WO2018007476A1

WO2018007476A1 - Composition, particularly of the emulsion type, and production method thereof

Info

Publication number: WO2018007476A1
Application number: PCT/EP2017/066846
Authority: WO
Inventors: Stephanie Da Costa; Kim Foong CHONG; Aurélie FIEVEZ; Hilde PEETERS
Original assignee: Oleon Nv; Oleon Sdn Bhd
Priority date: 2016-07-06
Filing date: 2017-07-05
Publication date: 2018-01-11
Also published as: KR20190026807A; JP7179248B2; MY197677A; KR102414484B1; WO2018007476A8; FR3053587A1; FR3053587B1; JP2019520383A

Abstract

The invention relates to a composition and, in particular, a multiple emulsion comprising two mutually immiscible phases, PGPR and citric esters of mono- and diglycerides. The invention also relates to a method for producing the composition according to the invention and to the uses of same, particularly in the fields of cosmetics and hygiene.

Description

COMPOSITION PARTICULARLY OF MULTIPLE EMULSION TYPE

AND PROCESS FOR PREPARING

The present invention relates to a composition and in particular to a multiple emulsion, as well as to a process for preparing an emulsion and to its uses, in particular in the cosmetics and hygiene fields.

An emulsion is a suspension of a liquid in the form of particles or droplets in another liquid, these two liquids being immiscible with each other. The two immiscible liquids of an emulsion are generally referred to as "aqueous phase" and "oily phase". However, it is possible to emulsify more than two phases. This is referred to as the general term multiple emulsion. The present multiple emulsion is a triple water-in-oil-in-water or "E / H / E" emulsion, and thus comprises three phases: two aqueous phases (E) and an oily phase (H). In such an E / O Eternary emulsion, drops of an internal aqueous phase (E _inte me) are dispersed in an oily phase (H), to form a primary emulsion, said primary emulsion being itself dispersed in a phase external aqueous (E _ex ternal) - The two aqueous phases (external _exte rnal and E) may be the same or different.

Such a multiple emulsion is particularly advantageous in the field of hygiene products and cosmetics. Indeed, it allows the formation of an oily film on the superficial part of the animal body (and more particularly human body) on which the emulsion is applied and the progressive release of active (s) contained (s) in the aqueous phase internal, said phase being dispersed in the oily phase, for a prolonged effect over time.

These triple emulsions E / H / E are nevertheless difficult to prepare and stabilize over time.

Indeed, they are generally obtained by the dispersion of a "water-in-oil" primary emulsion, in an aqueous phase, containing one or more hydrophilic surfactants.

This process is quite unstable and usually requires the addition of viscosifying agents to limit phase shift phenomena, which can significantly reduce the stability time of the emulsion.

In addition, some of these compounds may have incompatibilities with certain cosmetic active ingredients, in particular hair conditioners, which are cationic molecules difficult to stabilize.

Moreover, because of its high sensitivity to stirring, the industrial approach of manufacturing processes of multiple emulsions remains complicated. Indeed, it requires the use of a multiplication of stabilization steps such as the addition of additional surfactants and / or the use of expensive adapted industrial equipment.

There is therefore a need for compositions which make it possible to obtain multiple emulsions of improved stability, which are simple to prepare and / or involve compounds compatible with a large number of active compounds.

The work of the inventors has made it possible to demonstrate that a certain composition associating a given combination of surfactants makes it possible to obtain a multiple emulsion in a single emulsion step (that is to say without prior formation). a primary emulsion).

The invention therefore relates to a composition comprising two immiscible phases between them, said composition comprising:

at least one HLB emulsifying surfactant between 2 and 6 which is a polyglycerol polyricinoleate (PGPR),

at least 0.5% by weight of citric esters of mono- and di-glycerides relative to the total weight of the composition, and

an emulsifying surfactant of HLB between 2 and 6 other than

PGPR, with a ratio by weight, total amount of PGPR / total amount of HLB emulsifying surfactant between 2 and 6 other than PGPR, being between 2/1 and 9/1,

wherein the ratio by weight, total amount of HLB emulsifying surfactant (s) between 2 and 6 / total amount of citric esters of mono- and diglycerides, is in the range [0.5 / 1, 2 / 1 [.

It should be noted that in the context of the present application, and unless otherwise stated, the ranges of values indicated are inclusive. In particular, it will be noted that the writing [X, Y [in which X and Y represent two numbers, means that the terminal X is included in the range, while the terminal Y is excluded.

The immiscible phases between them are advantageously an aqueous phase and an oily phase.

The composition according to the invention comprises at least one emulsifying surfactant of HLB which is a polyglycerol polyricinoleate (PGPR). A PGPR of HLB between 2 and 6 is hydrophobic. It is dispersible in the oily phase. By HLB (Hydrophilic-Lipophilic Balance) is meant the balance between the size and strength of the hydrophilic group and the size and strength of the lipophilic group of the surfactant. The HLB value according to GRIFFIN is defined in J. Soc. Cosm. Chem. 1954 (volume 5), pages 249-256.

By PGPR, one targets a PGPR molecule or a mixture of different PGPR molecules.

Indeed, because of the multiplicity of hydroxyl functions present in glycerol and polyglycerol, and according to the process for obtaining PGPR, many reaction products are likely to form and a mixture of several PGPRs is generally formed. may differ from each other by:

the number of glycerol units forming the polyglycerol and the arrangement of these units,

the degree of esterification (ie, the number of hydroxyl groups esterified to the polyglycerol), and / or

the number of ricinoleic acid units forming the polyricinoleate.

Preferably, the PGPR of HLB between 2 and 6 comprises at least one non-esterified hydroxyl.

Preferably, the PGPR of HLB between 2 and 6 comprises predominantly (at least 50% by weight relative to the total weight of PGPR) a polyglycerol-3 polyricinoleate (PG-3-PR), a polyglyceryl-4 polyricinoleate (PG -4-PR), a polyglycerol-6 polyricinoleate (PG-6-PR) and a polyglycerol-7 polyricinoleate (PG-7-PR). More preferably, the PGPR predominantly comprises PG-3-PR or PG-4-PR.

The whole number following polyglycerol (or PG) represents the number of glycerol units forming polyglycerol.

Preferably, the PGPR of HLB between 2 and 6 comprises a number of ricinoleic acid unit forming the polyricinoleate (PR) of between 2 and 12, more preferably between 3 and 10, even more preferentially between 4 and 6, In particular, the number of ricinoleic acid units is 5.

More particularly, the polyglycerol polyricinoleate of HLB between 2 and 6 is linear and is represented by the following formula (I):

(I) in which :

R represents a hydrogen or a group of formula (II):

in which m represents an integer between 2 and 12, preferably between 3 and 10, more preferably between 4 and 6,

and

n represents an integer between 3 and 7, preferably between 3 and 4. The composition according to the invention also comprises citric esters of mono- and di-glycerides, which are esters of citric acid and mono- and di- -glycerides of fatty acid (s).

Such a mixture of esters is generally referred to as CITREM. CITREM is conventionally prepared from edible vegetable oil (s).

Advantageously, the mono- and di-glycerides of the citric esters of mono- and di-glycerides comprise acyl groups whose hydrocarbon chain comprises from 12 to 18 carbon atoms, preferably from 14 to 18 carbon atoms, preferably from 16 to 18 carbon atoms. 18 carbon atoms.

Preferably, CITREM is glycerol stearate citrate, that is to say esters of citric acid and mono- and di-glycerides, which mono- and di-glycerides comprise acyl groups whose hydrocarbon chain has 18 carbon atoms.

Usually, the CITREM are hydrophobic and therefore soluble and / or dispersible in an oily phase. CITREM can also be in a neutralized form, that is to say, in the form of salts which also makes them soluble and / or dispersible in an aqueous phase.

Advantageously, the CITREM has a purity (purity of the ester mixture) greater than 95%, preferably greater than 99%, preferably of 00%.

The composition according to the invention comprises, in addition to the PGPR, at least one other emulsifying surfactant of HLB between 2 and 6. The composition thus comprises at least two types of HLB emulsifying surfactant between 2 and 6, namely one or more PGPR (s) and one or more HLB emulsifying surfactant (s) between 2 and 6 other than PGPR.

This emulsifying surfactant of HLB between 2 and 6 other than PGPR is advantageously chosen from the group consisting of polyglycerol esters other than PGPR, sorbitan esters, sucroesters and mixtures thereof.

Such a surfactant has the effect of prolonging the stability of the emulsion prepared from the composition according to the invention.

By way of example of polyglycerol esters (other than PGPR) of HLB of between 2 and 6, mention may be made of polyglycerol-3 diisostearate, polyglycerol-4 isostearate, polyglycerol-2 diisostearate, and the like. polyglycerol-3 oleate, and polyglycerol-2 isostearate.

By way of example of sorbitan esters of HLB ranging from 2 to 6, mention may be made of sorbitan diisostearate, sorbitan isostearate, sorbitan oleate, sorbitan sesquioleate, sorbitan trioleate, and the like. sorbitan dioleate.

By way of example of HLB sucroesters of between 2 and 6, mention may be made of sucrose polystearate and sucrose distearate.

Preferably, the HLB emulsifying surfactant between 2 and 6 other than PGPR is selected from the group consisting of polyglycerol esters (other than PGPR), sorbitan esters and mixtures thereof.

Advantageously, the emulsifying surfactant of HLB between 2 and 6 other than PGPR may be a polyglyceryl-4 isostearate, such as for example obtained according to the production method described in the patent application FR1556521, the content of which is incorporated herein. request.

Thus, the process for producing polyglycerol-4 isostearate comprises reacting isostearic acid and glycerol carbonate, wherein:

the molar ratio of the glycerol carbonate to the isostearic acid used in the reaction is at least 2, and

the reaction is initiated in the presence of a compatibilizing agent which is a polyglycerol ester.

Such a polyglycerol-4 isostearate is dispersible in water. A multiple emulsion according to the invention containing this surfactant is more easily removed with water. Indeed, the surfactant being dispersible in water, unlike other polyglycerol esters which are insoluble in water, the polyglycerol-4 isostearate thus prepared is more easily driven by water. More preferably, the emulsifying surfactant of HLB between 2 and 6 other than PGPR is selected from the group consisting of sorbitan esters.

In particular, the emulsifying surfactant of HLB between 2 and 6 other than PGPR is a sorbitan isostearate.

Preferably, the ratio by weight, total amount of PGPR / total amount of HLB emulsifying surfactant between 2 and 6 other than PGPR, is between 2/1 and 6/1, more preferably between 3/1 and 5/1 .

Advantageously, this ratio by weight and 3/1.

A composition according to the invention makes it possible to obtain a multiple emulsion in an emulsion stage, in particular by simple stirring. It is therefore advantageously in emulsion form, for example at the end of a stirring step.

It makes it possible in particular to obtain a multiple emulsion such as a triple "water-in-oil-in-water" emulsion, with a stability greater than 1 month, preferably 3 months, at a temperature ranging from 4 to 50 ° C. and at atmospheric pressure, and especially at temperatures of 4 ° C +/- 5 ° C, 20 ° +/- 5 ° C, 42 ° C +/- 5 ° C or 50 ° C +/- 5 ° C.

Preferably, the composition according to the invention has a ratio by weight, total amount of surfactant (s) of HLB between 2 and 6 / total amount of citric esters of mono- and di-glycerides, between 0.5 and 1, 99, more preferably between 0.7 and 1.8, still more preferably between 0.8 and 1.5.

Advantageously, the composition according to the invention has a ratio by weight, total amount of surfactant (s) of HLB between 2 and 6 / total amount of citric esters of mono- and di-glycerides, 1/1.

Indeed, the ratio of 1/1 is particularly advantageous for preparing an emulsion from the composition according to the invention, said emulsion then having a non-sticky texture.

The composition according to the invention comprises at least 0.5% by weight of citric esters of mono- and di-glycerides (CITRE), on the total weight of the composition.

Preferably, the composition according to the invention comprises at least 0.8% by weight of citric esters of mono- and di-glycerides (CITREM), based on the total weight of the composition.

Advantageously, the composition according to the invention comprises at least 1.5% by weight of citric esters of mono- and di-glycerides (CITREM), on the total weight of the composition. Indeed, from 1.5% by weight of CITREM, the viscosity of the composition increases exponentially. So, depending on the desired viscosity of the composition, the formulator will choose the amount of citric esters of mono- and diglycerides.

More particularly, the composition comprises an amount of citric esters of mono- and di-glycerides (CITREM) of between 0.5 and 5% by weight relative to the total weight of the composition. Preferably, the amount of citric esters of mono- and diglycerides is between 0.8 and 4% by weight, more preferably between 1.5 and 4% by weight relative to the total weight of the composition.

Similarly, such a CITREM content makes it possible to increase the stability of the emulsion.

Advantageously, the citric esters of mono- and di-glycerides are obtained from edible vegetable oil, and more particularly from palm oil and / or sunflower oil.

Preferably, CITREM is obtained from sunflower oil.

According to its production process and its composition, the viscosity of CITREM can vary. For example, CITREM prepared from palm oil is generally solid, for example in powder form. In this case, it may be necessary to heat the CITREM to its melting temperature, generally between 50 ° C and 100 ° C, in order to liquefy it. CITREM thus liquefied can be mixed with other CITREM or other ingredients in liquid form.

The citric esters of mono- and di-glycerides may be in a neutralized form or not. Advantageously, they are in neutralized form.

The composition may further comprise an active agent and / or an additive. In particular, it may include one or more active (s) and / or one or more additive (s).

More particularly, the composition according to the invention may comprise one or more additive (s) and / or one or more active (s), soluble and / or dispersible in an aqueous phase and / or an oily phase.

Preferably, the additive and / or the active agent is / are chosen from among the substances intended to be brought into contact with the superficial parts of the animal body, and more particularly human, in particular, from those usually used in the field of animal and human hygiene products and cosmetics.

More generally, all the ingredients composing the composition according to the invention are selected from the ingredients having a good safety with respect to the animal body, more particularly human.

Indeed, the composition according to the invention makes it possible to obtain an emulsion which can be used as a hygiene product and / or cosmetic product and therefore comprises preferentially a cosmetic additive and / or a cosmetic active agent.

The cosmetic additive is preferably chosen from the group consisting of preservatives, humectants, stabilizers, perfumes, sequestering agents (EDTA), pigments, especially exfoliating fillers, soluble dyes, sunscreens and their mixtures.

The composition according to the invention allows easy solubilization of solar filters. In particular, it may comprise at least 5% by weight of sunscreens, preferably at least 10% by weight, more preferably at least 15% by weight, and even a content greater than 20% by weight relative to the total weight of the composition. . More particularly, it may comprise at least 5% by weight of solid organic solar filters, preferably at least 8% by weight relative to the total weight of the composition.

Advantageously, the sunscreen is chosen from organic and / or inorganic sunscreens, preferably from solid and / or liquid organic screening agents.

By way of example of solid organic sunscreens, mention may be made of diethylamino hydroxybenzoyl hexylbenzoate, butylmethoxydibenzoyimethane (BMDB), benzophenone-3, ethylhexyltriazone, 4-methylbenzylidene camphor, phenyl-salicylate, methylene bis- benzotriazolyl tetramethylbutylphenol, benzophenone-8 and bis-ethylhexyloxyphenol methoxy-phenyl triazine.

As an example of liquid organic filters, mention may be made of octyl methoxycinnamate, octocrylene, homosalate and polysilicone.

The cosmetic active agent is preferably chosen from the group consisting of moisturizers, such as hyaluronic acid; ceramides; water-soluble vitamins; antiseptics; antiseborrhoeic; antimicrobials such as benzoyl peroxide, salicylic acid, triclosan and azelaic acid; optical brighteners; and their mixtures.

The amount of each additive or active agent is that conventionally used in the field under consideration, and for example from 0.01 to 10% by weight relative to the weight of the composition.

The invention also relates to a combination of surfactants for emulsion comprising:

at least one HLB emulsifying surfactant between 2 and 6 which is a polyglycerol polyricinoleate (PGPR), mixed with at least one second emulsifying surfactant of HLB between 2 and 6 other than PGPR, with a ratio by weight, amount total PGPR / total amount of surfactant (s) emulsifying (s) of HLB between 2 and 6 other than PGPR, being between 2/1 and 9/1, and

citric esters of mono- and di-glycerides (CITREM), and in which the ratio by weight, total amount of surfactant (s) emulsifier (s) of HLB between 2 and 6 / total amount of citric esters of mono and di-glycerides, is in the range [0.5 / 1, 2/1 [.

The emulsifying surfactant of HLB between 2 and 6 other than PGPR is as described above.

Advantageously, the combination of surfactants according to the invention may be in admixture with a hydophobe substance, such as a triglyceride. This hydrophobic substance makes it possible to obtain a homogeneous mixture in the form of paste, which is easy to handle.

Preferably, the hydrophobic substance is a triglyceride.

Preferably, a triglyceride may be in the form of a mixture of triglycerides and is introduced into the combination of surfactants via a substance selected from the group consisting of vegetable oils, vegetable butters, animal oils and fats, a particular fraction of a of the above substances, or mixtures thereof. The particular substance or fraction consists of at least 90% by weight of triglycerides on the weight of the particular substance or fraction under consideration. A particular fraction of one of the above substances is obtained by any method known to those skilled in the art, in particular by distillation.

More preferably, the triglyceride is introduced into the combination of surfactants via a vegetable oil, a vegetable butter, a particular fraction thereof, or mixtures thereof. More preferably still, the triglyceride is introduced into the combination of surfactants via a vegetable oil, or a particular fraction of a vegetable oil.

By way of example of vegetable oil, mention may be made of coconut oil, palm kernel oil, palm oil, olive oil, walnut oil, rapeseed oil, corn oil, soybean oil, sunflower oil, grape oil, linseed oil, camphor oil, apricot kernel oil, olive oil avocado, macadamia nut oil, and sweet almond oil.

Examples of vegetable butter include shea butter, cocoa butter, mango butter, olive butter and kokum butter.

As an example of oil and animal fat, there may be mentioned fish oil, and tallow. Alternatively, the triglyceride can be synthesized by esterification or transesterification using, for example, a particular acid (s), such as 2-ethylhexanoic acid, caprylic acid or capric acid.

Preferably, the triglyceride comprises acyl groups whose hydrocarbon chain is saturated and comprises from 8 to 16 carbon atoms, more particularly from 8 to 14 carbon atoms, more particularly from 8 to 10 carbon atoms.

More particularly, the triglyceride comprises acyl groups whose hydrocarbon chain is branched. In particular, the triglyceride is triethylhexanoin.

The combination of surfactants according to the invention is ready for use to be added to an aqueous phase to obtain an emulsion or two immiscible phases to obtain the composition according to the invention. This combination of surfactants according to the invention may comprise other compounds including one or more active (s) and / or additive (s) as described above.

The invention furthermore relates to an emulsion comprising a composition according to the invention or a combination of surfactants according to the invention. More particularly, the invention relates to a composition according to the invention in the form of an emulsion.

The emulsion is advantageously a multiple emulsion, preferably a triple "water-in-oil-in-water" emulsion.

Advantageously, the multiple emulsion comprises two aqueous phases, identical or different, and an oily phase.

The multiple emulsion may also comprise two identical aqueous phases and an oily phase.

The oily phase generally comprises one or more hydrophobic substance (s), other than an HLB emulsifying surfactant of between 2 and 6 and CITREM.

Preferably, the hydrophobic substance has a Hansen solubility parameter relating to the polarity δΡ of less than or equal to 3 (J / cm ³ ) ¹ ' ² at 25 ° C.

The calculation of the Hansen solubility parameter is described in Solubility Parameters, Kirk-Othmer Encyclopedia of Chemical Technology, Suppl. Vol., 2nd ed., Standen, A., Ed., Interscience, New York, 1971, 889-910.

This hydrophobic substance may be chosen from the group consisting of mineral oils, silicones, fatty acids, fatty alcohols, esters (other than CITREM and an emulsifying surfactant of HLB comprising 2 and 6), and their ethoxylated derivatives. and their mixtures. More particularly, the mineral oil is liquid paraffin.

More particularly, the silicone is chosen from dimethicones and cyclopentasiloxane.

More particularly, the fatty acid is selected from stearic acid, cetyl acid and cetearyl acid.

More particularly, the fatty alcohol is chosen from stearic alcohol, cetyl alcohol and cetearyl alcohol.

More particularly, the ester other than CITREM and an HLB emulsifying surfactant of 2 and 6 are chosen from the group consisting of:

monoesters obtained from a monoalcohol, such as butanol, isopropanol, octanol, heptanol, ethylhexanol, stearyl alcohol, isostearyl alcohol, dodecanol, isodecanol , isononanol, isooctanol, and a monocarboxylic acid, such as caprylic acid, capric acid, heptanoic acid, palmitic acid, myristic acid, lauric acid and isostearic acid.

diesters obtained from a monoalcohol, as previously described, and a dicarboxylic acid, such as fumaric acid, adipic acid, succinic acid and sebacic acid;

diesters obtained from monopropylene glycol and a monocarboxylic acid as described above;

triesters obtained from tri-alcohol, such as trimethylolpropane and glycerol, and fatty acid (s), and especially triglycerides;

tetraesters obtained from a tetra-alcohol, such as pentaerythritol, and a monocarboxylic acid as described above;

and their mixtures.

Preferably, a triglyceride is as described above.

Preferably, the emulsions according to the invention comprise at least 5% by weight of triglyceride, more preferably at least 6% by weight, still more preferably at least 8% by weight, relative to the weight of the emulsion.

Preferably, the hydrophobic substance other than CITREM and an emulsifying surfactant of HLB of between 2 and 6, is chosen from the esters, more preferably from the group of esters described above.

In particular, the hydrophobic substance is chosen from trimethylolpropane triisostearate, monopropylene glycol caprate / caprylate, triethylhexanoin and mixtures thereof.

Advantageously, the hydrophobic substance is chosen from the substances intended to be brought into contact with the superficial parts of the animal body, and more particularly, human.

Advantageously, the hydrophobic substance is chosen from emollients in the field of cosmetics.

Preferably, in the emulsions according to the invention, the oily phase represents at least 8% by weight, preferably at least 10% by weight, relative to the weight of the multiple emulsion.

Preferably, the oily phase represents between 8 and 50% by weight, more preferably between 10 and 40% by weight, more preferably between 12 and 35% by weight, the percentages by weight being given relative to the weight of the emulsion. multiple.

Advantageously, the emulsion according to the invention does not comprise silicone substance.

Advantageously, in the multiple emulsion according to the invention, the sum of the aqueous phases, that is to say the internal aqueous phase and the external aqueous phase, represents between 50 and 92% by weight relative to the weight of the multiple emulsion.

The internal aqueous phase and the external aqueous phase may be identical, or different if one or more additive (s) and / or active (s) is / are added specifically to the external aqueous phase.

The multiple emulsion according to the invention preferably has a pH of between 4 and

10. The pH can be adjusted by adding citric acid for example, depending on the desired use of the multiple emulsion.

The stability of a multiple emulsion according to the invention is greater than two months, preferably greater than three months, at a temperature ranging from 4 to 50 ° C, especially from 4 ° C +/- 5 ° C, 20 ° + / - 5 ° C, 42 ° C +/- 5 ° C or 50 ° C +/- 5 ° C, preferably greater than three months.

The present invention also relates to a cosmetic composition and / or hygiene product comprising an emulsion according to the invention.

By hygiene product and / or cosmetic product, any mixture intended to be placed in contact with the superficial parts of the human body (epidermis, hair and hair systems, nails, lips and external genital organs) or with the teeth and oral mucosa, in view, exclusively or mainly, to clean, perfume, modify the appearance, protect, maintain or repair body odors.

The invention therefore also relates to a hygiene product and / or a product cosmetic composition comprising an emulsion according to the invention optionally with an additive and / or an active ingredient, such as a cosmetic additive and / or a cosmetic active agent.

By way of example of such products, mention may be made of cleansing products for the skin, mucous membranes and / or hair, shower gels or creams, shampoos, shaving products and make-up remover products. skin, conditioners, rinsing masks and exfoliating products.

The emulsion according to the invention can also be used as a cleaning product for an animal such as an animal shampoo. Such an animal cleaning product may be used on any superficial part of the animal body such as hair, claws, mucosa and may comprise additives and / or cosmetic active agents as mentioned above, and / or veterinary active ingredients such as those against parasites.

The invention also relates to a method for cleaning a superficial part of the animal or human body, such as the skin, scalp, hair, hair, eyelashes, eyebrows, nails, claws and mucous membranes, comprising a step of applying a multiple emulsion according to the invention to the surface portion, and a step of rinsing the surface portion. The superficial part of the animal or human body cleaned by the emulsion is left clean as well as soft and hydrated according to the cosmetic active ingredients present in the product.

Preferably, the superficial parts of the animal body, and more particularly human, are the skin, the hair and the hairs.

However, the uses of the emulsion according to the invention are numerous and are not limited to the fields of hygiene, cosmetics and veterinary.

Advantageously, the emulsion according to the invention comprises components of renewable origin, such as vegetable oil derivatives.

The hygiene product and / or cosmetic product according to the invention has a stability of several months at a temperature ranging from 4 to 50 ° C, especially at 4 ° C +/- 5 ° C, 20 ° +/- 5 ° C, 42 ° C +/- 5 ° C or 50 ° C +/- 5 ° C, preferably greater than three months.

The emulsion included in the hygiene product and / or cosmetic product also allows the action of several cosmetic active ingredients, for example detangling and protecting, simultaneously, prolonged or consecutive to one another, in particular because of the presence of these assets in the different phases of the multiple emulsion.

The invention also relates to a method for preparing an emulsion, comprising an emulsion step: an oil phase comprising at least one HLB emulsifying surfactant of between 2 and 6 which is a polyglycerol polyricinoleate (PGPR), and, at least one emulsifying surfactant of HLB between 2 and 6 other than PGPR,

in an aqueous phase,

the oily phase and / or the aqueous phase comprising at least 0.5% citric esters of mono- and di-glycerides (CITREM), the weight of the emulsion, and the ratio by weight, total amount of surfactant ( s) emulsifier (s) of HLB between 2 and 6 / total amount of citric esters of mono- and di-glycerides, being in the range [0.5 / 1, 2/1 [.

PGPR, CITREM, HLB surfactants ranging from 2 to 6 other than PGPR, oily and aqueous phases are as previously described, as well as their advantageous and preferred modes.

In the process for preparing the emulsion, the ratio by weight, total amount of PGPR / total amount of emulsifying surfactants of HLB between 2 and 6 other than PGPR, is between 2/1 and 9/1.

The addition of one or more surfactant (s) (s) of HLB between 2 and 6 other than PGPR makes it possible to further stabilize the emulsion prepared by the process.

The citric esters of fatty mono- and di-glycerides may be in a neutralized form or in an unneutralized form.

Also, according to a particular embodiment of the methods according to the invention, one or more CITREM in neutralized form are used. It (s) is / are introduced into the oily phase, into the aqueous phase or into the oily phase and the aqueous phase. Indeed, in a neutralized form, CITREM are in the form of salts and have the capacity to be introduced into an oily phase or in an aqueous phase. These may be CITREM Radiamuls Citrem 2932 K (neutralized) and / or Radiamuls Citrem 2935 K (neutralized).

Preferably, the CITREM (s) is (are) introduced into the oily phase. According to a second particular embodiment of the methods according to the invention, one or more CITREM in unneutralized form are used. It (s) is / are then introduced (s) in the oily phase. Indeed, in an unneutralized form, CITREMs have the capacity to be introduced only in an oily phase. It may be CITREM Radiamuls Citrem 2931 K (not neutralized) and / or Radiamuls Citrem 2934 K (unneutralized). According to a third particular embodiment of the methods according to the invention, a combination of at least one CITREM in a neutralized form and at least one CITREM in an unneutralized form is used.

Preferably, the citric esters of mono- and di-glycerides (CITREM) are contained in the oily phase.

^The method of the emulsion step is advantageously performed by adding the oily phase in the aqueous phase at a flow rate of 5g / min and 40g / min, preferably 8 to 20 g / min, typically 10 g / min.

Advantageously, the addition of the oily phase in the aqueous phase is carried out with stirring, preferably at 700 rpm (revolutions per minute).

The formation of the emulsion is carried out at a stirring speed of at least 5000 revolutions per minute, preferably at least 6000 revolutions per minute, more particularly at 8000 revolutions per minute.

The stirring lasts at least one minute, preferably at least 5 minutes, more particularly 10 minutes.

The process can be carried out at room temperature or when hot. For example, it can be implemented at a temperature ranging from 15 ° C to 90 ° C, it is preferably carried out at room temperature in order to introduce temperature sensitive assets.

The process can therefore be carried out hot, especially when one or more

CITREM used (s) present (s) a certain viscosity or is / are in a solid form. For example, the process is carried out hot when the CITREM is derived from palm oil, in particular when CITREM sold under the reference "Radiamuls Citrem 2932 K®" (neutralized) is used.

In the case where the process is carried out hot, the various components of the oily phase are then introduced into a vessel and then heated if necessary to a temperature such as that corresponding to the melting temperature of the component having the highest melting temperature. to be liquefied and to obtain a homogeneous mixture. The components are then mixed for 5 to 15 minutes at a rate of 100 to 600 rpm (rpm) before being added to the aqueous phase itself previously heated, for example at this same temperature.

In this case where the emulsion is hot, for example at a temperature of 80 ° C, the emulsion should be allowed to return to a room temperature with moderate agitation such as 300 rpm (revolutions per minute).

Alternatively, the process can be carried out at ambient temperature, especially when one or more CITREM used (s) are in liquid form at room temperature. For example, the process is carried out at ambient temperature when the CITREM is derived from sunflower oil, in particular when using the CITREM marketed under the reference "Radiamuls Citrem 2934 K®" (unneutralized), or when using neutralized CITREMs.

In the case where the process is carried out at ambient temperature (20 ° C. +/- 5 ° C.), the various components of the oily phase are introduced into a container at ambient temperature. The components are then mixed for 5 to 10 minutes at a rate of 100 to 600 rpm before being added to the aqueous phase itself at this temperature.

The process may comprise the addition of active (s) and / or additive (s) in the oily phase and / or in the aqueous phase according to their hydrophilic, hydrophobic or amphiphilic properties.

Preferably, the active agent (s) and / or additive (s) are integrated in the aqueous phase, which will become both the internal aqueous phase and the external aqueous phase of the multiple emulsion prepared according to the process according to the method. invention.

Alternatively, each active ingredient or additive, in whole or in part, can be integrated into the external aqueous phase, independently by adding it to the emulsion after the emulsion step of the emulsion preparation process according to the invention.

Indeed, after the emulsion step, the process may comprise one or more subsequent stages of addition of additive (s) and / or active (s), including moisturizers, thickeners and hair conditioners which are difficult to stabilize.

The active ingredient and the additive are as previously described for the emulsion.

This step of adding an additive and / or an active agent can be carried out with stirring, in particular at 300 rpm.

The method may further comprise a pH adjustment step as previously described.

The invention also relates to a process for preparing a combination of surfactants for emulsion according to the invention as described above, comprising a mixing step

an HLB emulsifying surfactant of between 2 and 6 which is a polyglycerol polyricinoleate (PGPR), and an HLB emulsifying surfactant of between 2 and 6 other than PGPR, with a ratio by weight, total amount of PGPR / total amount of surfactant (s) emulsifier (s) of HLB between 2 and 6 other than PGPR, being between 2/1 and 9/1,

with

citric esters of mono- and di-glycerides (CITRE), in which the ratio by weight, total amount of surfactant (s) emulsifier (s) of HLB between 2 and 6 / total amount of citric esters of mono- and diglycerides, varying in the range [0.5 / 1, 2/1].

Advantageously, the combination of surfactants obtained by this process makes it possible to prepare a multiple emulsion in particular, a triple "water-in-oil-in-water" emulsion.

The surfactant combination is at least 1.6% by weight based on the weight of the emulsion. Preferably, up to 10% by weight relative to the weight of the emulsion, typically from 1.66 to 9% by weight.

The invention finally relates to the use of the emulsion according to the invention, in a hygiene product, a cosmetic product and / or a cleaning product for animals.

The invention will be better understood from the examples given for illustrative purposes.

EXAMPLE 1 Preparation of a Multiple Emulsion "Sun Lotion SPF 30" According to the Invention

a) Products used

Novethix L-10 Acrylates / Beheneth-25

Thickener 0.7 Polymer *** ethacrylate Copolymer

E

Deionized water Aqua Solvent qs

ethylhexylglycerine

Ethylhexylglycerin and preservative and 0.5

Phenoxyethanol (additive)

Phenoxyethanol ^****

Perfume Perfume (additive) 0.25

H: oily phase

E: aqueous phase

QSP: Sufficient amount to reach 100

* References of products available for sale by OLEON NV.

References of products available for sale by BASF

Product reference available for sale by Lubrizol

* Product reference available for sale by Thor personal

TABLE 1 Composition of a Multiple Emulsion According to the Invention

of type "SPF 30 Sun Lotion" a) Preparation of the oily phase H

The oily phase is prepared by introducing into a container the surfactants, triethylhexanoin and sunscreens mentioned in Table 1 above and in the amounts indicated.

The oily phase is heated to 80 ° C to obtain a liquid and clear mixture, then stirred at 300 rpm. b) Preparation of the aqueous phase E

The aqueous phase is prepared by introducing into a container the water and the thickener in the amounts indicated in Table 1.

The aqueous phase is heated to 80 ° C, then stirred at 700 rpm for one minute to obtain a liquid and clear mixture. c) Preparation of the multiple emulsion

The oily phase H is added to the aqueous phase E over a period of 5 minutes, with stirring at 300 rpm.

Once the addition is complete, the composition is stirred for 10 minutes at 8000 rpm, the triple emulsion E / H / E obtained is allowed to cool to room temperature with stirring of 300 rpm.

Once the temperature reaches 30 ° C, the preservative and the fragrance, according to the amounts indicated in Table 1 above are added with stirring at 400 rpm. d) Stability

Such a multiple emulsion is stable for at least 3 months at a temperature ranging from 4 to 50 ° C, especially at 4 ° C +/- 5 ° C, 20 ° C +/- 5 ° C, 42 ° C +/- 5 ° C and / or 50 ° C +/- 5 ° C.

The multiple emulsion allows a controlled release of sunscreens which is present in the oily phase. Thus, there will be an immediate and prolonged effect.

The multiple emulsion thus obtained makes it possible to solubilize a large content of sunscreens. These represent in fact 23.5% by weight on the weight of the emulsion.

EXAMPLE 2 Preparation of another multiple emulsion "BOTTLE hand cream" according to the invention

a) Products used

International nomenclature

Phases Reference Function% cosmetic ingredients (INCI) by weight

Polyglyceryl-3-polyricinoleate &

Radia 7887 ^* Surfactant 2.0 sorbitan isostearate

Radiamuls Citrem

CITREM [Glyceryl stearate citrate] Surfactant 2.0 2932K *

Jolee 7610 ^* Triethylhexanoin Emollient 9.6

H

Radia 7207 ^* Monopropylene glycol emollient 5.0 caprate / caprylate

Radia 7907 ^* Monoglyceride caprylate Anti-microbial agent 0.5

Radia7380 ^* Trimethylolpropane triisostearate Emollient 3.0

Radia 7607 ^*

Butyrospermum Parkii Emollient 2.0 Shea Butter Radia 4810 ^* Glycerin Moisturizing Agent 2.0

E Ammonium

Aristoflex AVC ^** AcryloyldimethyltaurateA / P Thickening Agent 0.1 Copolymer

carbomer

141 G ^* * ^* Carbomer Thickener 0.3

Radia 4710 ^* Monopropylene glycol Moisturizing Agent 2.0

_********

1,3-butylene glycol moisturizing agent

Deionized water Aqua Solvent QSP 100

Ethylhexylglycerol Ethylhexylglycerin and Preservative

ne and 1, 0

Phenoxyethanol (Additive)

phenoxyethanol **

***

Perfume Perfume 0.2

Total 100

H: oily phase

E: aqueous phase

QSP: Sufficient amount to reach 100

* References of products available for sale by OLEON NV.

"Product reference available for sale by the company Clariant.

* ^{** Product} reference available for sale by Evonik.

* ^{*** Product} reference available for sale by Brenntag.

* ^{**** Product} reference available for sale by Thor personal care.

Table 2: Composition of an emulsion according to the invention of the "moisturizing hand cream" type a) Preparation of the oily phase H

The oily phase is prepared by introducing into a container the seven compounds mentioned in Table 2, above, and in the amounts indicated. This mixing is carried out with stirring at 200 rpm at a temperature of 80 ° C. The mixture obtained is homogeneous and clear. b) Preparation of the aqueous phase E

The aqueous phase is prepared by introducing into a container the water and the five compounds mentioned above and in the amounts indicated in Table 2.

The aqueous phase is heated to 80 ° C, then stirred at 8000 rpm for one minute to obtain a homogeneous and clear mixture. c) Preparation of the multiple emulsion according to the invention

The oily phase is added to the aqueous phase in 5 minutes, with stirring at 300 rpm.

Once the addition is complete, the composition is stirred for 10 minutes at 8000 rpm. A triple E / H / E emulsion is obtained.

Once the temperature reaches 30 ° C., the preservative and the fragrance, according to the amounts indicated in Table 2, above, are added under agitation of 400 revolutions per minute. d) Stability

Such a multiple W / O / W emulsion is stable for at least 3 months at a temperature ranging from 4 to 50 ° C, in particular at 4 ° C +/- 5 ° C, 20 ° C +/- 5 ° C, 42 ° C +/- 5 ° C or 50 ° C +/- 5 ° C.

This fluid emulsion spreads very easily on the skin and shows a rapid penetration. It leaves the skin fresh and hydrated.

The multiple emulsion allows an immediate and prolonged hydration thanks to the active present in the internal and external aqueous phase.

Claims

1. Composition comprising two phases immiscible with each other, said composition comprising:

at least one HLB emulsifying surfactant between 2 and 6 other than PGPR, with a ratio by weight, total amount of PGPR / total amount of HLB emulsifying surfactant (s) between 2 and 6 other than PGPR, being between 2/1 and 9/1,

wherein the ratio by weight, total amount of HLB emulsifying surfactant (s) between 2 and 6 / total amount of citric esters of mono- and diglycerides, is in the range [0.5 / 1, 2/1 [.

2. Composition according to claim 1, wherein the ratio by weight, total amount of surfactant (s) emulsifier (s) of HLB between 2 and 6 / total amount of citric esters of mono- and di-glycerides, is 1/1.

3. Composition according to claim 1 or 2, comprising an amount of citric esters of mono- and di-glycerides of 0.5 and 5% by weight relative to the total weight of the composition.

4. Composition according to any one of claims 1 to 3, wherein the citric esters of mono- and di-glycerides are obtained from palm oil and / or sunflower oil.

The composition of any one of claims 1 to 4, wherein the HLB emulsifying surfactant between 2 and 6 other than the

PGPR, is a polyglycerol ester, a sorbitan ester and / or a sucroester.

6. Composition according to any one of claims 1 to 5, further comprising an active agent and / or an additive.

7. A combination of surfactants for emulsion comprising:

at least one HLB emulsifying surfactant of between 2 and 6 which is a polyglycerol polyricinoleate (PGPR), mixed with at least one second emulsifying surfactant of HLB between 2 and 6 other than PGPR, with a ratio by weight, amount total of PGPR / total amount of surfactant (s) emulsifier (s) of HLB between 2 and 6 other than PGPR, being between 2/1 and 9/1, and

citric esters of mono- and di-glycerides, and

8. Composition according to any one of claims 1 to 6 in emulsion form.

9. Emulsion comprising a combination of surfactants according to claim 7.

10. Process for preparing an emulsion, comprising an emulsion step:

an oil phase comprising at least one HLB emulsifying surfactant of between 2 and 6 which is a polyglycerol polyricinoleate (PGPR), and, at least one emulsifying surfactant of HLB between 2 and 6 other than PGPR,

in an aqueous phase,

the oily phase and / or the aqueous phase comprising at least 0.5% citric esters of mono- and di-glycerides, on the weight of the emulsion, and the ratio by weight, total amount of surfactant (s) emulsifying (s) of HLB between 2 and 6 / total amount of citric esters of mono- and di-glycerides, being in the range [0.5 / 1, 2/1 [.

11. Process for preparing a combination of emulsion surfactants according to claim 7, comprising a mixing step: an HLB emulsifying surfactant between 2 and 6 which is a polyglycerol polyricinoleate (PGPR), and an emulsifying surfactant of HLB between 2 and 6 other than PGPR, with a ratio by weight, total amount of PGPR total amount of surfactant (s) emulsifier (s) of HLB between 2 and 6 other than

PGPR, being between 2/1 and 9/1,

with

citric esters of mono- and di-glycerides,

12. Cosmetic composition and / or hygiene product comprising a composition according to claim 8 or an emulsion according to claim 9.