DE3125710C2 - - Google Patents

Description

The present invention relates to a cosmetic agent, consisting of a dispersion of lipid beads. Aqueous dispersions of this type are already in the FR-PS 23 15 991 described.

The lipid spheres of these dispersions are characterized by their Layer structure, which consists of two or several layers of lipid, consisting of layers of one aqueous phase are separated from each other. So you can for encapsulating water-soluble active ingredients in the aqueous compartments existing between the lipid layers, such as pharmaceutical or cosmetic active ingredients, serve and shield them from the outside.

The aforementioned French patent also describes a method for the preparation of an aqueous dispersion of Lipid beads, in which the first step is the Lipids, which are the concentric layers of the beads should form with the aqueous solution to be encapsulated in contact, the ratio of lipophilic / hydrophilic Lipids is selected so that the latter in Swell water or in the encapsulated aqueous phase and form a flat lamella phase; in a second stage an aqueous solution is added to the lamella phase, which form the external continuous phase of the dispersion and thirdly you stir the whole thing vigorously, whereby  a dispersion of spheres is obtained between their concentric ones Layers of the aqueous phase to be encapsulated is included.

To form the concentric layers of the beads can be done according to the teaching of this French patent both amphiphilic or ionic or non-ionic lipids use. Of the non-ionic amphiphilic lipids one prefers:

• the straight-chain or branched polyglycerol ethers of the following formulas: where n is an integer from 1 to 6, pure straight-chain or branched, saturated or unsaturated aliphatic chain having 12 to 30 carbon atoms, hydrocarbon residues of lanolin alcohols or 2-hydroxyalkyl residues of long-chain α- diols;
• - The polyoxyethylene fatty alcohols;
• - The esters of polyols, which optionally oxyethylene and especially the polyoxyethylene sorbitol esters;
• - the glycolipids of natural or synthetic origin, for example the cerebroside.

Of the cosmetic active ingredients that are in the lipid beads the French patent counts for example: substances that are used for care the skin surface are determined, such as moisturizing agents, artificial tanning agents, coloring agents for the skin, water-soluble sun filters, antiperspirants, deodorants, Astringents, refreshing, toning, healing, keratolytic, depilatory products, perfumed water and extracts of animal or vegetable tissues.

It has been observed that the above cosmetic products in the form of an aqueous dispersion of lipid beads classic preparations in the form of oil and water emulsions have the advantage of being less aggressive and therefore less irritating when applied to the skin surface be applied.

The present invention describes a cosmetic Agents based on an aqueous dispersion of lipid beads, with which one can take advantage of the Dispersion of beads with the advantages, which are result from the presence of cosmetic oils.

The present invention thus relates to a cosmetic Agent consisting of an aqueous dispersion of beads, consisting of ordered molecular layers, between which an internal aqueous phase is enclosed, wherein these layers consist of at least one non-ionic, amphiphilic lipid. The remedy is labeled by at least one oil in the aqueous, external Phase surrounding the beads is dispersed.  

This oil is selected from esters of fatty acids and Polyols, especially liquid triglycerides, and esters of fatty acids and branched alcohols of the formula:

R-COOR ′

wherein

R for the rest of a higher fatty acid with 8 to 20 Carbon atoms and R'a branched hydrocarbon chain with 3 to 20 Carbon atoms

represents.

It has now surprisingly been found that the non-ionic amphiphilic beads the oil-in-water dispersion can stabilize without a conventional Emulsifier must be added and without beads be destroyed. However, it is known that stability an emulsion essentially from the presence of a Emulsifier depends on its molecules on the surface the oil droplets are absorbed and a kind of continuous Form membrane, which is the direct contact between two neighboring droplets, for example one Vibration, prevented. In the present case, the Those skilled in the art can therefore assume that the non-ionic amphiphilic lipids of the beads play the role of an emulsifier could play and on the surface of the oil droplets could be absorbed, but this stabilization would also cause the concentric layers the beads would be destroyed. However, this is not the case Case, and it is surprisingly found that the non-ionic amphiphilic beads according to the present invention Dispersion of at least one vegetable oil, as defined above,  can stabilize in an external aqueous phase by they disperse around the oil droplets and thus their Get shape.

In US-PS 39 57 971 are dispersions of beads ionic amphiphiles or liposomes, which are included in cosmetic lotions or creams, d. H. Water-in-oil or oil-in-water emulsions. According to the beads do not exist in the present invention from ionic amphiphiles, but from non-ionic Amphiphiles. In addition, it was found that one with the liposomes do not have a dispersion of any of the above Vegetable oils can stabilize in water while completely surprisingly the beads of non-ionic amphiphile such a dispersion according to the present invention can stabilize.

The preparation of the cosmetic composition according to the invention therefore takes place in two stages: In a first stage poses an aqueous non-ionic amphiphilic lipid Dispersion of beads by, as in the FR-PS 23 15 991 or described in FR-PS 22 21 122 is working. In a second stage, if the aqueous dispersion of the beads is produced, in particular an oil, which you can then stir in the external, dispersed aqueous phase.

The cosmetic composition according to the invention preferably contains 2 to 10% by weight of non-ionic, amphiphilic lipids, which form the walls of the beads, and 2 to 40% by weight of dispersed Oil (s) based on the total weight of the agent. The weight ratio of the nonionic is advantageously amphiphilic lipids to the (or the) dispersed Oil (s) between 0.2 / 1 and 1/1.  

The oils which are included in the agents according to the invention are selected from esters of fatty acids and polyols, especially liquid triglycerides and the esters of fatty acids and branched alcohols of the Formula:

R-COO-R ′,

wherein

R for the rest of a higher fatty acid with 8 to 20 carbon atoms stands and R'a branched hydrocarbon chain with 3 to 20 Represents carbon atoms.

The esters of fatty acids and polyols include in particular Sunflower, corn, soybean, pumpkin, grape seed, jojoba oils and glycerol tri-capro capylate. To the esters higher Fatty acids and branched alcohols belong to Purcellinöl.

The cosmetically active ingredients of the invention Means can be encapsulated inside or outside the beads be. According to a preferred embodiment contains the oil phase of the agent one or more lipid-soluble cosmetic substances. In the manufacture of the invention The latter are previously dissolved in the oil, which are added to the dispersion of the lipid beads should. Lipid-soluble cosmetic active ingredients include especially sun filters, such as 2-ethyl-hexyl-p-dimethylaminobenzoate or compounds that are dry or to improve aging skin, especially non-saponifiable as well as saponifiable constituents of soy, avocado, Tocopherols, vitamins E, F and antioxidants.

The oil-in-water dispersion, which is the external medium of the dispersion of Pellet represents at least one additive, in particular a gelling agent or a perfume. The addition is added to the dispersion together with the oil.  

The gel-forming agent can be used in concentrations of 0.1 to 2 wt .-%, based on the total weight of the agent used will. About the gel-forming agents that can be used include the cellulose derivatives, such as hydroxyethyl cellulose; synthetic polymers; Derviates from algae, such as Satiagum, or natural rubber, such as tragacanth. Preferably used one uses as a gelling agent hydroxyethyl cellulose, a mixture of carboxyvinyl acids (acrylic acid polymer), Satiagum or tragacanth.

The non-ionic amphiphilic lipids, which are the concentric ones Layers of the beads of the agent according to the invention are:

• - Esters of straight-chain or branched polyglycerols
• - Ether of straight-chain or branched polyglycerols of the formulas: wherein n is an integer between 2 and 6 and represents a straight-chain or branched, saturated aliphatic chain having 16 to 20 carbon atoms or the hydrocarbon radical of a lanolin alcohol;
• - polyoxyethylene sterols.

In the formation of the flat lamellar phase which is obtained when the non-ionic, amphiphilic lipids are brought into contact with the aqueous phase to be encapsulated, various auxiliaries can be added to the lipids in order, for example, to vary the permeability or the surface charge of the beads. One can optionally use long-chain alcohols and diols, sterols, especially cholesterol and β- sitosterol, long-chain amines and their quaternary ammonium derivatives, especially didodecyl-dimethylammonium bromide, hydroxyalkylamines, polyoxyethylene fatty amines, esters of long-chain amino alcohols, their salts and quaternary ammonium Add phosphoric acid esters of fatty alcohols, especially dicetyl phosphate, alkyl sulfates, for example sodium cetyl sulfate, certain polymers, such as polypeptides and proteins.

In addition to the aids listed above, you can also use a Add preservatives such as methyl p-hydroxybenzoate.

The aqueous phase, be it internal or external, may contain a water-soluble cosmetic that is commonly used to care for the face, hands, or body. These substances include moisturizing agents such as glycerin, sorbitol, pentaerythritol, inositol, pyrrolidone carboxylic acid and their salts; artificial tanning agents such as dihydroxyacetone, erythrulose, glyceraldehyde, γ- dialdehydes such as tartaric acid aldehyde; Colorants for the skin; Sun filters, antiperspirants, deodorants, astringents, refreshing, toning, healing keratolytic, depilatory products, perfumed water, extracts from animal or vegetable tissues, such as proteins, amniotic fluid, polysaccharides and antiseborrhea agents.

To describe the invention in more detail below some embodiments are purely illustrative.

The preparation of those described in the examples below Cosmetic products are made in two stages. In a first stage, the process of FR-PS 23 15 991 an aqueous dispersion ago. The watery Lipid bead dispersion is made from:

• - a non-ionic, amphiphilic lipid;
• - sterols, such as cholesterol or β- sitosterol;
• - optionally dicetyl phosphate;
• - If appropriate, water-soluble cosmetic active ingredients and
• - demineralized water, which is a preservative may contain.

In a second stage, you add the oil that you pass through intensive mechanical stirring at room temperature, preferably at about 40 ° C, dispersed. During this second Step can optionally be lipid-soluble cosmetic Add active ingredients, perfumes and / or gel-forming agents.  

Example 1 Comparative experiments between an inventive cosmetic agent and a known agent

Two means (A) and (B) are produced, essentially are the same, with the difference that the mean (B) no oil is added in the second phase.

Agent (A) contains the following components:

1st stage

non-ionic, amphiphilic lipid of the formula:

where R is a hexadecyl radical and
n has a statistical mean of 3 3.8 g β- sitosterol 3.8 g dicetyl phosphate 0.4 g methyl p-hydroxybenzoate 0.3 g demineralized water 66.7 g

2nd stage

25 g of sunflower oil are added to the above dispersion stir the whole thing vigorously to get the final dispersion receive.

The cosmetic agent (B) is produced in the same way, but without sunflower oil in a second phase admits, but the 25 g of oil by an equal amount demineralized water replaced.  

The cosmetic agent (A) thus differs from cosmetic agent (B) only in that it contains 25 g of sunflower oil contains.

1) Measurements of the coefficient of friction of the skin in Distribution of cosmetic products (A) and (B)

The coefficient of friction of the skin is when distributing of cosmetic products (A) and (B) on the forearm a test subject with a rotating button measured; to do this, measure the resistance of the button at its rotation. The button comes with a constant Force (20 or 50 g) pressed on.

The following results are obtained:

It is found that agent (B), i.e. H. the watery Dispersion of the lipid spheres, which contains no oil, significantly increases the coefficient of friction of the skin, while the inventive agent (A), d. H. a Dispersion of beads, which contains an oil, the has the opposite effect. This significant lowering of the Coefficient of friction of the skin in cosmetics means that with the inventive agent (A) the skin a lot becomes softer.  

2) Measurement of the elastic modulus of the human Stratum corneum, performed in vitro before and after Apply the cosmetic agents A and B described above

These measurements are carried out with a laboratory device, which determines the elasticity of the skin is. Such a device is in FR-PS 78 25 149 described.

The test conditions are as follows:
relative humidity: 72% ± 2
Temperature: 30 ° C ± 0.2
Amount of product applied: 5 mg / cm²

The following results are obtained:

Products tested% medium reduction in elastic modulus
1 h 30 min after application

Product (B) 0 Product (A)
according to the invention + 15

The above results clearly show the difference in the plasticity of the cornea, depending on whether you have a dispersion of beads without oil phase or with oil phase applies.  

Example 2 Nourishing fluid for the body 1st stage

As described above, an aqueous dispersion of lipid beads is prepared from the following compounds:
non-ionic, amphiphilic lipid of the general formula:

wherein

R represents a hexadecyl radical and
n represents a mean statistical value of 3 4.5 g of β- sitosterol 4.5 g of dicetyl phosphate 1.9 g of methyl p-hydroxybenzoate 0.3 g of pyrrolidone carboxylic acid sodium salt 2.0 g of demineralized water 56.5 g

2nd stage

The dispersion obtained after the 1st stage is added from beads the following connections to:

Perfume 0.4 g Sunflower oil10.0 g Mixture of vinyl carboxylic acids 0.4 g Triethanolamine 0.4 g demineralized water 20.0 g  

Example 3 Nourishing fluid for the face 1st stage

As described above, an aqueous dispersion of lipid beads is prepared from the following substances:
non-ionic amphiphilic lipid of the general formula

where R is a hexadecyl radical and
n is 2 is 6.0 g cholesterol 1.6 g dicetyl phosphate 0.4 g methyl p-hydroxybenzoate 0.3 g demineralized water 61.1 g

2nd stage

The dispersion of. Obtained from the 1st stage is used Beads the following connections to:

Perfume 0.2 g Grape seed oil 20.0 g Mixture of vinyl carboxylic acids 0.2 g Triethanolamine 0.2 g demineralized water10.0 g  

Example 4 Nourishing fluid for the hands 1st stage

As described above, an aqueous dispersion is made from lipid beads from the following compounds:

polyoxyethylene phytosterols
(statistical distribution of the mean value equal to 5) 6.0 g cholesterol 2.0 g methyl p-hydroxybenzoate 0.3 g demineralized water 45.7 g

2nd stage

The dispersion obtained from the first stage is used the following substances from beads:

Perfume 0.2 g Jojoba oil 25.0 g Mixture of vinyl carboxylic acids 0.4 g Triethanolamine 0.4 g demineralized water 20.0 g

Example 5 Body care fluid 1st stage

As described above, an aqueous dispersion of lipid beads is prepared from the following compounds:
non-ionic, amphiphilic lipid of the general formula:

where R is a hexadecyl radical and
n has an average statistical value of 3, 4.0 g of cholesterol, 4.0 g of methyl p-hydroxybenzoate, 0.3 g of demineralized water, 45.5 g

2nd stage

The dispersion of. Obtained in the first stage is used Beads the following connections to:

Perfume 0.4 g Corn oil 25.0 g Mixture of vinyl carboxylic acids 0.4 g Triethanolamine 0.4 g demineralized water 20.0 g

Example 6 Facial care fluid 1st stage

As described above, an aqueous dispersion of lipid beads is prepared from the following compounds:
non-ionic amphiphilic lipid of the general formula

where R is a hexadecyl radical and
n has a statistical mean of 3 has 0.95 g of β- sitosterol 0.95 g of dicetyl phosphate 0.10 g of methyl p-hydroxybenzoate 0.30 g of demineralized water 64.80 g

2nd stage

The dispersion of the beads obtained in the first phase add the following:

Perfume 0.4 g soybean oil 10.0 g non-saponifiable soy constituents 2.0 g hydroxyethyl cellulose with a Brookfield viscosity
from 3400-5500 m Pas (1%; 25 ° C) 0.5 g demineralized water 20.0 g

Example 7 Sunscreen 1st stage

As described above, an aqueous dispersion of lipid beads is prepared from the following compounds:
non-ionic amphiphilic lipid of the general formula

where R is a hexadecyl radical and
n has a statistical mean value of 3 3.6 g β- sitosterol 3.6 g didodecyl-dimethyl-ammonium bromide 0.8 g methyl p-hydroxybenzoate 0.3 g demineralized water 45.9 g

2nd stage

The bead dispersion obtained from the first stage the following substances are added:

Perfume 0.4 g Pumpkin oil 22.0 g 2-ethylhexyl p-dimethylamino benzoate 3.0 g Tragacanth gum 0.4 g demineralized water 20.0 g

Example 8 Care fluid for the hands 1st stage

As indicated above, an aqueous dispersion of lipid beads is made from the following compounds:
non-ionic, amphiphilic lipid of the general formula

where R is a hexadecyl radical and
n has a statistical mean of 3 3.8 g β- sitosterol 3.8 g dicetyl phosphate 0.4 g methyl p-hydroxybenzoate 0.3 g glycerol 3.0 g demineralized water 42.5 g

2nd stage

The dispersion of. Obtained from the first stage Beads are given the following compounds:

Perfume 0.2 g Purcellin oil 25.0 g Satiagum 1.0 g demineralized water 20.0 g

Example 9 Body care fluid 1st stage

As indicated above, an aqueous dispersion of lipid beads is made from the following compounds:
non-ionic amphiphilic lipid of the general formula

where R is a hexadecyl radical and
n a statistical mean 3 has 3.8 g β- sitosterol 3.8 g dicetyl phosphate 0.4 g methyl p-hydroxybenzoate 0.3 g demineralized water 60.5 g

2nd stage

Add to the resulting bead dispersion following connections to:

Perfume 0.4 g Glycerin tricapro caprylate 10.0 g Mixture of carboxyvinyl acids 0.4 g Triethanolamine 0.4 g demineralized water 20.0 g  

Example 10 Facial care cream 1st stage

As indicated above, an aqueous dispersion of lipid beads is made from the following compounds:
non-ionic, amphiphilic lipid of the general formula

where R is a hexadecyl radical and
n a statistical mean 3 has 3.8 g b- sitosterol 3.8 g dicetyl phosphate 0.4 g preservative 0.3 g demineralized water 47.6 g

2nd stage

The dispersion obtained from the first stage is added Beads the following connections to:

Sunflower oil 35.0 g Perfume 0.6 g Mixture of vinyl carboxylic acids 0.2 g Triethanolamine 0.2 g demineralized water 8.1 g

Claims (13)

1. Cosmetic composition, consisting of an aqueous dispersion of beads, composed of ordered molecular layers, between which an inner aqueous phase is enclosed, and wherein these layers consist of at least one non-ionic, amphiphilic lipid, characterized in that at least one oil is dispersed in the aqueous, external phase surrounding the beads, which is selected from esters of fatty acids and polyols, especially liquid triglycerides, and esters of fatty acids and branched alcohols of the formula: R-COOR'worinR for the rest of a higher fatty acid with Is 8 to 20 carbon atoms and R'is a branched hydrocarbon chain with 3 to 20 carbon atoms. 2. Composition according to claim 1, characterized in that the esters are selected from fatty acids and polyols are among sunflower, corn, soybean, pumpkin, Grape seed, jojoba oils and glycerin tri-caprocaprylate. 3. Means according to claim 1, characterized in that one as an ester of higher fatty acids and branched Alcohols used purcellin oil. 4. Agent according to one of claims 1 to 3, characterized characterized that it is 2 to 10 wt .-% non-ionic (s) amphiphilic (s) lipid (s) that cover the walls of the Beads and 2 to 40% by weight of dispersed Oil (s), based on the total weight of the agent, contains, the weight ratio of non-ionic, amphiphilic lipid (s) to the dispersed oil (s) is approximately between 0.2 / 1 and 1/1. 5. Agent according to one of claims 1 to 4, characterized in that the external phase 0.1 to 2 wt .-% contains gel-forming agent (s), based on the total weight of the agent. 6. Composition according to claim 5, characterized in that the gel-forming agent is selected from cellulose derivatives, synthetic polymers, derivatives of algae or natural rubber.   7. Composition according to one of claims 1 to 6, characterized in that that the external phase is at least one Perfume and / or one or more lipid-soluble contains cosmetic ingredients. 8. Composition according to claim 7, characterized in that the lipid-soluble cosmetic ingredients, one Sun filter, a substance that makes the condition drier or to improve aging skin, or an antioxidant represent. 9. Composition according to one of claims 1 to 8, characterized in that the non-ionic, amphiphilic lipids which represent the walls of the beads,

• Esters of straight-chain or branched polyglycerols,
• Ether of straight-chain or branched polyglycerols of the formulas: wherein n represents a number between 2 and 6 and represents straight or branched, saturated aliphatic chain with 16 to 20 carbon atoms or the hydrocarbon radical of a lanolin alcohol; or
• - polyoxyethylene sterols

are.   10. Composition according to claim 9, characterized in that auxiliaries are added to the nonionic amphiphilic lipids, selected from alcohols and long-chain diols, sterols, in particular cholesterol and β- sitosterol, long-chain amines and their quaternary ammonium derivatives, hydroxyalkylamines, polyoxyethylene fatty amines , Esters of long-chain amino alcohols and their salts and their quaternary ammonium derivatives, polymers, phosphoric acid esters of fatty alcohols, especially dicetyl phosphate. 11. Agent according to one of claims 1 to 10, characterized characterized in that the inner aqueous phase or the external phase is at least one water-soluble cosmetic compound included. 12. Composition according to claim 11, characterized in that the water-soluble compound is selected from humectants such as glycerol, sorbitol, pentaerythritol, inositol, pyrrolidone carboxylic acid and their salts; artificial tanning agents such as dihydroxyacetone, erythrulose, glyceraldehyde, γ- dialdehydes such as tartaric acid aldehyde; Colorants for the skin; Sun filters; Antiperspirants, deodorants, astringents, refreshing, toning, healing, keratolytic, depilatory agents; perfumed water, animal or vegetable extracts such as proteins, polysaccharides, amniotic fluid and antiseborrhea agents.