FR2568142A1 - - Google Patents

Abstract

THE INVENTION RELATES TO AN EMULSIONING SYSTEM FOR EMULSIONS OF THE WATER-IN-OIL TYPE. THIS EMULSIONING SYSTEM CONSISTS OF AN ALKALINE-EARTH OR METAL LANOLATE AND A STEROL, SITE LANOLATE BEING OBTAINED BY DIRECT ACTION OF LANOLIC ACID AND OF AN ALKALINE-EARTH OR METAL ACETATE, IN ANHYDROUS MEDIUM. USE FOR THE PREPARATION OF COSMETIC AND PHARMACEUTICAL EMULSIONS.

Description

The present invention relates to a novel emulsifying system

  presenting in the form of a mixture of an alkaline earth or metal lanolate and a sterol and the use of this emulsifying system for producing water-in-oil type emulsions for the cosmetic industry or pharmaceutical. In French Patent No. 72.10843, it has already been proposed

  to use as an emulsifying system for emulsions of the type "eaudans-

  the oil ", a mixture consisting of a lanolate taken from the group consisting of lanolates of magnesium, calcium, lithium, zinc and aluminum and

  hydrogenated lanolin and / or lanolin alcohol.

  According to this patent, the emulsions obtained are described as more economical because, among others, richer in water and having a good storage stability at temperatures far removed from ambient temperature. From a cosmetic point of view, these emulsions do not, however, exhibit all the desirable properties generally sought for creams.

  intended for application on the face. These emulsions of the water-in-water type

  oil are lacking flexibility and have a certain tendency to bleach

skin to the application.

  Furthermore, the use of hydrogenated lanolin and / or lanolin alcohol raises certain difficulties because of not only the price of these raw materials but also the fluctuations in their quality due to peroxidation leading to the formation of odors and color changes. In order to provide more flexibility and to overcome the disadvantages of the emulsions of the French patent 72.10843, various co-emulsifiers of

  lanolates were tested, including sterols such as cholesterol.

  Although the emulsions obtained were more flexible and more pleasant to use, they nevertheless proved to be worse.

  stability than those of French Patent No. 72.10843.

  After having pursued numerous studies on this emulsion-

  consisting of a lanolate and a sterol, it was found that the problem of the stability of the emulsions was not related to the nature of the co-emulsifier, ie the sterol, but to the lanolate itself according to the synthesis process

employee.

  In the French patent no. 72.10843, the lanolates are prepared by the following two methods: 1 - either by double decomposition, which method consists firstly of producing the sodium or potassium salt of lanolic acid at a dilution such that it is in isotropic solution and then to precipitate

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  this solution the salt of the desired lanolic acid, by the addition of a solution of a mineral salt for example a chloride, 2 - or by direct action of an alkaline hydroxide, alkaline-earthy

  or metallic on lanolic acid.

  These two processes have in common the fact that they are carried out in an aqueous medium and that therefore results in the presence of certain basic soaps

  undesirable problems.

  The presence of these basic soaps being likely to affect the stability of the emulsions when the lanolate is combined with a sterol, other processes for the preparation of lanolates have been tried, in particular the process of reacting the lanolic acid with an acetate directly. alkaline earth or metal and to be removed by heating under vacuum the acid

acetic formed.

  It was then quite surprising that the lanolates prepared by this latter method, combined with a sterol such as cholesterol, resulted in very stable water-in-oil emulsions.

  having good spreading properties.

  Moreover, the lanolates obtained by this process have a better solubility in the fatty phase of the emulsions because of the absence

total of basic soaps.

  The subject of the present invention is therefore, as a product

  new industrial system, an emulsifying system for emulsions of the "water-based" type.

  the oil "consisting of an alkaline earth or metal lanolate and a sterol, said lanolate being obtained by direct action of the acid

  lanolin and an alkaline-earth or metal acetate, in anhydrous medium.

  According to the invention, the alkaline earth and metal lanolates are preferably lanolates of calcium, magnesium, zinc, copper

or aluminum.

  Alkaline earth lanolates, especially magnesium lanolate,

  make it possible to obtain excellent emulsions of the water-loving type.

  oil of great stability and easy application due to the good

spreading properties.

  As mentioned above, the process for obtaining the

  lanolates, for use in combination with a sterol as co-

  emulsifier, is of paramount importance.

  This process, simple in its implementation, consists in reacting directly, in anhydrous medium, the lanolic acid and an alkaline earth metal or metal acetate and to be removed, by heating under vacuum, the acid

  shaped acetic, thus making it possible to move the balance as much as possible.

  The reaction is generally carried out under nitrogen at a temperature of between 80 and 150 ° C. for a time sufficient to eliminate, to a maximum, by vacuum distillation, the acetic acid formed during the reaction. The yield of the reaction is generally between 90 and 99% relative to the starting lanolic acid. If desired, the lanolates obtained can be further purified by adding, to the mixture, an aromatic solvent such as toluene which allows, by azeotropic entrainment, at a temperature of between 140 ° C. and 140 ° C., to eliminate traces of acid. possibly acetic

remaining.

  According to a variant of this process, the reaction between the lanolic acid and the alkaline-earth or metal acetate may be carried out and terminated in the presence of a high-boiling oil, cosmetically

  or pharmaceutically acceptable such as for example vaseline oil.

  Thus, at the end of the reaction, the lanolates in solution in an oil which can constitute a part of the fatty phase of emulsions of the water-in-oil type are obtained. Among the sterols that can be used as co-emulsifiers of the new emulsifying system according to the invention, mention may be made especially of

cholesterol, and e-sitosterol.

  In the emulsifying system according to the invention, the weight ratio of lanolate / sterol weight is between about 95/5 and 40/60 the ratio

  preferential being about 90/10.

  According to one variant of the invention, the alkaline earth or metal lanolate may be associated with at least one alkaline earth or metal salt of another fatty acid such as, for example, a stearate or oleate of calcium, magnesium or zinc. of copper or aluminum, the proportion of the alkaline earth metal salt of this other fatty acid generally not being

  not more than 25% by weight relative to the weight of the alkaline lanolate

earthy or metallic.

  According to this variant, the mixture of the alkaline earth or metal lanolate and the alkaline earth metal salt of another fatty acid is obtained using the process as described above but starting from an acid mixture. lanolica and the other fatty acid that we want to associate

in the chosen proportion.

  The subject of the present invention is also flexible emulsions of the water-in-oil type comprising a water phase, a fatty phase and a

  emulsifying system as defined above.

  These emulsions, which may constitute cosmetic or pharmaceutical vehicles, have a viscosity of between 80 and 85 poises.

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  to say weaker than those of the emulsions of French Patent No. 72 10843

  which are of the order of 100 to 110 poises.

  In these emulsions, the concentration of emulsifying system according to the invention is generally between 3 and 20% and preferably between 5 and 12% relative to the total weight of the emulsion. The weight ratio of the fatty phase to the emulsifier is included

  between 95/5 and 50/50 but preferably this ratio is about 90/10.

  Fatty products constituting the fatty phase of the emulsions include: hydrocarbon-based oils such as paraffin oil, purcellin oil, perhydrosqualene and microcrystalline wax solutions in oils; animal or vegetable oils such as sweet almond oil, avocado oil, calophylum oil, lanolin, castor oil, horse oil, pore oil, sesame oil, lemon olive oil, jojoba oil, shea oil, hoplostethus oil, mineral oils whose initial point of distillation at atmospheric pressure is about 250 C and the end point of the order of

410 C,

  saturated or unsaturated esters such as alkyl myristates, such as isopropyl, butyl or cetyl, hexadecyl stearate, ethyl or isopropyl palmitates, octanoic acid triglycerides;

  and decanoics and cetyl ricinoleate.

  The fatty phase may also contain silicone oils soluble in other oils, such as dimethylpolysiloxane, methyl

  phenyl polysiloxane and the silicone-glycol copolymer.

  In order to promote the retention of oils, it is also possible to use waxes such as carnauba wax, candelilla wax,

  beeswax, microcrystalline wax and ozokerite.

  When the emulsions are intended for cosmetic use, those

  They can be in the form of moisturizing sunscreens or moisturizing creams for the face, body or hands as well as in the form of moisturizing blushes or foundations. In this case, the concentration of the water phase of the emulsion is generally between 20 and 70% but preferably between 40 and 60% by weight relative to the total weight of the emulsion. These compositions can also be in the form of moisturizing solar sticks or moisturizing sticks for the face, the body, as well as in the form of sticks for lips or eye makeup. In this case, the concentration of the water phase in the emulsion is generally

  between 5 and 70% by weight relative to the total weight of the emulsion.

  The cosmetic compositions may contain all the ingredients generally used in cosmetics and in particular dyes, pigments, sunscreens, perfumes, preservatives such as methyl para-hydroxybenzoate or propyl para-hydroxybenzoate and coemulsifiers such as for example the product sold by the Company

  Goldschmidt under the name of "PROTEGIN W."

  These compositions may further contain certain active ingredients not only for the maintenance of the skin but also to improve its properties.

  properties including its elasticity.

  Among these substances, mention may in particular be made of humectants such as thiamorpholinone and its derivatives, vitamins, revitalizing agents, protein derivatives such as elastin and collagen, etc. The emulsions according to the invention may also constitute a vehicle for certain therapeutic active ingredients, the compositions are

presenting in the form of creams.

  Among the preferred active substances for this type of vehicle, mention may in particular be made of:

  - Anti-inflammatories, especially corticosteroids such as hydro-

  cortisone, difluprednate, beta-methasone or dexamethasone, - antibiotics such as erythromycin, clindamycin or neomycin. Keratolytics such as retinoic acid or benzoyl peroxide, antipsoriatic agents such as anthralin and its derivatives and etretinate; vitamins and derivatives such as vitamin A palmitate, biotin or d-panthenol; antifungal agents such as imidazole derivatives or tolnaftate, and, - sex hormones, natural or synthetic, such as progesterone

or testosterone.

  The method for preparing the water-in-oil emulsions consists, in a first stage, in dissolving the lanolate in the fatty phase at a temperature of approximately 100 ° C. and with vigorous stirring, and in a second stage, in adding the sterol. at a temperature of approximately 80 ° C., after which the mixture is cooled to a temperature of approximately 40 ° C. and the water phase, previously heated to the same temperature, is introduced with vigorous stirring and the emulsion is then cooled at room temperature while stirring. If you wish,

  the emulsion can be refined by passing it through a roll mill.

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  This process as just described above makes it possible to obtain creams more particularly. To obtain the sticks, the water is preheated to 80 ° C. and added to the uncooled mixture, and the emulsion obtained is then cast at this temperature into molds suitable for forming sticks. In order to better understand the invention, will now be given, by way of illustration, various examples of alkaline earth and metal lanolate preparation as well as several examples of emulsions of the type "water-in-oil" for cosmetic use or

pharmaceutical.

PREPARATION OF LANOLATES

  Preparation of zinc lanolate In a suitable container provided with a device for the vacuum removal of acetic acid by distillation and

  With the addition of nitrogen, 221.7 g of lanolic acid (0.5 mol) are placed.

  The vessel is heated to a temperature of 80 ° C. until the lanolic acid is melted, then 53.77 g of sodium acetate are added in one go.

zinc, 2H 2 O (0.245 moles).

  The mixture is then brought to 120.degree.-12.degree. C. in order to eliminate by distillation

  water, and acetic acid formed. The vacuum is then progressively applied to the apparatus (1.99 K Pa) and the temperature is gradually raised.

up to 137 C.

  After 35 minutes, a first distillate of acetic acid is obtained and

  water (37 g) then a second distillate (1.66 g) after 40 minutes at a

  about 130-135 ° C. under 1.99 K Pa.

  100 g of toluene are then added and the remaining traces of acetic acid are then azeotropically entrained under pressure.

  atmospheric and at a temperature of 120 to 130 C.

  This last treatment makes it possible to eliminate acetic acid at a rate

  97.6% compared to the theory.

  Zinc lanolate (233.6 g) is obtained with a yield of 98% and has a total acidity of 2.075 meq / g

(theory: 2.11 meq / g).

  Preparation of Copper Lanolate In a suitable container provided with a device for the vacuum removal of acetic acid by distillation and a nitrogen inlet, 221.7 g of lanolic acid (0.5 mole) to 90 C under

nitrogen until complete melting.

  50 g (0.245 mole) of copper acetate monohydrate are then added and the mixture is stirred at a temperature of between 117.degree.

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  and 125 ° C. After slowing down the distillation, the equipment is evacuated and the temperature is gradually increased to 135 ° C.

1.99 K Pa.

  This gives a first distillate (33.7 g) of acetic acid and water and then a second distillate (1.15 g) after one hour under 1.99 K Pa at C. A subsequent purification was not proved necessary, the copper lanolate obtained no longer showing traces of residual acetic acid. 252 g of copper lanolate are thus obtained with a yield of

100%.

  Preparation of magnesium lanolate 2444.2 g of lanolic acid (5.5 moles) are introduced into a 6-liter three-necked flask equipped with a vacuum distillation device and a nitrogen inlet. at about 90 ° C under nitrogen. After melting of the lanolic acid, 578.2 g of magnesium acetate 4 H 2 O (2.7 moles) are then added all at once, and the heating is continued to approximately 108 ° C. At this temperature, acetic acid and water of hydration of magnesium acetate begin to distill. The temperature of the reaction mixture is then brought

  gradually at 130 C while distilling the acetic acid formed.

  The temperature is maintained at 130 ° C. for about 2 hours and then, when the distillation is reduced, the apparatus is placed under vacuum in order to

  promote the elimination of the remaining acetic acid.

  After 1 hour at 130-135 ° C. under 1.99 K Pa, a first distillate (461 g) is obtained. 2505 g of vaseline oil are then added and the heating is continued at 130 ° -135 ° C. under vacuum (6.65 Pa) for 1 hour and a

second distillate (47 g).

  Magnesium lanolate in 50% solution in petrolatum oil

  can be used as is for the production of emulsions of the type eaudans-

oil.

COSMETIC COMPOSITIONS

  EXAMPLE 1: Stick for the lips Calcium lanolate 50% in petrolatum oil ........ 17.00 g Cholesterol .................. .................

........... 3.00 g Beeswax ............................... .......... DTD: .... 8.00 g Castor oil ........................... ............... 10, 00 g Vaseline oil ............................ .............. 12.00 g D and C dyes orange n 17 ......................... ..... 0.50 g Colorants D and C red 8 ................................... .. 0.50 g Titanium oxide ......................................... 2.30 g Water + methyl parahydroxybenzoate 0.2% ............. QSP 100.00 g -8- EXAMPLE 2: Moisturizing body stick Lanolate magnesium 50 % in Vaseline oil ...... 8.10 g Cholesterol ................................ ........ DTD: ........ 0.90 g Purcellin Oil ......................... ............... DTD:. 3.00 g Vaseline Hulle .......................................... 12 , 00 g Ozokerite .............................................. ... 8.00 g Water + methyl para-hydroxybenzoate 0.2% ............. QSP 100.00 g EXAMPLE 3: Moisturizing face stick 50% magnesium lanolate in Vaseline oil ...... 12.00 g Cholesterol .......................... DTD: ..... .................. 8.00 g Perhydrosqualene ........................... DTD: ............... 5.00 g Ozokerite ............................ .............. DTD: ........ 15.00 g Water + 0.2% methyl para-hydroxybenzoate .......... .QSP 100.00 g EXAMPLE 4 - Moisturizing Copper Lanolate Treatment Cream .................................. ....... 3.32 g Cholesterol .......... DTD: .......................... ............ 0.35 g Vaseline oil ........... DTD: .................. ............. 23.33 g Sunflower oil ................ DTD: ............ ............ 10.00 g Lanolin ................................. DTD: ........ ........ 5.00 g Water + methyl para-hydroxybenzoate 0.2% ....... DTD: ...... QSP 100.00 g EXAMPLE 5 - Moisturizing foundation Zinc lanolate ... DTD: ........................................ 6, 37 g Cholesterol ............... DTD: .............................. ... 2.25 g Vaseline ......................... DTD: .. 10.00 g Vaseline oil ...... .................................... 26.38 g Iron Oxide + Titanium Oxide ... .......................... 7.00 g Water + 0.2% methyl para-hydroxybenzoate ........ ... QSP 100.00 g EXAMPLE 6 Moisturizing sun cream Calcium lanolate 50% in petrolatum oil ........ 6.65 g Cholesterol ............ .................. DTD: ..... 0.35 g Vaseline oil .................. ........................ 20.00 g Silicone oil ................... ....................... 10, 00 g Solar filter "PARSOL 1789" (butyl methoxy dibenzoyl methane) sold by the company GIVAUDAN ...... 3.00 g Water + 0.2% methyl parahydroxybenzoate. .......... QSP 100.00 g EXAMPLE 7 Tinted moisturizing cream 50% magnesium lanolate in petrolatum oil ...... 6.00 g B-Sitosterol ..... ..................................... DTD: .... 4.00 g Paraffin oil ......................................... 29.00 g Silicone oil .. ........................................ 3.00 g..DTD: 9 2 682568 1 42

  Purcellin oil ......................................... 5,00 g Oxide of iron + titanium oxide ............................. 3.00 g Water + 0.2% methyl parahydroxybenzoate .. ......... QSP 100.00 g EXAMPLE 8 Moisturizing cream after sun 50% magnesium lanolate in Vaseline oil ...... 17.00 g Cholesterol ....... ..............................

.......... 3.00 g Isopropyl myristate ................................ ..DTD: ... 10.00 g Vaseline oil .................................... ...... 38.00 g Beeswax .................................... ......... 5.00 g Lanolin .................................... ............... 5.00 g Dpanthenol .............................. .................. 2.00 g Water + 0.2% methyl para-hydroxybenzoate ............ QSP 100.00 g EXAMPLE 9 Moisturizing facial cream 50% magnesium lanolate in petrolatum oil ...... 5.70 g Cholesterol .................... ............ DTD: ................ 0.15 g Paraffin oil ............. ................... DTD: ......... 23.15 g Isopropyl palmitate ............ ...................... DTD: ... 4.00 g Purcellin oil ................ ......................... 3.00 g Sesame oil .................. .......................... 4.00 g Water + 0.2% methyl para-hydroxybenzoate ........ ... QSP 100.00 g EXAMPLE 10: Hydra care cream aunt 50% magnesium lanolate in Vaseline oil ..... 2.85 g Cholesterol ........................... ...... DTD: ............... 0.15 g Vaseline oil .................... .............. DTD: ........ 4.00 g Protegin W sold by the company GOLDSCHMIDT ............... DTD: 30.00 g Water + methyl para-hydroxybenzoate 0.2% ............. QSP 100.00 g..DTD:

Claims (11)

  1. Emulsifying system for water-in-oil emulsions   characterized in that it consists of an alkaline metal lanolate   earth or metal and a sterol, said lanolate being obtained by direct action of lanolic acid and an alkaline earth or metal acetate, in an anhydrous medium.   2. Emulsifier according to claim 1, characterized in that the alkaline earth or metal lanolate is taken from the group consisting of lanolates of calcium, magnesium, zinc, copper or aluminum.   3. Emulsifier according to claim 1, characterized in that the sterol is cholesterol, or e-sitosterol   4. Emulsifier according to any one of the claims   preceding, characterized in that the weight ratio of lanolate / sterol weight is between 95/5 and 40/60 and is preferably about / 10. 5. Emulsion of the water-in-oil type comprising a water phase, a fatty phase and an emulsifying system, characterized in that said emulsifying system is that as claimed in any one of the Claims 1 to 4.   Emulsion according to claim 5, characterized by the fact   it has a viscosity of between 80 and 85 poise.   Emulsion according to any one of claims 5 and 6,   characterized in that the concentration of emulsifying system is between 3 and 20% and preferably between 5 and 12% with respect to total weight of the emulsion.   Emulsion according to any one of claims 5 to 7,   characterized in that the weight ratio of the fatty phase to the emulsifier system is between 95/5 and 50/50 and is preferably about 90/10.   9. Emulsion according to any one of claims 5 to 8,   characterized in that it is in the form of a cream and contains the water phase at a concentration of between 20 and 70%, but preferably between 40 and 60% by weight relative to the total weight of the emulsion.   Emulsion according to any one of claims 5 to 8,   characterized in that it is in the form of a stick, and contains the water phase at a concentration of between 5 and 70% by   weight relative to the total weight of the emulsion.   11. Emulsion according to any one of claims 5 to 10,   - 1i - 2568142 characterized in that it contains at least one active ingredient with cosmetic or therapeutic action and any conventional ingredient of   cosmetic or therapeutic compositions.