DE3125710A1 - "COSMETIC AGENTS" - Google Patents

Description

PATENT AGENCIES'J'E
J. RBITSTÖTTER W. KINZEBACH

PROF. DR. DR. DIPL. ING. DR. PHIL. DIPL. CHBM.

W. BUNTE (ΐ958-ΐ97β) K. P. HÖLLER

DR. ING. DR. RER. NAT. DIPL. OHEM.

TBLEFONi (08B) 37 0BB3 TELEXl 52IB208 ISAR D

BAUERSTRASSB 22, 8000 MUNICH

Munich, the 3Q. June 1980 M / 22 160

L ¹ OREAL
14, rue Royale

F-75008 Paris (France)

Cosmetic means

POSTAL ADDRESS ι POSTFACH 780, D -8000 MUNICH 43

M / 22 160

The present invention relates to a cosmetic agent consisting of a dispersion of lipid spheres. Aqueous dispersions of this type have already been described in FR-PS 2,315,991.

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

The aforementioned French patent also describes a process for the preparation of an aqueous dispersion of Lipid spheres, in which in a first stage the lipids, which are the concentric layers of the spheres should form, with the aqueous, encapsulated solution in contact, the ratio of lipophilic / hydrophilic Lipids is selected so that the latter swell in water or in the aqueous phase to be encapsulated and form a flat lamellar phase; in a second stage, an aqueous solution is added to the lamellar phase, which to form the external continuous phase of the dispersion, and thirdly, the whole is then vigorously stirred, whereby

Μ / 22 160

a dispersion of spheres is obtained, between them concentric Layers ^ ie the aqueous phase to be encapsulated is included.

To form the concentric layers of the spheres, one can use the teaching of this French patent specification use both amphiphilic, or ionic or non-ionic lipids. Of the non-ionic amphiphilic lipids one prefers:

- the straight-chain or branched polyglycerol ethers of the following formulas:

R (-OCH ₀ -CHOH-CH ₀ -) OH

2 2 η

and

R- (-O-CH-CHI OH

CH-OH

wherein

η is an integer from 1 to 6,

R is a straight or branched, saturated or unsaturated aliphatic chain with 12 to 30 carbon atoms is, hydrocarbon radicals of lanolin alcohols or 2-hydroxy-alkyl radicals of long-chain α-diols;

- the polyoxyethylene fatty alcohols;

- the esters of polyols, which may be oxyethylene are, and especially the polyoxyethylene sorbitol esters;

the glycolipids of natural or synthetic origin, for example the cerebrosides.

^ ILLi - ^: -> · - ·: ■ ·: ··: 3ΐ25

Μ / 22 160

The French patent is one of the cosmetic active ingredients that can be encapsulated in the lipid spheres for example on: substances that are intended to care for the surface of the skin, such as moisturizing agents, artificial tanning agents, dyes for the skin, water-soluble sun filters, antiperspirants, deodorants, Astringents, refreshing, toning, healing, keratolytic, depilatory products, perfumed waters and extracts of animal or vegetable tissues.

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

The present invention describes a cosmetic

Agent based on an aqueous dispersion of lipid; globules, with which one can take advantage of the ! Dispersion of beads can combine with the advantages that 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, these layers consisting of at least one non-ionic, amphiphilic lipid. The invention is characterized by at least one oil dispersed in the aqueous external phase surrounding the beads.

_ .. ... -.> ^: .Λ r .. "., Ir.Wj ;. 1 312571

Μ / 22 160 -

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

R-COOR '

R stands for the residue of a higher fatty acid having 8 to 20 carbon atoms

and
R 'is a branched hydrocarbon chain with 3 to 2 carbon atoms

represents.

It has now surprisingly been found that the nonionic amphiphilic beads can be used to stabilize the oil-in-water dispersion without a conventional emulsifying agent having to be added or the beads being destroyed. It is known, however, that the stability of an emulsion depends essentially on the presence of an emulsifying agent, the molecules of which are absorbed on the surface of the oil droplets and form a kind of uninterrupted membrane which prevents direct contact between two adjacent droplets, for example in the event of a shock . In the present case, the skilled person could therefore be assumed that the non-ionic amphphilen lipids of the beads could play the role of an emulsifying agent and could be absorbed at the surface of the oil droplets _t wobeidiese stabilization but would also cause the concentric layers of the beads would be destroyed . However, this is not the case and it is surprisingly found that the nonionic amphiphilic beads according to the present invention are a dispersion of at least one vegetable oil as defined above _;

M / 22 160

can stabilize in an external aqueous phase by dispersing around the oil droplets and 'thus their Maintain shape.

U.S. Patent 3,957,971 discloses dispersions of beads Ionic amphiphiles or liposomes described, which are included in cosmetic lotions or creams, i.e. water-in-oil or oil-in-water emulsions. According to According to the present invention, the beads are not composed of ionic amphiphiles but of non-ionic ones Amphiphiles. In addition, it has been found that the liposomes are not used to disperse any of the abovementioned Vegetable oils can stabilize in water, while completely surprisingly the spheres of non-ionic amphiphiles can stabilize such a dispersion according to the present invention.

The production of the cosmetic agent according to the invention therefore takes place in two stages: In a first stage, an aqueous one is made from non-ionic amphiphilic lipids Dispersion of spheres, as described in FR-PS 2 315 991 or in FR-PS 2 221 122 is working. In a second stage, when the aqueous dispersion of the beads is prepared, in particular an oil is added, which is then dispersed in the external, aqueous phase by stirring.

The cosmetic agent 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 (s) oil (s), based on the total weight of the agent. The weight ratio of the nonionic amphiphilic lipids to the (or the) dispersed ones is advantageously oil (s) between 0.2 / 1 and 1/1.

Μ / 22 160 -

4f

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

R - COO-R ¹ ,
wherein

R for the best of a higher fatty acid with 8 to 20 carbon atoms stands

R 'is a branched hydrocarbon chain with 3 to 20 Represents carbon atoms.

The esters of fatty acids and polyols include in particular Sunflower, corn, soy, pumpkin, grape seed, jojoba oils and glycerine tri-capro-caprylate. Higher to the esters Purcellin oil is one of the fatty acids and branched alcohols.

The cosmetically active ingredients of the invention Means can be encapsulated inside or outside of the spheres be. According to a preferred embodiment contains the oil phase of the agent is one or more lipid-soluble cosmetic substances. In the preparation of the agent according to the invention, the latter are previously dissolved in the oil, which to add to the lipid bead dispersion. The lipid-soluble cosmetic active ingredients include in particular solar filters, such as 2-ethyl-hexyl-p-dimethylaminobenzoate or compounds intended to improve the condition of dry or aging skin, especially unsaponifiable ones as well as saponifiable components of soy, avocado, tocopherols, vitamins E, F, and antioxidants.

The oil-in-water dispersion, which vojn the external environment of the dispersion Is beads, can contain at least one additive, in particular a gel-forming agent or a perfume. The addition is added to the dispersion together with the oil.

M / 22 160

IZ

Dasgelbildede ¹ · agent may be obtained at concentrations of 0.1 to 2 wt .-% _f based on the total weight of the agent used. The gelling agents which can be used include the cellulose derivatives, such as hydroxyethyl cellulose; synthetic polymers; Derivatives of algae, such as satiagum, or natural gums, such as tragacanth. The gelling agent used is preferably hydroxyethyl cellulose, a mixture of carboxyvinyl acids which is commercially available under the name "CARBOPOL 940", satiagum or tragacanth.

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

- Ethers or esters of straight-chain or branched polyglycerols of the formulas:

R.

respectively.
R.

och "choh-ch

OCH ₉ - CH

wherein

η stands for an integer between 2 and 6

and
R represents a straight or branched, saturated aliphatic chain having 16 to 20 carbon atoms or the hydrocarbon radical of a lanolin alcohol;

- polyoxyethylene sterols.

M / 22 160 - Uf -

At. the formation of the flat lamellar phase that is obtained, when the non-ionic, amphiphilic lipids are brought into contact with the aqueous phase to be encapsulated various auxiliaries are added to the lipids, for example the permeability or the surface charge of the beads to vary. Here you can optionally alcohols and diols with a long chain, sterols, in particular Cholesterol and ß-sitosterol, long-chain amines and their quaternary ammonium derivatives, in particular didodecyl-dimethylammonium bromide, Hydroxyalkylamines, polyoxyethylene fatty amines, esters of long-chain amino alcohols. their salts and quaternary ammonium derivatives, phosphoric acid esters of fatty alcohols, in particular dicetyl phosphate, Certain alkyl sulfates, for example sodium cetyl sulfate Add polymers such as polypeptides and proteins.

In addition to the auxiliaries listed above, a preservative such as methyl p-hydroxybenzoate can also be added.

The aqueous phase, be it internal or external, can be a Contain water-soluble cosmetic agent, usually for the care of the face, hands or body is used. These substances include moisturizing agents such as glycerine, sorbitol, pentaerythritol, inositol, Pyrrolidonecarboxylic acid and its salts; artificial tanning agents such as dihydroxyacetone, erythrulose, glyceraldehyde, γ-dialdehydes such as tartaric aldehyde; Colorants for the skin; Sun filters, antiperspirants, deodorants, astringents, refreshing, toning, healing, keratolytic products, perfumed waters, animal or vegetable extracts Tissues such as proteins, amniotic fluid, polysaccharides, and antiseborrhea agents.

Μ / 22 160

■ «■

In order to describe the invention in more detail, some embodiments are given below, purely by way of illustration.

The cosmetic agents described in the examples below are produced in two stages. In a first stage, an aqueous dispersion is prepared using the process described in French Pat. No. 2,315,991. The watery one Dispersion of lipid spheres is made from:

- a non-ionic, amphiphilic lipid,

- sterols such as cholesterol or ß-sitosterol; optionally dicetyl phosphate;

- optionally water-soluble cosmetic ingredients and

demineralized water, which may contain a preservative.

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

M / 22 160

example 1

Comparative tests between an inventive cosmetic agent and a known agent

Two remedies (A) and (B) are produced, which are essentially the same, with the difference that the remedy (B) no oil added in the second phase.

The agent (A) contains the following components:

1st stage

non-ionic, amphiphilic lipid of the formula:

OCH ₂ -

OH

CH ₂ OH

where R stands for a hexadecyl radical and η has a statistical mean of 3 3.8g

ß-sitosterol 3.8 g

Dicetyl phosphate 0.4g

Methyl p-hydroxybenzoate 0.3 g

demineralized water 66.7 g

2nd stage

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

Cosmetic agent (B) is produced in the same way, but without adding sunflower oil in a second phase, but rather the 25 g of oil with an equal amount Replaces demineralized water.

M / 22 160

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

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

The coefficient of friction of the skin is increased when spreading of the cosmetic products (A) and (B) on the forearm of a test person with a rotating button measured; this is done by measuring the resistance of the button as it rotates. The push button is with a constant Force (20 or 50 g) pressed on.

The following results are obtained:

Correction of the coefficient of friction of the skin, measured for 15 minutes after application

with a force of 20 g

with a force of 50 g

Medium (B)

+ 209

+ 245

Agent (A) according to the invention containing 25% sunflower oil

- 40

- 60

It is found that the agent (B), i.e. the aqueous dispersion of lipid spheres which does not contain oil, significantly increases the coefficient of friction of the skin, while the agent (A) according to the invention, i.e. a Dispersion of beads, which contains an oil, has the opposite effect. This significant lowering of the In cosmetics, the coefficient of friction of the skin means that the skin with the agent (A) according to the invention does a lot

M / 22 160

2) Measurement of the modulus of elasticity of the human stratum corneum, carried out in vitro before and after application of the cosmetic agents A and B described above

These measurements are made with a laboratory device designed to measure the elasticity of the skin is. Such a device is described in FR-PS 78.25149.

The experimental conditions are as follows:

relative humidity: 72% _ + 2

Temperature: 30 ⁰ C + 0.2

Amount of product applied: 5 mg / cm * The following results are obtained:

Products tested% mean reduction in the modulus of elasticity

1 hour 30 minutes 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 one has a dispersion of beads without an oil phase or with an oil phase.

M / 22 160

Example 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:

R {. OCH ₂ - CH

OH

CH ₂ OH

wherein

R stands for a hexadecyl radical and η a mean statistical value of 3 represents

ß-sitosterol dicetyl phosphate methyl p-hydroxybenzoate Pyrrolidoncarboxylic acid sodium salt demineralized water

2nd stage

The dispersion obtained after the 1st stage is added of spheres the following connections to:

4.5 G 4.5 G 1.9 G 0.3 G 2.0 G 56.5 G

Perfume sunflower oil

Mixture of vinyl carboxylic acids sold under the trade name "CARBOPOL 940"

Triethanolamine demineralized water

0, 4th G 10, 0 G 0, 4th G 0, 4th G 20, 0 G

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Μ / 22 160 -

Example 3

Nourishing fluid for the face

1st stage

An aqueous dispersion is prepared as described above of lipid globules from the following substances:

non-ionic amphiphilic lipid of the general formula:

R - (- 0CH ₀ -CH-) OH

2, η

CH ₂ OH

where R stands for a hexadecyl radical and η is 2
cholesterol
Dicety! Phosphate
Methyl p-hydroxybenzoate demineralized water

2nd stage

The following compounds are added to the dispersion of beads obtained from the 1st stage:

Perfume grapeseed oil

■ Mixture of vinyl carboxylic acids. ^under the trade name "CARBOPOL 940"

Tria thano1amiη ■ demineralized water

6.0 G 1.6 G 0.4 G • 0.3 G 61.1 G

0.2 G 20.0 G 0.2 G 0.2 G 10.0 G

M / 22 160

- ΨΓ-

Example 4

Caring fluid for the hands

1st stage

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

polyoxyethylene phytosterols (statistical
Distribution of the mean equal to 5) 6.0 g

Cholesterol 2.0 g

Methyl p-hydroxybenzoate 0.3 g

demineralized water 45.7 g

2nd stage

The following substances are added to the dispersion of beads obtained from the first stage:

Perfume jojoba oil

Mixture of vinyl carboxylic acids, among which
Trade name ¹¹ CARBOPOL 940 "

Triethanolamine ■ demineralized water

0 , 2 G 25th ,O· G 0 , 4 G 0 , 4 G

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:

OCH "-CH

£ · ι

OH

CH ₀ OH

M / 22 160

- ψ-

wherein R stands for a hexadecyl radical and

η has a mean statistical value of 3 4.0 g

Cholesterol 4.0 g

Methyl p-hydroxybenzoate 0.3 g

demineralized water 4 5.5 g

2nd stage

The following compounds are added to the dispersion of beads obtained in the first stage:

Perfume corn oil

Mixture of vinyl carboxylic acids, among which Marketed under the trade name "CARBOPOL 940"

Triethanolamine ^L demineralized water

0.4 G 25.0 G 0.4 G 0.4 G 20.0 G

Example 6

Facial care fluid

1st stage

An aqueous dispersion is prepared as described above of lipid spheres from the following compounds:

non-ionic amphiphilic lipid of the general formula

OH

CH ₂ OH

where R stands for a hexadecyl radical and η has a statistical mean of 3

ß-sitosterol dicetyl phosphate methyl p-hydroxybenzoate demineralized water

0.95 g

0.95 g

0.10 g

0.30 g

64.80 g

■ '* · —fr ■

M / 22 160

0.4 G 10.0 G 2.0 G 0.5 G 20.0 G

2nd stage

To the dispersion of the beads obtained in the first phase one admits the following means:

Perfume
Soybean oil
ρnon-saponifiable soy components

Hydroxyethyl cellulose sold under the trade name "Natrosol 250 HHR"

- demineralized water

Example 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

OCH ₀ -CH

-OH

CH ₂ OH

where R stands for a hexadecyl radical and η has a statistical mean of 3

ß-sitoserine didodecyl-dimethyl-ammonium-bromide Methyl p-hydroxybenzoate demineralized water

3.6 g

3.6 g

0.8 g

0.3 g

45.9 g

M / 22 160

2nd stage

23

The following substances are added to the dispersion of beads obtained from the first stage:

Perfume Pumpkin Oil ■ 2-ethylhexyl-p-dimethylamino-benzoate Tragacanth gum demineralized water

0.4 g

22.0 g

3.0 g

0.4 g

20.0 g

example

Care fluid for the hands

1st stage

As indicated above, an aqueous dispersion of lipid beads is prepared from the following compounds:

non-ionic, amphiphilic lipid of the general formula

OCH

OH

CH ₂ OH

where R stands for a hexadecyl radical and η has a statistical mean of 3 ß-sitosterol dicetyl phosphate methyl p-hydroxybenzoate Glycerin demineralized water

3.8 G 3.8 G 0.4 G 0.3 G 3.0 G 42.5 G

M / 22 160

.2. step

The following compounds are added to the dispersion of spheres obtained from the first stage:

Perfume purcellin oil Satiagum demineralized water

0.2 g

25.0 g

1.0 g

20.0 g

Example 9 Personal Care Fluid

1st stage

As indicated above, an aqueous dispersion of lipid beads is prepared from the following compounds:

non-ionic amphiphilic lipid of the general formula

CH ₂ OH

where R stands for a hexadecyl radical and η has a statistical mean value of 3

ß-sitosterol dicetyl phosphate methyl p-hydroxybenzoate demineralized water

2nd stage

3.8
3.8
0.4
0.3
60.5

g g g g g

The following compounds are added to the resulting dispersion of beads:

Perfume 0.4

Glycerine tricapro caprylate 10.0

rMixture of carboxyvinyl acids, under the

g g

Marketed under the trade name "CARBOPOL 940"

Triethanolamine ^L demineralized water

0.4 g

0.4 g
20.0 g

3T25710

M / 22 160

Example 10

Cream for facial care 1st stage

As indicated above, an aqueous dispersion of lipid beads is prepared from the following compounds:

non-ionic, amphiphilic lipid of the general formula

- CH

CH ^ OH

OH

where R stands for a hexadecyl radical and η has a statistical mean value of 3

ß-sitosterol Dicety! phosphate preservative demineralized water

3,
3,

0.4

0.3

47.6

g g g g g

step

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

Sunflower oil perfume

Mixture of vinyl carboxylic acids, among which Marketed under the trade name "CARBOPOL 940"

Triethanolamine demineralized water

35.0 G 0.6 G 0.2 G 0.2 G 8.1 G

Hh

Claims (12)

M / 22 160 claims 1. Cosmetic agent, consisting of an aqueous dispersion of beads, built up ^of ordered molecular layers, between which an inner aqueous phase is enclosed, and these layers consist of .at least one non-ionic, amphiphilic lipid, characterized in that at least one oil in the aqueous, external phase surrounding the beads, is dispersed, which is selected from esters of fatty acids and polyols, especially liquid Triglycerides, and esters of fatty acids and ver. branched alcohols of the formula: R-COOR ' wherein R stands for the residue of a higher fatty acid having 8 to 20 carbon atoms and
R ^{1 is} a branched hydrocarbon chain with 3 to Carbon atoms
represents. M / 22 160 2. Composition according to claim 1, characterized in that the esters of the fatty acids and the polyols are selected are among sunflower, corn, soy, pumpkin, grape seed, jojoba oils and glycerine tri-caprocar > rylat. 3. Composition according to claim 1, characterized in that one is used as an ester of higher fatty acids and branched Alcohols used purcellin oil. 4. Agent according to one of claims 1 to 3, characterized in that it contains 2 to 10% by weight, non-ionic (s) amphiphilic lipid (s) that form the walls of the beads and 2 to 40% by weight of dispersed (s) Oil (s), based on the total weight of the agent, 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 that the external phase contains 0.1 to 2 wt .-% gelling agent (s), based on the total weight of the means. 6. Means according to claim 5, characterized in that the gel-forming agent is selected from cellulose derivatives, synthetic polymers and algae derivatives or natural rubbers. ._.: _: .. -__ _ ^ :: L:. · I.iiiwi - ■! ■ - - ■ ■ 312571 Μ / 22 160 - 3 - 7. Agent 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, a Sun filter, a substance believed to improve the condition of dry or old skin, or an antioxidant represent" 9. Agent according to one of claims 1 to 8, characterized in that the non-ionic, amphiphilic Lipids, which are the walls of the beads - ethers or esters of straight-chain or branched polyglycerols of the formulas: R - (OCH ₀ CHOHCH ₀ -) OH or R (OCH ₀ -CH) OH 2. ι η CH ₂ OH wherein η means a number between 2 and 6, and
R is a straight or branched, saturated aliphatic © chain with 16 to 20 carbon atoms, or the hydrocarbon radical of a lanolin cabbage; or - are polyoxyethylene sterols. M / 22 160 -A- 10. Means according to claim 9, characterized in that auxiliaries are added to the non-ionic amphiphilic lipids, selected from alcohols and Long chain diols, sterols, especially cholesterol and ß-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. Composition according to one of claims 1 to 10, characterized in that the inner aqueous phase or the external phase contain at least one water-soluble cosmetic compound. 12. Composition according to claim 11, characterized in that the water-soluble compound is selected from Moisturizing agents such as glycerine, sorbitol, pentaerythritol, inositol, pyrrolidone carboxylic acid and their Salt; artificial tanning agents such as dihydroxyacetone, erythrulose, glyceraldehyde, γ-dialdehydes, such as tartaric aldehyde; Colorants for the skin; Solar filters; Antiperspirants, deodorants, astringents, refreshing, toning, healing, keratolytic, depilatory agents; perfumed Water, animal or plant extracts such as proteins, polysaccharides, amniotic fluid and Antiseborrhea agents.