition, skin care products are said to exist Protect environmental influences, especially from the sun and wind, and skin aging delay.

Medical topical compositions typically contain one or more Medicines in effective concentration. For the sake of simplicity, it becomes clean Differentiate between cosmetic and medical use and correspond corresponding products to the legal provisions of the Federal Republic of German country (e.g. cosmetics regulation, food and drug law).

Emulsions are generally understood to be heterogeneous systems consisting of two there are no or only miscible liquids that are more common can be referred to as phases. One of the two is liquid in an emulsion dispersed in the form of very fine droplets in the other liquid.

Are the two liquids water and oil and oil droplets are finely distributed in Water, it is an oil-in-water emulsion (O / W emulsion, e.g. Milk). The basic character of an O / W emulsion is characterized by the water. With egg This is a water-in-oil emulsion (W / O emulsion, e.g. butter) swept principle, whereby the basic character is determined here by the oil.

In simple emulsions, one phase is finely dispersed, one phase Emulsifier shell enclosed droplets of the second phase (water droplets in W / O- or lipid vesicles in O / W emulsions). In a multiple emulsion (second degree) however, in such droplets there are finely dispersed droplets of the first phase emulsified. In these droplets, in turn, even finer disperse droplets can be used present (third degree multiple emulsion) and so on.

Just like with the simple emulsions of W / O or O / W emulsions speaks (water-in-oil or oil-in-water), there are W / O / W- in multiple emulsions, O / W / O, O / W / W, W / O / W / O emulsions and so on.  

Multiple emulsions in which the respective inner and outer water phases or different internal and external oil phases (e.g. W / O / W'- and O / W / O'-emulsions), are accessible to the preparation by two-pot processes. Such emulsions in which the inner and outer water or oil phases are not are different, both by one and two-pot processes available.

The second degree multiple emulsions are sometimes called "bimultiple systems", such third degrees are called "trimultiple systems" etc. (W. Seifriz, Studies in Emulsions, J. Phys. Chem., 29 (1925) 738-749).

Processes for producing multiple emulsions are known per se to the person skilled in the art. There are two-pot processes in which a simple emulsion (e.g. a W / O- Emulsion) and by adding another phase (e.g. a water phase) with a corresponding emulsifier (e.g. an O / W emulsifier) into a multiple Emulsion (e.g. a W / O / W emulsion) is transferred.

A second method is to use an oil phase and an emulsifier mixture Water phase in a one-pot process in a multiple W / O / W emulsion convict. The emulsifiers are dissolved in the oil phase and with the water phase united. The prerequisite for such a procedure is that the HLB values (HLB = Hydrophilic-lipophilic balance) of the individual emulsifiers used differentiate from each other.

The definition for the HLB value for polyol fatty acid esters is given by the formula I.

HLB = 20. (1 - S / A)

Formula II applies to a group of emulsifiers whose hydrophilic content consists only of ethylene oxide units

HLB = E / 5

in which
S = saponification number of the ester,
A = acid number of the recovered acid
E = mass fraction of ethylene oxide (in%) in the total molecule
mean.

Emulsifiers with HLB values of 6-8 are generally W / O emulsifiers, such with HLB values of 8-18 are generally O / W emulsifiers.

Literature: "Cosmetics - Development, production and application of cosmetic products"; W. Umbach (ed.), Georg Thieme Verlag 1988.

Hydrophilic emulsifiers (with high HLB values) are usually O / W emulsifiers. Accordingly, hydrophobic or lipophilic emulsifiers (with low HLB values) are in usually W / O emulsifiers.

US Pat. No. 4,931,210 describes a process for producing W / O / W Emulsion, polyglycerol polyricinoleates being used as emulsifiers.

So although multiple emulsions are known per se and it is quite simple Processes for their production still exist in such systems to this day lacks which microscopically over longer storage times (for example over several Years) or in a wide temperature range (for example from -10 ° C to + 50 ° C) or stable against extreme temperature fluctuations (rocking stability, for example are from -15 to + 50 ° C). This is meant to mean that the multiple emulsions of the prior art over time in simple W / O or O / W emulsions deln, so have a low storage stability in the sense of multiplicity. This is particularly disadvantageous as these conversion products are extremely inhomogeneous Result in droplet size distribution.

At best, such conversion products are unattractive or from a cosmetic point of view inelegant. Often, however, with the inhomogeneous size distribution of the droplets lack of macroscopic stability associated, i.e. stability against the decomposition separation into separate phases.  

In this regard too, the conventional multiple emulsions were always either insufficiently stable, or the transfer from the laboratory scale to the large-scale production was not feasible.

W / O / W emulsions with high water content, which also have a storage stability have, as is required for marketable products, especially those with a higher water content of more than 75 wt .-% water content and yet very good sensory properties, still pose a serious Problem. Due to the very high water content of the emulsions "break up" them of the skin particularly quickly - sensory unpleasant - in its main components (hydro phile and hydrophobic components).

According to the teaching of DE-OS 41 31 678 and WO 92/18227 stable multiple emuls Sions, especially W / O / W emulsions are obtained when emulsifier mixtures are used, which consist of at least one hydrophobic and one hydrophilic Emulsifier exist.

These publications describe processes for the preparation of stable multiple emulsions wrote, characterized in that the hydrophilic emulsifiers of Wasserpha se and the hydrophobic emulsifiers of the oil phase and both Pha then be united.

If you follow this teaching, it is possible to kosme in a relatively simple way table elegant multiple emulsions, especially to stable W / O / W emulsions caught, but improvements would still be desirable here.

The object of the present invention was therefore to provide stable multiple emulsions supply and the disadvantages of the preparations of the prior art remove.

Furthermore, it was the object of the invention to develop methods which are simple in enable way, targeted multiple emulsions with the desired beneficial To produce properties.  

Finally, it was the object of the invention to develop such processes which also lead to reproducibly stable W / O / W emulsions on an industrial scale would ren.

Surprisingly, it has been found, and this is the solution to the problem, that multiple emulsions of the W / O / W type, consisting of a continuous outer water phase, an oil phase dispersed therein and a second (inner) dispersed in this oil phase Water phase containing

• a) at least 85% by weight of water and optionally water-soluble sub punch a total of at least 85 wt .-%, based on the total weight of the preparations and a content of lipids, emulsifiers and lipophilic Components totaling a maximum of 15% by weight,
• b) at least one surface-active substance selected from the group of substances of the general formula (I)
  
  • - Wherein A and A 'the same or different organic radicals, selected from the group of branched and unbranched, saturated and unsaturated alkyl and acyl radicals and hydroxyacyl radicals having 10-30 carbon atoms, and also from the group of hydroxyacyl groups connected via ester functions, according to Scheme
    
  • - where R 'is selected from the group of branched and unbranched alkyl groups with 1 to 20 carbon atoms and R "is selected from the group of branched and unbranched alkylene groups with 1 to 20 carbon atoms and b can assume numbers from 0 to 200,
  • a represents a number from 1 to 100, preferably 2 to 60, in particular 5 to 40,
  • - X is a single bond or the group
    represents
  • R ₁ and R _{2 are selected} independently of one another from the group H, methyl,
  • - R _{3 is} selected from the group H, and the branched and unbranched, saturated and unsaturated alkyl and acyl radicals with 1-20 carbon atoms.
• c) containing one or more lipid components, which the lipid phase of Include emulsion,
• d) wherein the weight ratio of (b) to (c) from the range 0.10 to 0.25 ge is chosen

remedy the disadvantages of the prior art.  

Surprisingly, the preparations according to the invention are in use the skin extremely pleasant and are characterized by very high cosmetic elegance out. It is with the means that the person skilled in the art without further inventive action are, almost any viscosity can be achieved, so that the present invention for example as a flowable dosage form (such as a lotion) or as a semi-solid until solid preparation (such as a cream) can be designed.

The total amount of the surfactant sub used in the present invention punching in the finished cosmetic or dermatological preparations in part from the range of 0.1-10.0% by weight, preferably 0.5-7.5% by weight, in particular their chosen 1.0-5.0 wt .-%, based on the total weight of the preparations.

The preparations according to the invention particularly advantageously contain more than 85% by weight. of water and optionally water-soluble substances, based on the Total weight of the preparations.

It is known that emulsifiers of the type W / O emulsi described above Have onions with a high water content generated. Nevertheless, the known stand technology does not show the way to the present invention.

The preparation of the W / O / W emulsions according to the invention is advantageously carried out in such a way that

• 1. a water phase with
• 2. at least one surface-active substance selected from the group of substances of the general formula (I)
  
  • - Wherein A and A 'the same or different organic radicals, selected from the group of branched and unbranched, saturated and unsaturated alkyl and acyl radicals and hydroxyacyl radicals having 10-30 carbon atoms, and also from the group of hydroxyacyl groups connected via ester functions, according to Scheme
    
  • - where R 'is selected from the group of branched and unbranched alkyl groups with 1 to 20 carbon atoms and R "is selected from the group of branched and unbranched alkylene groups with 1 to 20 carbon atoms and b can assume numbers from 0 to 200,
  • a represents a number from 1 to 100, preferably 2 to 60, in particular 5 to 40,
  • - X is a single bond or the group
    represents
  • R ₁ and R _{2 are selected} independently of one another from the group H, methyl,
  • R _{3 is} selected from group H, and the branched and unbranched, saturated and unsaturated alkyl and acyl radicals with 1-20 carbon atoms,
• 3. one or more lipid components which surround the lipid phase of the emulsion grasp,
• 4. wherein the weight ratio of (b) to (c) from the range 0.10 to 0.25 ge is chosen

produces a W / O emulsion and this

• 1. gives to a second water phase,
• 2. which advantageously contains at least one second surface-active substance,
• 3. stirred and the W / O / W emulsion thus formed, if desired, one or subjected to several homogenization steps,
• 4. wherein the water phases mentioned under (a ') and (a ") in total at least 85% by weight, based on the total weight of the preparation.

The structural formula is not to be interpreted in such a way that all the radicals R ₁ , R ₂ and R ₃ represented in brackets must be the same in the entire molecule through the index a. Rather, these residues can be found in any of the a fragments

can be freely chosen.

To use an example for particularly advantageous in the sense of the present invention The surface-active substance is polyethylene glycol 30 dipolyhydroxy stearate (PEG-30 dipolyhydroxystearate), which is available from the company ICI Surfactants is sold under the trademark ARLACEL® P135.

The total amount of surfactants used in the present invention in the cosmetic or dermatological preparations according to the invention advantageously from the range of 0.05-5.0% by weight, preferably 01-2.5% by weight selected, based on the total weight of the preparations.

It is advantageous if the second surfactant mentioned under (e) or substances is selected from the group of customary O / W emulsifiers.

In the context of the present disclosure is used as a generic term for fats, oils, waxes and the like, sometimes the term "lipids" is used, as will be appreciated by those skilled in the art is quite common. The terms "oil phase" and "lipid phase" also become synonymous applied.  

The constituents of the lipid phase can advantageously be selected from the group of polar and non-polar lipid components, for example selected from the group Vaseline (petrolatum), paraffin oil and polyolefins. Polyde are among the polyolefins cene and hydrogenated polyisobutenes are the preferred substances.

For the purposes of the present invention, the oil phase can also advantageously be substances contain, selected from the group of esters of saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or uns branched alcohols with a chain length of 3 to 30 carbon atoms and from the group the ester of aromatic carboxylic acids and saturated and / or unsaturated, ver branched and / or unbranched alcohols with a chain length of 3 to 30 carbon atoms. Such ester oils can then advantageously be selected from the group of isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononyl isononanoate, 2-ethylhe xyl palmitate, 2-ethylhexyl laurate, 2-hexyldecyl stearate, 2-octyldodecyl palmitate, oleyl oleate, Oleylerucat, Erucyloleat, Erucylerucat as well as synthetic, semi-synthetic and natural che mixtures of such esters, such as. B. Jojoba oil.

Furthermore, the oil phase can advantageously be selected from the group of the branched ones and unbranched hydrocarbons and waxes, the silicone oils, the dialkyl ethers, the group of saturated or unsaturated, branched or unbranched alcohols hole, as well as the fatty acid triglycerides, especially the triglycerol esters and / or unsaturated, branched and / or unbranched alkane carboxylic acids Chain length from 8 to 24, especially 12-18 C atoms. The fatty acid triglycerides can advantageously be selected from the group of synthetic, semi-synthetic and natural oils, e.g. B. olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, palm kernel oil and the like.

According to the invention, fat and / or wax particles to be used advantageously in the oil phase Components can be selected from the group of vegetable waxes, animal waxes, mines Oral waxes and petrochemical waxes can be selected. Favorably according to the invention  are, for example, candelilla wax, carnauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, berries wax, ouricury wax, montan wax, jojoba wax, shea butter, beeswax, shelf lacquer wax, walrus, lanolin (wool wax), pretzel fat, ceresin, ozokerite (earth wax), par Affine waxes and micro waxes.

Further advantageous fat and / or wax components are chemically modified waxes and synthetic waxes, such as those under the trade names Syncrowax HRC (glyceryl tribehenate), Syncrowax HGLC (C _16-36 fatty acid triglyceride) and Syncrowax AW 1C (C _18-36 - Fatty acid) available from CRODA GmbH such as montan ester waxes, Sasol waxes, hydrogenated jojoba waxes, synthetic or modified beeswaxes (e.g. dimethicone copolyol beeswax and / or C _30-50- alkyl beeswax), polyalkylene waxes, polyethylene glycol waxes, but also chemically modified fats , such as B. hydrogenated vegetable oils (for example hydrogenated castor oil and / or hydrogenated coconut fat glycerides), triglycerides such as trihydroxystearin, fatty acids, fatty acid esters and glycol esters such as C _20-40 alkyl stearate, C _20-40 alkyl hydroxystearoyl stearate and / or glycol montanate. Also advantageous are certain organosilicon compounds which have similar physical properties to the fat and / or wax components mentioned, such as stearoxytrimethylsilane.

According to the invention, the fat and / or wax components can be used both individually and also be present in a mixture.

Any mixtures of such oil and wax components are also advantageous To use the sense of the present invention. It can also be advantageous if necessary be adhesive, waxes, for example cetyl palmitate, as a lipid component of the oil phase clog.

Of the hydrocarbons are paraffin oil, hydrogenated polyolefins (e.g. hydrogenated Po lyisobutene) squalane and squalene advantageous for the purposes of the present invention use.  

The oil phase can also advantageously contain cyclic or linear silicone have oils or consist entirely of such oils, although preferred will, in addition to the silicone oil or the silicone oils, an additional content of others To use oil phase components.

Cyclomethicone (octamethylcyclotetrasiloxane) can advantageously be used. But other silicone oils are also advantageous for the purposes of the present invention apply, for example hexamethylcyclotrisiloxane, polydimethylsiloxane, poly (methyl phenylsiloxane).

Advantageously according to the invention, the oil phase can also comprise constituents, selected from the group of classic fats, essentially triglycerides.

The oils according to the invention are preferably selected from the group of triglycerides with the following structure:

wherein R ₁ , R ₂ and R _{3 are} independently selected from the group of ver branched and unbranched, alkyl carboxyl or alkenyl carboxyl groups having 12 to 24 carbon atoms. It may be advantageous if one or more aliphatic hydrogen atoms of the alkylcarboxyl or alkenylcarboxyl groups are substituted by hydroxyl groups.

It is particularly advantageous if R ₁ , R ₂ and / or R _{3 have} 16 to 20 carbon atoms and are selected from the group of mono- to tri-unsaturated carboxylic acid residues.

If R ₁ , R ₂ and / or R ₃ carry hydroxyl groups, the preferred alkenyl carboxyl residue is the ricinoleic acid residue.

It is also particularly advantageous to use oils from the group of soybean oil, sunflower oil and wheat choose germ oil and castor oil.

The aqueous phase of the preparations according to the invention optionally contains some alcohols, diols or polyols of low C number, and their ethers, preferably Ethanol, isopropanol, propylene glycol, glycerin, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, Diethylene glycol monomethyl or monoethyl ether and analog products, also Alko get lower C number, e.g. As ethanol, isopropanol, 1,2-propanediol, glycerin and in particular in particular one or more thickeners, which one or which is advantageously chosen can be selected from the group consisting of silicon dioxide, aluminum silicates, polysaccharides and their derivatives, e.g. B. hyaluronic acid, xanthan gum, hydroxypropylmethyl cellulose, particularly advantageously from the group of polyacrylates, preferably a polyacrylate the group of so-called carbopoles, for example carbopoles of types 980, 981, 1382, 2984, 5984, or types ETD (Easy-to-disperse) 2001, 2020, 2050, individually or in any combination with each other.

A particular advantage of the present invention is that it allows high Use concentrations of polyols, especially glycerin.

Under (e) designated O / W emulsifiers can, for example, advantageously be selected from the group of polyethoxylated or polypropoxylated or polyethoxylated and polypropoxylated products, e.g. B .:

• - The fatty alcohol ethoxylates
• - the ethoxylated wool wax alcohols,
• the polyethylene glycol ether of the general formula RO - (- CH ₂ -CH ₂ -O-) _n -R ',
• the fatty acid ethoxylates of the general formula R-COO - (- CH ₂ -CH ₂ -O-) _n -H,
• the etherified fatty acid ethoxylates of the general formula R-COO - (- CH ₂ -CH ₂ -O-) _n -R ',
• the esterified fatty acid ethoxylates of the general formula R-COO - (- CH ₂ -CH ₂ -O-) _n -C (O) -R ',
• - The polyethylene glycol glycerol fatty acid ester  
• - The ethoxylated sorbitan esters
• - the cholesterol ethoxylates
• - The ethoxylated triglycerides
• the alkyl ether carboxylic acids of the general formula RO - (- CH ₂ -CH ₂ -O-) _n -CH ₂ -COOH and n represent a number from 5 to 30,
• - the polyoxyethylene sorbitol fatty acid ester,
• - The alkyl ether sulfates of the general formula RO - (- CH ₂ -CH ₂ -O-) _n -SO ₃ -H
• the fatty alcohol propoxylates of the general formula RO - (- CH ₂ CH (CH ₃ ) -O-) _n -H,
• the polypropylene glycol ether of the general formula RO - (- CH ₂ -CH (CH ₃ ) -O-) _n -R ',
• - the propoxylated wool wax alcohols,
• the etherified fatty acid propoxylates R-COO - (- CH ₂ -CH (CH ₃ ) -O-) _n -R ',
• the esterified fatty acid propoxylates of the general formula R-COO - (- CH ₂ CH (CH ₃ ) -O-) _n -C (O) -R ',
• the fatty acid propoxylates of the general formula R-COO - (- CH ₂ -CH (CH ₃ ) -O-) _n -H,
• - the polypropylene glycol glycerol fatty acid ester
• - The propoxylated sorbitan esters
• - the cholesterol propoxylates
• - the propoxylated triglycerides
• - The alkyl ether carboxylic acids of the general formula RO - (- CH ₂ -CH (CH ₃ ) O-) _n -CH ₂ -COOH
• - The alkyl ether sulfates or the acids of these sulfates on the general formula RO - (- CH ₂ -CH (CH ₃ ) -O-) _n -SO ₃ -H
• the fatty alcohol ethoxylates / propoxylates of the general formula ROX _n Y _m -H,
• the polypropylene glycol ether of the general formula ROX _n -Y _m -R ',
• the etherified fatty acid propoxylates of the general formula R-COO-X _n -Y _m -R ',
• - The fatty acid ethoxylates / propoxylates of the general formula R-COO-X _n -Y _m -H.

According to the invention, the polyethoxylated or polypropoxylated or polyethoxylated and polypropoxylated O / W emulsifiers chooses from the group of substances with HLB values of 11-18, especially advantageous with HLB values of 14.5-15.5, provided the O / W emulsifiers are saturated Re have R and R '. The O / W emulsifiers have unsaturated radicals R and / or R ', or if isoalkyl derivatives are present, the preferred HLB value can be such Emulsifiers are also lower or higher.

It is advantageous to choose the fatty alcohol ethoxylates from the group of the ethoxylated stearyl alcohols, cetyl alcohols, cetyl stearyl alcohols (cetearyl alcohols). The following are particularly preferred:
Polyethylene glycol (13) stearyl ether (Steareth-13), polyethylene glycol (14) stearyl ether (Steareth-14), polyethylene glycol (15) stearyl ether (Steareth-15), polyethylene glycol (16) - stearyl ether (Steareth-16), polyethylene glycol (17) stearyl ether (Steareth-17), polyethylene glycol (18) stearyl ether (Steareth-18), polyethylene glycol (19) stearyl ether (Steareth-19), polyethylene glycol (20) stearyl ether (Steareth-20),
Polyethylene glycol (12) isostearyl ether (isosteareth-12), polyethylene glycol (13) isostearyl ether (isosteareth-13), polyethylene glycol (14) isostearyl ether (isosteareth-14), polyethylene glycol (15) isostearyl ether (isosteareth-15), polyethylene glycol (16) isostearyl ether (isosteareth-16), polyethylene glycol (17) isostearyl ether (isosteareth-17), polyethylene glycol (18) isostearyl ether (isosteareth-18), polyethylene glycol (19) isostearyl ether (isosteareth-19), polyethylene glycol (20) isostearyl ether (isosteareth- 20),
Polyethylene glycol (13) cetyl ether (Ceteth-13), polyethylene glycol (14) cetyl ether (Ceteth-14), polyethylene glycol (15) cetyl ether (Ceteth-15), polyethylene glycol (16) cetyl ether (Ce teth-16), polyethylene glycol (17) cetyl ether (Ceteth-17), polyethylene glycol (18) cetyl ether (Ceteth-18), polyethylene glycol (19) cetyl ether (Ceteth-19), polyethylene glycol (20) cetyl ether (Ceteth-20),
Polyethylene glycol (13) isocetyl ether (isoceteth-13), polyethylene glycol (14) isocetyl ether (isoceteth-14), polyethylene glycol (15) isocetyl ether (isoceteth-15), polyethylene glycol (16) - isocetyl ether (isoceteth-16), polyethylene glycol (17) isocetyl ether (Isoceteth-17), polyethylene glycol (18) isocetyl ether (isoceteth-18), polyethylene glycol (19) isocetyl ether (isoceteth-19), polyethylene glycol (20) isocetyl ether (isoceteth-20),
Polyethylene glycol (12) oleyl ether (oleth-12), polyethylene glycol (13) oleyl ether (oleth-13), polyethylene glycol (14) oleyl ether (oleth-14), polyethylene glycol (15) oleyl ether (oleth-15),
Polyethylene glycol (12) lauryl ether (Laureth-12), polyethylene glycol (12) isolauryl ether (Iso laureth-12),
Polyethylene glycol (13) cetyl stearyl ether (ceteareth-13), polyethylene glycol (14) cetyl stearyl ether (ceteareth-14), polyethylene glycol (15) cetyl stearyl ether (ceteareth-15), poly ethylene glycol (16) cetyl stearyl ether (ceteareth-16), polyethylene glycol cetylstearyl ether (Ceteareth-17), polyethylene glycol (18) cetylstearylether (Ceteareth-18), polyethylene glycol (19) cetylstearylether (Ceteareth-19), polyethylene glycol (20) cetylstearylether (Ceteareth-20).

It is also advantageous to choose the fatty acid ethoxylates from the following group:
Polyethylene glycol (20) stearate, polyethylene glycol (21) stearate, polyethylene glycol (22) steaate, polyethylene glycol (23) stearate, polyethylene glycol (24) stearate, polyethylene glycol (25) - stearate,
Polyethylene glycol (12) isostearate, polyethylene glycol (13) isostearate, polyethylene glycol (14) isostearate, polyethylene glycol (15) isostearate, polyethylene glycol (16) isostearate, polyethylene glycol (17) isostearate, polyethylene glycol (18) isostearate, polyethylene glycol (19) isostearate , Polyethylene glycol (20) isostearate, polyethylene glycol (21) isostearate, polyethylene glycol (22) isostearate, polyethylene glycol (23) isostearate, polyethylene glycol (24) isostearate, polyethylene glycol (25) isostearate,
Polyethylene glycol (12) oleate, Polyethylene glycol (13) oleate, Polyethylene glycol (14) oleate, Polyethylene glycol (15) oleate, Polyethylene glycol (16) oleate, Polyethylene glycol (17) oleate, Polyethylene glycol (18) oleate, Polyethylene glycol (19) oleate, Polyethylene glycol (20) oleate.

Sodium lau can advantageously be used as the ethoxylated alkyl ether carboxylic acid or its salt reth-11-carboxylate can be used.

Sodium laureth 1-4 sulfate can advantageously be used as alkyl ether sulfate.

Polyethylene glycol (30) cholesteryl can advantageously be used as the ethoxylated cholesterol derivative ether can be used. Polyethylene glycol (25) soyasterol has also proven itself.

Polyethylene glycol (60) evening prim can advantageously be used as ethoxylated triglycerides rose glycerides can be used (evening primrose = evening primrose).

Another advantage is the polyethylene glycol glycerol fatty acid ester from the group Polyethylene glycol (20) glyceryl laurate, polyethylene glycol (21) glyceryl laurate, polyethylene glycol col (22) glyceryl laurate, polyethylene glycol (23) glyceryl laurate, polyethylene glycol (6) glyceryl caprat / caprinate, polyethylene glycol (20) glyceryl oleate, polyethylene glycol (20) glyceryl iso stearate, polyethylene glycol (18) glyceryl oleate cocoate to choose.

It is also favorable to sorbitan esters from the group of polyethylene glycol (20) sorbi tanmonolaurate, polyethylene glycol (20) sorbitan monostearate, pelyethylene glycol (20) sorbi tanmonoisostearate, polyethylene glycol (20) sorbitan monopalmitate, polyethylene glycol (20) - to choose sorbitan monooleate.

Particularly advantageous preparations are also obtained when added or Active ingredients antioxidants are used. According to the invention contain the accessories beneficial one or more antioxidants. As cheap, but still optional antioxidants can all be used for cosmetic and / or suitable or customary antioxidants used in matological applications become.  

The antioxidants are advantageously selected from the group consisting of amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (e.g. urocanic acid) and their derivatives, peptides such as D, L-carnosine, D. -Carnosine, L-carnosine and their derivatives (e.g. Anserin), carotenoids, carotenes (e.g. α-carotene, β-carotene, Ψ-lycopene) and their derivatives, lipoic acid and its derivatives (e.g. Dihydrolipoic acid), aurothioglucose, propylthiouracil and other thiols (e.g. thioredoxin, glutathione, cy stone, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl -, Palmitoyl, oleyl, y-linoleyl, cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and sulfoximine compounds (e.g. B. Buthioninsulfoximine, Homocysteinsulfoximin, Bu thioninsulfone, Penta-, Hexa-, Heptathion insulfoximine) in very low tolerable doses (e.g. B. pmol to µmol / kg), also (metal) chelators (e.g. α-hydroxyfatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid, bile acid , Biliary extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (e.g. γ-linolenic acid, linoleic acid, oleic acid), folic acid and their derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and derivatives (e.g. ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and derivatives (vitamin A palmitate) as well as konyferyl benzoate of benzoin, rutinic acid and its derivatives, ferulic acid and their derivatives, butylhydroxy toluene, butylated hydroxyanisole, nordihydroguajak resin acid, nordihydroguajaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, zinc and its derivatives (e.g. ZnO, ZnSO ₄ ) selenium and its derivatives (e.g. sel lenmethionine), stilbene and their derivatives (e.g. B. stilbene oxide, trans-stilbene oxide) and the derivatives suitable according to the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these active substances.

Oil-soluble antioxidants can be particularly advantageous for the purposes of the present invention dantien are used.

An astonishing property of the present invention is that according to the invention Preparations very good vehicle for cosmetic or dermatological active ingredients in  are the skin, with preferred active ingredients being antioxidants that protect the skin can protect against oxidative stress. Preferred antioxidants are among them Vitamin E and its derivatives as well as Vitamin A and its derivatives.

The amount of antioxidants (one or more compounds) in the preparations is preferably 0.001 to 30% by weight, particularly preferably 0.05-20% by weight, in particular 1-10 wt .-%, based on the total weight of the preparation.

If vitamin E and / or its derivatives are the antioxidant (s) advantageous, the respective concentrations of which range from 0.001-10% by weight, based on the total weight of the formulation.

If vitamin A or vitamin A derivatives or carotenes or their derivatives the or the antioxidants are advantageous, their respective concentrations from the Range of 0.001-10% by weight based on the total weight of the formulation choose.

It is of course known to the person skilled in the art that cosmetic preparations mostly do not are conceivable without the usual auxiliaries and additives. The invention Accordingly, cosmetic and dermatological preparations can also be used Contain cosmetic auxiliaries, as they usually ver in such preparations are used, for example, consistency generators, stabilizers, fillers, preserves agents, perfumes, anti-foaming agents, dyes, pig elements that have a coloring effect, thickeners, surface-active substances, Emulsifiers, softening, moisturizing and / or moisturizing substances, anti-inflammatory substances, additional active ingredients such as vitamins or proteins ine, light stabilizers, insect repellents, bactericides, virucides, water, salts, antimicrobial, proteolytic or keratolytically active substances, medicines or other common components of a cosmetic or dermatological formulation such as alcohols, polyols, polymers, foam stabilizers, organic solutions medium or electrolytes.  

The latter can be selected, for example, from the group of salts followed by the anions: chlorides, also inorganic oxo-element anions, of these in particular special sulfates, carbonates, phosphates, borates and aluminates. Even on organic Anion-based electrolytes are advantageous, e.g. B. lactates, acetates, benzoates, pro pionates, tartrates, citrates, amino acids, ethylenediaminetetraacetic acid and their salts and others. Preferred cations of the salts are ammonium and alkyl ammonium, alkali metal, alkaline earth metal, magnesium, iron or zinc ions ver turns. There is no need to mention that in cosmetics only physiologically un questionable electrolytes should be used. Potassium is particularly preferred chloride, common salt, magnesium sulfate, zinc sulfate and mixtures thereof.

Mutatis mutandis, corresponding requirements apply to the formulation of medicinal products preparations.

The W / O / W emulsions according to the invention can be used as the basis for cosmetic or serve dermatological formulations. These can be put together as usual be set and for example for the treatment and care of the skin and / or the Hair, as a lip care product, as a demo product and as a make-up or make-up removal product can be used in decorative cosmetics or as a sunscreen. For use are the cosmetic and dermatological preparations according to the invention in the usual way for cosmetics or dermatics on the skin and / or hair sufficient amount applied.

Accordingly, cosmetic or topical dermatological compositions can be used gene in the sense of the present invention, depending on its structure, for example ver can be used as skin protection cream, cleansing milk, sunscreen lotion, nutrient cream, day or night cream, etc. It may be possible and advantageous that Compositions according to the invention as a basis for pharmaceutical formu lations to use.

Those cosmetic and dermatological preparations which are in in the form of a sunscreen. These preferably contain in addition the active substance combinations according to the invention additionally at least one UV-A fil  ter substance and / or at least one UV-B filter substance and / or at least one inorganic pigment.

However, it is also advantageous for the purposes of the present invention to use such cosmetics human and dermatological preparations, their main purpose is not protection from sunlight, but it does contain UV protection contain substances. So z. B. in day creams usually UV-A or UV-B Filter substances incorporated.

UV protection substances, as well as antioxidants and, if desired, Preservatives, an effective protection of the preparations themselves against ver coarse.

Preparations according to the invention can also advantageously contain substances ten, which absorb UV radiation in the UVB range, the total amount of filters substances z. B. 0.1 wt .-% to 30 wt .-%, preferably 0.5 to 10 wt .-%, esp is particularly 1.0 to 6.0 wt .-%, based on the total weight of the preparation to provide cosmetic preparations that the hair or the Protect skin from the entire range of ultraviolet radiation. You can also serve as a sunscreen for hair or skin.

If the emulsions according to the invention contain UVB filter substances, they can be oil-soluble or water-soluble. Oil-soluble UVB filters advantageous according to the invention are e.g. B .:

• - 3-benzylidene camphor derivatives, preferably 3- (4-methylbenzylidene) camphor, 3- Benzylidene camphor;
• - 4-aminobenzoic acid derivatives, preferably 4- (dimethylamino) benzoic acid (2- ethylhexyl) ester, 4- (dimethylamino) benzoic acid amyl ester;
• - Esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester, 4-Me isopentyl thoxy cinnamate;
• - Esters of salicylic acid, preferably salicylic acid (2-ethylhexyl) ester, salicylic acid re (4-isopropylbenzyl) ester, salicylic acid homomethyl ester,  
• Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzo phenone;
• Esters of benzalmalonic acid, preferably 4-methoxybenzalmalonic acid di (2- ethylhexyl) ester,
• - Derivatives of 1,3,5-triazine, preferably 2,4,6-trianilino- (p-carbo-2'-ethyl-1'- hexyloxy) -1,3,5-triazine.

The list of UVB filters mentioned in combination with the invention Active ingredient combinations can of course not be used as limitie be dynamic.

It can also be advantageous to use W / O / W emulsions according to the invention with UVA filters to formulate, which are usually contained in cosmetic preparations. These substances are preferably dibenzoyl derivatives thans, especially 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione and 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione.

Cosmetic and dermatological preparations according to the invention can also contain inorganic pigments that are commonly used in cosmetics to protect the Skin against UV rays. These are oxides of titanium, Zinc, iron, zirconium, silicon, manganese, aluminum, cerium and mixtures thereof, as well as variations in which the oxides are the active agents. Especially it is preferably pigments based on titanium dioxide.

The following can also be used:

• - Fats, waxes and other natural and synthetic fat bodies, preferred wise esters of fatty acids with low C alcohols, e.g. B. with isopropanol, Propylene glycol or glycerin, or esters of fatty alcohols with alkanoic acids low C number or with fatty acids;
• - Alcohols, diols or polyols of low C number, and their ethers, preferably Ethanol, isopropanol, propylene glycol, glycerin, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or  
• - monobutyl ether, diethylene glycol monomethyl or monoethyl ether and analog products.

Preparations according to the invention can also contain active substances (one or more compounds) which are selected from the group: acetylsalicylic acid, atropine, azulene, hydrocortisone and its derivatives, for. B. hydrocortisone-17-valerate, vitamins, e.g. B. ascorbic acid and its derivatives, vitamins of the B and D series, very cheap vitamin B ₁ , vitamin B _12, vitamin D ₁ , but also bisabolol, unsaturated fatty acids, namely the essential fatty acids (often called vitamin F) ), in particular γ-linolenic acid, oleic acid, eicosapentaenoic acid, docosahexaenoic acid and its derivatives, chloramphenicol, caffeine, prostaglandins, thymol, camphor, extracts or other products of plant and animal origin, e.g. B. evening primrose oil, borage oil or currant seed oil, fish oils, cod liver oil but also ceramides and ceramide-like compounds and so on. It is also advantageous to choose the active ingredients from the group of lipid-replenishing substances, for example Purcellin oil, Eucerit® and Neoce rit®.

The amount of such active substances (one or more compounds) in the preparations according to the invention is preferably 0.001 to 30% by weight, particularly preferably 0.05-20% by weight, in particular 1-10% by weight, based on the total weight of the Preparation.

The following examples are intended to illustrate the present invention without it restrict. The numerical values in the examples mean percentages by weight, be drew on the total weight of the respective preparations.  

example 1

W / O / W lotion

Example 2

W / O / W cream

Example 3

W / O / W lotion

Example 4

W / O / W cream

Example 5

W / O / W cream

Claims (5)

1. Containing multiple emulsions of the W / O / W type, consisting of a continuous outer water phase, an oil phase dispersed therein and a second (inner) water phase dispersed in this oil phase

• a) at least 85% by weight of water and optionally water-soluble substances totaling at least 85% by weight, based on the total weight of the preparations and a content of lipids, emulsifiers and lipophilic constituents of at most 15% by weight in total,
• b) at least one surface-active substance selected from the group of substances of the general formula (I)
  
  • - Wherein A and A 'the same or different organic radicals, selected from the group of branched and unbranched, saturated and unsaturated alkyl and acyl radicals and hydroxyacyl radicals having 10-30 carbon atoms, and also from the group of hydroxyacyl groups connected via ester functions, according to Scheme
    
  • - where R 'is selected from the group of branched and unbranched alkyl groups with 1 to 20 carbon atoms and R "is selected from the group of branched and unbranched alkylene groups with 1 to 20 carbon atoms and b can assume numbers from 0 to 200,
  • a represents a number from 1 to 100, preferably 2 to 60, in particular 5 to 40,
  • - X is a single bond or the group
    represents
  • R ₁ and R _{2 are selected} independently of one another from the group H, methyl,
  • R _{3 is} selected from group H, and the branched and unbranched, saturated and unsaturated alkyl and acyl radicals having 1-20 carbon atoms,
• c) containing one or more lipid components which comprise the lipid phase of the emulsion,
• d) wherein the weight ratio of (b) to (c) is selected from the range 0.10 to 0.25 ge.

2. The process for producing the W / O / W emulsions according to the invention is advantageously carried out in such a way that

• 1. a water phase with
• 2. at least one surface-active substance selected from the group of substances of the general formula (I)
  
  • - Wherein A and A 'the same or different organic radicals, selected from the group of branched and unbranched, saturated and unsaturated alkyl and acyl radicals and hydroxyacyl radicals having 10-30 carbon atoms, and also from the group of hydroxyacyl groups connected via ester functions, according to Scheme
    
  • - where R 'is selected from the group of branched and unbranched alkyl groups with 1 to 20 carbon atoms and R "is selected from the group of branched and unbranched alkylene groups with 1 to 20 carbon atoms and b can assume numbers from 0 to 200,
  • a represents a number from 1 to 100, preferably 2 to 60, in particular 5 to 40,
  • - X is a single bond or the group
    represents
  • R ₁ and R _{2 are selected} independently of one another from the group H, methyl,
  • R _{3 is} selected from group H, and the branched and unbranched, saturated and unsaturated alkyl and acyl radicals with 1-20 carbon atoms,
• 3. one or more lipid components which comprise the lipid phase of the emulsion,
• 4. wherein the weight ratio of (b) to (c) is selected from the range 0.10 to 0.25 ge,

produces a W / O emulsion and this

• 1. gives to a second water phase,
• 2. which advantageously contains at least one second surface-active substance,
• 3. stirred and, if desired, the W / O / W emulsion thus formed is subjected to one or more homogenization steps,
• 4. wherein the water phases mentioned under (a ') and (a ") should total at least 85% by weight, based on the total weight of the preparation.

3. Multiple emulsions according to claim 1 or method according to claim 2, characterized ge indicates that the surfactant is the polyethylene glycol 30 dipolyhy droxystearate is selected. 4. Multiple emulsions according to claim 1 or method according to claim 2, characterized ge indicates that the total amount of surfactant selected from the group of substances of the general formula (I) in the cosmetic or dermatological preparations in the range of 0.05-5.0 wt .-%, preferred 0.1-2.5% by weight is selected, based on the total weight of the preparations. 5. Multiple emulsions according to claim 1 or method according to claim 2, characterized ge indicates that the cosmetic or dermatological preparations more than Contain 85 wt .-% of water and water-soluble substances, based on the Total weight of the preparations.