EP3681465A1 - COMBINAISON EMULSIFIANTE POUR l'OBTENTION D'EMULSIONS DE FAIBLE VISCOSITE - Google Patents
COMBINAISON EMULSIFIANTE POUR l'OBTENTION D'EMULSIONS DE FAIBLE VISCOSITEInfo
- Publication number
- EP3681465A1 EP3681465A1 EP18765124.5A EP18765124A EP3681465A1 EP 3681465 A1 EP3681465 A1 EP 3681465A1 EP 18765124 A EP18765124 A EP 18765124A EP 3681465 A1 EP3681465 A1 EP 3681465A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- emulsion
- mono
- mel
- hydroxy acid
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/60—Sugars; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
- A61K8/062—Oil-in-water emulsions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/37—Esters of carboxylic acids
- A61K8/375—Esters of carboxylic acids the alcohol moiety containing more than one hydroxy group
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/60—Sugars; Derivatives thereof
- A61K8/602—Glycosides, e.g. rutin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/14—Preparations for removing make-up
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/59—Mixtures
- A61K2800/592—Mixtures of compounds complementing their respective functions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/59—Mixtures
- A61K2800/596—Mixtures of surface active compounds
Definitions
- the present invention relates to the preparation of an emulsion such as an oil-in-water emulsion and more particularly the use of an MEL as a co-emulsifier.
- the present invention also relates to an emulsifying combination, a composition and an emulsion comprising it, as well as methods of preparation and related uses.
- An emulsion is a dispersion 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”.
- the emulsion according to the invention is more particularly an oil-in-water emulsion thus comprising an oily phase dispersed in an aqueous phase.
- US Pat. No. 3,895,692 describes a process for preparing an oil-in-water emulsion that can be carried out at ambient temperature, the emulsion being weakly viscous, stable and composed of dispersed fine droplets.
- This process uses a mixture of emulsifiers, one or more co-surfactant (s) and oils.
- the emulsifier mixture consists of at least one non-ionic primary emulsifier (such as, for example, polyglycerol laurate) and at least one secondary emulsifier containing one or more acid functional (s).
- the aqueous phase must represent at least 70% by weight of the emulsion.
- emulsify more than 30% by weight of an oily phase relative to the weight of the emulsion it may be advantageous to emulsify more than 30% by weight of an oily phase relative to the weight of the emulsion.
- Such emulsions are advantageous for applications requiring the quantity of product to be sprayed to be limited, and in particular the quantity of water. This is the case for phytopharmaceutical products to spray on crops.
- oily phase-rich emulsions are also sought for applications as massage fluids, cleaning fluids, serums concentrated in actives, etc.
- the present invention provides an alternative solution for forming an oil-in-water emulsion, in particular a new emulsifying combination:
- the invention thus relates to the use of at least one mannosylerythritol lipid (MEL) as a co-emulsifier of a hydroxy acid ester and fatty acid mono- and diglycerides, said hydroxy acid comprising at least one 4 carbon atoms.
- MEL mannosylerythritol lipid
- co-emulsifier a compound capable of optimizing the properties of the emulsion (stability %) obtained with an emulsifier.
- mannosylerythritol lipid or MEL is meant a molecule comprising a hydrophilic portion formed by the mannosylerythritol group, and a hydrophobic portion formed by at least one acyl group.
- MEL is meant more particularly a molecule having the following general formula (I):
- R 1 and R 2 which are identical or different, represent an acyl group comprising an unsaturated or saturated acyclic carbon chain
- R 3 and R 4 identical or different, represent an acetyl group or a hydrogen atom.
- R 1 , R 2 , R 3 , R 4 are identical to those indicated in Formula (I).
- MELs denotes at least two molecules of formulas (I), (II) or (III) which are different in their substitution (acyl groups, acetyls) or by their stereoisomerism, more particularly at least two molecules of formulas ( II) different.
- MELs are generally classified into four classes of molecules, denoted from A to D, according to their degree of acetylation in R 3 and R 4 .
- the class of MELs-A comprises molecules of formula (I) having two acetyl groups at R 3 and R 4 .
- the class of MELs-B and the class of MELs-C contain molecules of formula (I) having a single acetyl group at R 4 and R 3 respectively.
- MELs can vary in their structure, by the nature of the fatty acids that make up their hydrophobic part. This variation is generally a function of the process used to obtain the MELs.
- MELs are generally obtained by processes involving the cultivation of fungi, and more particularly yeasts.
- the MEL (s) referred to by the present application are obtained by a fermentation process, comprising the following steps:
- strains from which MELs can be obtained are well known to those skilled in the art.
- MELs-A, MELs-B, MELs-C or MELs-D a class of MELs
- Pseudozyma antarctica, Pseudozyma aphidis, Pseudozyma rugulosa and Pseudozyma parantarctica predominantly produce MELs-A of formula (III).
- Pseudozyma graminicola, Pseudozyma siamensis and Pseudozyma hubeiensis predominantly produce MELs-C of formula (III).
- Pseudozyma tsukubaensis mainly produces MELs-B of formula (IV) and Pseudozyma crassa produces for the most part MELs-A of formula (IV).
- the MELs are obtained by a fermentation process using a strain producing MELs of formula (II).
- the MELs are obtained by a fermentation process using a strain selected from Pseudozyma aphidis, Pseudozyma rugulosa, Pseudozyma antarctica or Pseudozyma parantarctica, preferentially from Pseudozyma aphidis, Pseudozyma antarctica or Pseudozyma parantarctica, more preferably the strain is Pseudozyma aphidis.
- the carbonaceous substrate is typically a glycerol, an n-alkane or an oil, in particular of renewable origin.
- the renewable oil is a vegetable or animal oil, more preferably a vegetable oil.
- the vegetable oil is chosen from the group consisting of a soybean oil, a sunflower oil, an olive oil and a rapeseed oil. More particularly, the vegetable oil is a soybean oil or a rapeseed oil, more particularly, a rapeseed oil.
- These renewable oils are particularly rich in acyl groups having a carbon chain containing 18 carbon atoms, such as acyl groups derived from oleic, linoleic and / or linolenic acid.
- the fermentation process generally lasts at least 3 days, preferably at least 7 days.
- the MELs are obtained by a fermentation process using:
- a vegetable oil preferably a rapeseed oil or a soybean oil, as a carbon substrate.
- Such a strain is usually grown in a reactor in a medium comprising glucose, water and / or salts (such as magnesium sulfate, monopotassium phosphate, sodium nitrate, and / or ammonium nitrate ).
- This culture medium is also used in the fermentation process.
- the fermentation medium of the fermentation process comprises a culture medium and the carbon substrate.
- the various components of the medium are sterilized separately before introduction into the reactor.
- the temperature of the medium is preferably between 20 ° C and 40 ° C, more preferably between 25 ° C and 35 ° C. It should be noted that in the context of the present application, and unless otherwise stated, the ranges of values indicated are inclusive.
- the reaction crude obtained at the end of the fermentation process is what is called in the present application, the crude fermentation.
- the fermentation crude generally comprises at least two MELs, at least the residual carbon substrate and / or a by-product of the carbon substrate, the strain and water, the by-product of the carbonaceous substrate resulting from the fermentation.
- the objective of the MEL recovery step is to separate one or more MEL (s) from one or more of the other components of the fermentation crude, such as residual carbonaceous substrate and / or a by-product of the carbonaceous substrate, a stump, and / or water.
- the fermentation crude comprises at least two MELs, at least one triglyceride and / or at least one fatty acid, water and a strain of the genus Pseudozyma.
- the carbon substrate is an oil of renewable origin
- a by-product of the carbonaceous substrate is a fatty acid.
- the residual vegetable oil is therefore composed of at least one triglyceride.
- the separation of one or more MEL (s) from one or more of the other components of the crude fermentation can be done by any separation method known to those skilled in the art.
- the separation of one or more MEL (s) from one or more of the other components may comprise one or more of the following methods:
- the strain can be separated by decantation, filtration, and / or centrifugation;
- the water may be separated by decantation, evaporation, centrifugation, and / or passage over an inorganic substrate which is an adsorbent;
- MELs recovered can therefore include:
- fatty acid is meant a free fatty acid and / or salt form.
- the amount of fatty acid (s) and / or triglyceride (s) present in the MELs recovered may be between 0.5 and 60% by weight, preferably between 1 and 50% by weight, relative to the total weight recovered MELs.
- the fatty acid (s) comprises (s) a carbon chain comprising between 8 and 24 carbon atoms, preferably between 8 and 20 carbon atoms.
- the triglyceride (s) comprises (s) acyl groups whose acyclic carbon chain, saturated or unsaturated, contains between 8 and 24 carbon atoms, preferably between 16 and 18 carbon atoms. More particularly, the carbon chain is linear and contains only carbon and hydrogen atoms, optionally substituted by a hydroxyl (OH) function.
- the MELs recovered can therefore be in a more or less purified form, that is to say in a mixture with other components of the fermentation medium.
- mixture of MELs when the MELs recovered are in admixture with at least one fatty acid and / or at least one triglyceride, optionally water and / or a strain, this mixture is called "mixture of MELs".
- a first mixture of MELs is a fermentation crude, i.e., at least two MELs with the other components of the fermentation crude.
- the fermentation crude may be subject to one or more separation methods, leading to other preferred MEL mixtures having the following characteristics:
- an MEL content greater than or equal to 30% by weight, preferably greater than or equal to 40% by weight, more preferably greater than or equal to 50% by weight;
- a content of other components including fatty acid (s), triglyceride (s), water, and / or strain) less than or equal to 70% by weight, preferably less than or equal to 60% by weight, more preferably less than or equal to at 50% by weight;
- mixtures of MELs more or less concentrated in MELs can be obtained.
- the mixture of MELs has the following characteristics:
- a content of other components including fatty acid (s), triglyceride (s), water, and / or strain) of not more than 45% by weight;
- the percentages by weight being given with respect to the weight of the mixture of MELs.
- the water content and / or strain is less than or equal to 10% by weight, preferably less than or equal to 5% by weight, relative to the weight of the mixture of MELs.
- the mixture of MELs has the following characteristics:
- an MEL content greater than or equal to 90% by weight, preferably greater than or equal to 95% by weight, more preferably greater than or equal to 98% by weight;
- a content of other components including fatty acid (s), triglyceride (s), water, and / or strain) less than or equal to 10% by weight, preferably less than or equal to 5% by weight, more preferably less than or equal to 2% by weight;
- the content of water and / or strain is less than or equal to 2% by weight, relative to the weight of the mixture of MELs.
- Such a mixture of MELs may, for example, be obtained using a fermentation process as described above, comprising several separation steps as described above, these separation steps preferably including a liquid extraction. / liquid and / or a passage on a mineral substrate.
- the passage over a mineral substrate may be a chromatography, such as adsorption chromatography on a silica column, carried out using suitable solvents.
- suitable solvents are known to those skilled in the art.
- the co-emulsifier according to the invention comprises at least two MELs.
- ester of hydroxy acid and mono- or di-glycerides of fatty acid is meant an ester comprising a hydroxy acid radical and at least one mono- or di-glyceride group in which at least one ester function results from the reaction between an acidic function of the hydroxy acid radical with an alcohol function of the mono- or diglyceride.
- the hydroxy acid radical comprises from 4 to 8 carbon atoms, more preferably from 4 to 6 carbon atoms.
- the hydroxy acid radical comprises at least two acid functions, preferably from 2 to 3 acid functions.
- an ester of hydroxy acid and mono- and di-glycerides of fatty acid (s) it is intended all esters of mono- and di-glycerides of fatty acid (s) comprising an identical hydroxy acid radical , in which
- the residual acid function (s) of the hydroxy acid radical can be neutralized, or
- One or more function (s) alcohol (s) of the hydroxy acid radical can be acetylated (s).
- esters because of the possible plurality of hydroxyl functions present in the mono- and diglycerides, and acid functions present in the hydroxy acid radical, a mixture of esters is likely to form, said esters differing only:
- glycerides namely mono or di-glycerides involved in the esterification reaction.
- the fatty acid (s) of the mono- and di-glycerides comprises (s) from 8 to 22 carbon atoms, more preferably from 10 to 18 carbon atoms, more preferably still from 12 to 18 carbon atoms. carbon.
- the emulsifier is an ester of hydroxyacid and mono- and di-glycerides of fatty acid, said mono- and di-glycerides of fatty acid (s) being constituted of a fatty acid .
- the emulsifier is a hydroxy acid ester and mono- and di-glycerides of fatty acids, said mono- and diglycerides of fatty acid (s) of the emulsifier consisting of at least two different fatty acids.
- the fatty acid mono- and di-glyceride hydroxyacid ester is a citric acid and acid mono- and di-glyceride ester.
- (s) fat more generally referred to as CITREM, or a mono- and diacetylated tartaric acid ester of mono- and di-glycerides of fatty acid (s), generally referred to as DATEM.
- CITREM and DATEM are conventionally prepared from vegetable oil (s) or from fatty acid (s) derived from vegetable oil.
- the hydroxy acid ester and mono- and di-glycerides of fatty acid (s), said hydroxy acid having at least 4 carbon atoms is an ester (optionally neutralized) of citric acid of mono- and di- oleic acid glycerides (that is to say mono- and di-glycerides having acyl groups whose hydrocarbon chain has 18 carbon atoms).
- This ester is advantageous because it is liquid at ambient temperature, and thus makes it possible to obtain an emulsion at ambient temperature.
- MEL s
- s a co-emulsifier of a hydroxy acid ester and mono- and di-glycerides of fatty acid, said hydroxy acid having at least 4 carbon atoms, makes it possible to reduce the size of the particles of the dispersed phase (oily phase) of the oil-in-water emulsions compared to the emulsions obtained with the emulsifier alone. This reduction in size is at least 20%, preferably at least 40%.
- MEL s
- s hydroxy acid ester and mono- and di-glycerides of fatty acid (s), said hydroxy acid having at least 4 carbon atoms
- MEL fatty acid
- s hydroxyacid ester and mono- and di-glycerides of fatty acid (s), said hydroxy acid having at least 4 carbon atoms, necessary to obtain an oil-in-water emulsion.
- the invention therefore relates to an emulsifying combination comprising:
- MEL mannosylerythritol lipid
- the emulsifying combination comprises a hydroxy acid ester and mono- and di-glycerides of fatty acid (s), said hydroxy acid having at least 4 carbon atoms as an emulsifier, and at least one MEL as co- emulsifier.
- the MEL and the fatty acid mono- and di-glyceride hydroxy acid ester (s), said hydroxy acid having at least 4 carbon atoms, are as previously described before, including the advantageous and preferred.
- the combination of a hydroxy acid ester and mono- and di-glycerides of fatty acid (s) in which the hydroxy acid has at least four carbon atoms, and at least one MEL has a synergistic effect.
- MEL When used alone, MEL does not provide a stable oil-in-water emulsion.
- a hydroxy acid ester and mono- and di-glycerides of fatty acid (s), said hydroxy acid having at least 4 carbon atoms, and at least one MEL makes it possible to obtain an emulsion oil-in-water with improved properties compared to an emulsion obtained from a hydroxy acid ester and mono- and di-glycerides of fatty acid (s), said hydroxy acid having at least 4 carbon atoms, alone .
- the emulsifying combination has a good low-content emulsifying property. Indeed, an emulsifier and co-emulsifier content of 3% by weight relative to the weight of an emulsion is sufficient to form an oil-in-water emulsion with all the advantages listed below.
- the emulsifying combination makes it possible to obtain a stable oil-in-water emulsion.
- stable is meant that at room temperature, no phase shift is observed at 42 days after the preparation of the emulsion.
- the emulsifying combination makes it possible to obtain a more stable oil-in-water emulsion than an emulsion obtained with the emulsifier alone.
- the emulsifying combination makes it possible to obtain an oil-in-water emulsion whose particle size of the dispersed phase (ie, the oily phase) is finer than that of the particles of an emulsion obtained with the emulsifier. only.
- low viscosity is meant that the dynamic viscosity at 25 ° C is less than 100 mPa.s, preferably less than 75 mPa.s, more preferably less than 50 mPa.s.
- the emulsifying combination according to the invention can be carried out at room temperature and atmospheric pressure, in particular during the preparation of an oil-in-water emulsion.
- the emulsifying combination makes it possible to obtain an oil-in-water emulsion easily, for example by simple stirring, such as mechanical stirring, without other means such as a homogenizer. under high pressure or a sonifier are needed.
- simple stirring such as mechanical stirring
- other means such as a homogenizer.
- high pressure or a sonifier are needed.
- the characteristics of the emulsifying combination according to the invention are more fully described in Example 4 below.
- the hydroxy acid ester and mono- and di-glycerides of fatty acid, said hydroxy acid having at least 4 carbon atoms, and the MEL are of renewable origin and do not exhibit toxicity nor for the environment neither for users. More preferably, the fatty acid mono- and di-glyceride hydroxyacid ester, said hydroxy acid having at least 4 carbon atoms, and the MEL are biodegradable.
- the weight ratio MEL (s) / hydroxy acid ester and mono- and di-glycerides of fatty acid (s), said hydroxy acid having at least 4 carbon atoms is between 5/95 and 50/50.
- the ratio by weight is between 5/95 and 40/60. Such a ratio allows a better stability of the oil-in-water emulsion obtained with the emulsifying combination according to the invention.
- the hydrophilic-lipophilic balance (HLB) of the emulsifying combination is between 9 and 13.
- HLB Hydrophilic-Lipophilic Balance
- GRIFFIN Hydrophilic-Lipophilic Balance
- the emulsifying combination according to the invention comprises at least 50% by weight of hydroxy acid ester and mono- and di-glycerides of fatty acid (s), said hydroxy acid having at least 4 carbon atoms, relative to the weight of the emulsifying combination.
- this comprises or consists of:
- the invention also relates to a process for the preparation of an emulsifying combination comprising a step of mixing a hydroxyacid ester and mono- and di-glycerides of fatty acid (s), said hydroxy acid having at least 4 carbon atoms and at least one MEL.
- hydroxy acid ester and mono- and di-glycerides of fatty acid (s), said hydroxy acid having at least 4 carbon atoms, and the (s) MEL (s) used in the preparation process of An emulsifying combination according to the invention are as described above including advantageous and preferential modes.
- the mixing step is carried out at a temperature at least equal to the highest melting temperature of the emulsifiers used.
- the mixing can be carried out at room temperature.
- the mixing can be carried out at a temperature between 40 and 80 ° C, more preferably between 50 and 70 ° C.
- the at least one MEL and the fatty acid mono- and di-glyceride hydroxyacid ester, said hydroxy acid having at least 4 carbon atoms, may be heated independently of each other beforehand when mixing or heated during mixing.
- the ratio by weight MEL (s) / hydroxyacid ester and mono- and diglycerides of fatty acid (s), said hydroxy acid having at least 4 carbon atoms is preferably between 5/95 and 50/50, more preferably between 5/95 and 40/60.
- the emulsifying combination is in the form of a homogeneous mixture, it can be used immediately or stored for later use.
- the emulsifying combination is fluid at ambient temperature and can therefore easily be handled at ambient temperature, especially during the preparation of compositions.
- the invention also relates to a composition
- a composition comprising:
- hydroxyacid ester and mono- and di-glycerides of fatty acid (s), said hydroxy acid having at least 4 carbon atoms,
- MEL mannosylerythritol lipid
- the MEL and the fatty acid mono- and di-glyceride hydroxy acid ester (s), said hydroxy acid having at least 4 carbon atoms are as previously described before, including the advantageous and preferred.
- the composition according to the invention comprises at least two MELs.
- the ratio by weight MEL (s) / hydroxyacid ester and mono- and diglycerides of fatty acid (s), said hydroxy acid having at least 4 carbon atoms is preferably between 5/95 and 50/50, more preferably between 5/95 and 40/60.
- composition according to the invention further comprises a hydrophobic substance.
- hydrophobic substance is intended to mean a substance that may be present in the oil phase of an emulsion, with the exception of the emulsifier (s) and co-emulsifier (s) and especially the emulsifier and co-emulsifier mentioned in the emulsifying combination according to the invention.
- the hydrophobic substance may be selected from the group consisting of mineral oils, silicones, fatty acids, fatty alcohols, esters other than MELs and esters of hydroxy acid and acid mono- and di-glycerides ( s) wherein the hydroxy acid has at least four carbon atoms, their ethoxylates and mixtures thereof.
- the mineral oil is liquid paraffin.
- the silicone is chosen from dimethicones and cyclopentasiloxane.
- the fatty acid is selected from stearic acid, cetyl acid and cetearyl acid.
- the fatty alcohol is chosen from stearic alcohol, cetyl alcohol and cetearyl alcohol.
- ester other than a MEL and a fatty acid mono- and di-glyceride hydroxyacid ester, said hydroxy acid having at least 4 carbon atoms, is chosen from the group consisting of :
- monoesters obtained from a monoalcohol such as methanol, ethanol, butanol, isopropanol, octanol, heptanol, ethylhexanol, stearyl alcohol, isostearyl alcohol, , dodecanol, isodecanol, isononanol, isooctanol, isopentanol, and a monocarboxylic acid having from 6 to 22 carbon atoms, such as caprylic acid, capric acid, heptanoic acid, palmitic acid, myristic acid, lauric acid, isostearic acid and oleic acid.
- a monoalcohol such as methanol, ethanol, butanol, isopropanol, octanol, heptanol, ethylhexanol, stearyl alcohol, isostearyl alcohol, , dodecanol, isode
- triesters obtained from glycerol and fatty acid (s), and in particular triglycerides
- tetraesters obtained from a tetra-alcohol, such as pentaerythritol, and a monocarboxylic acid as described above;
- the hydrophobic substance is selected from the most polar compounds.
- the hydrophobic substance is chosen from esters, more preferably from the group of esters described above.
- the hydrophobic substance is chosen from capric / caprylic triglycerides, pentaerythritol tetraisostearate, monopropylene glycol diheptanoate, ethylhexyl laurate, isoamyl laurate, triethylhexanoin, neopentyl glycol di-heptanoate, isononyl isononanoate, isopropyl myristate, diisoamyl sebacate, bis-2-ethylhexyl succinate, di-2-ethylhexyl sebacate and mixtures thereof.
- the hydrophobic substance is liquid at ambient temperature and at atmospheric pressure.
- the hydrophobic substance chosen will not advantageously be a silicone.
- the hydrophobic substance is chosen from substances intended to be brought into contact with the superficial parts of the animal body, and more particularly, human.
- the hydrophobic substance is edible.
- the composition comprises at least two hydrophobic substances, chosen from the hydrophobic substances mentioned above.
- composition according to the invention further comprises a hydrophilic alcohol.
- the hydrophilic alcohol is selected from the more polar alcohols.
- the hydrophilic alcohol is chosen from the group consisting of glycerol, ethanol, monopropylene glycol, sorbitol, xylitol, 1,3-butylene glycol, dipropylene glycol, benzyl alcohol and phenoxyethanol. octyldodecanol.
- the amount of alcohol may be between 0 and 70% by weight relative to the total weight of the composition, preferably between 0 and 30% by weight.
- the amount of alcohol may be between 0 and 70% by weight relative to the total weight of the composition, preferably between 0 and 30% by weight.
- composition may also include other hydrophilic substances such as preservatives, antioxidants, rheology modifiers, stabilizers and / or pH adjusting agents.
- the aqueous phase comprises all the hydrophilic substances, water and the hydrophilic alcohol.
- the total amount of MEL (s) and ester (s) of hydroxy acid and mono- and di-glycerides of fatty acid (s), said hydroxy acid comprising at least 4 atoms of carbon is preferably at least 2.5% by weight, more preferably at least 2.8% by weight, more preferably at least 3% by weight, the percentages by weight being expressed by relative to the weight of the composition.
- Total amount of MEL (s) and ester (s) of hydroxy acid and mono- and diglycerides of fatty acid (s), said hydroxy acid having at least 4 carbon atoms means the total amount of weight of molecules of MEL (s) and of molecules of hydroxyacid ester (s) and mono- and di-glycerides of fatty acid (s), said hydroxy acid having at least 4 carbon atoms.
- the total amount of hydrophobic substance (s) (or oily phase) in the composition is at least 1% by weight relative to the weight of the composition. Preferably, this amount is between 1 and 50% by weight, more preferably between 5 and 45% by weight relative to the total weight of the composition.
- the total amount of hydrophobic substance (s) (or oily phase) in the composition is at least 20% by weight, preferably at least 25% by weight, more preferably at least 30% by weight. by weight relative to the total weight of the composition.
- the ratio by weight of the total quantity of MEL (s) and ester (s) of hydroxy acid and mono- and di-glycerides of fatty acid (s), said hydroxy acid having at least 4 carbon atoms / total amount of hydrophobic substance (s) is between 0.060 and 3,000, more preferably between 0.070 and 0.600, more preferably still between 0.075 and 0.300.
- the amount of aqueous phase is preferably at least 40% by weight, more preferably at least 50% by weight, more preferably at least 60% by weight relative to the weight of the composition.
- the composition according to the invention is in the form of an oil-in-water emulsion.
- the invention also relates to a method for preparing a composition
- a method for preparing a composition comprising a step of mixing a hydroxy acid ester and mono- and diglycerides of fatty acid (s), wherein the hydroxy acid comprises at least 4 carbon atoms, at least one MEL and water.
- the MEL and the fatty acid mono- and di-glyceride hydroxyacid ester, said hydroxy acid having at least 4 carbon atoms, are as described above, including advantageous and preferential modes.
- the composition comprises at least two MELs.
- the invention more particularly a process for preparing an oil-in-water emulsion comprising an aqueous phase, an oily phase and:
- an emulsifier an ester of hydroxyacid and mono- and di-glycerides of fatty acid (s), said hydroxy acid comprising at least 4 carbon atoms, and
- a co-emulsifier at least one MEL
- said method comprising the following steps:
- the emulsifier and the co-emusifier can each be added individually to the aqueous phase and / or the oily phase.
- the MEL and the fatty acid mono- and di-glyceride hydroxy acid ester, said hydroxy acid having at least 4 carbon atoms, the aqueous phase and the oily phase are as described above before , including advantageous and preferential modes.
- the oil-in-water emulsion comprises at least two MELs.
- the preparation of the aqueous phase is carried out by mixing the hydrophilic substance (s).
- the preparation of the oily phase is carried out by mixing the hydrophobic substance (s).
- the contacting of the oily phase with the aqueous phase is preferably carried out by adding the oily phase to the aqueous phase with stirring.
- This agitation is preferably at least 400 rpm, more preferably at least 500 rpm.
- Homogenization by stirring is carried out at a stirring speed of preferably at least 7000 rpm, more preferably at least 8000 rpm.
- the preparation of the aqueous phase is carried out at room temperature or at an equal temperature or higher than the highest melting temperature of the substances constituting the aqueous phase.
- the preparation of the oily phase is carried out at room temperature or at an equal temperature or higher than the highest melting temperature of the substances constituting the oily phase.
- the hydroxyacid ester and mono- and diglycerides of fatty acid (s), said hydroxy acid having at least 4 carbon atoms, is present in the aqueous phase.
- an emulsifying combination prior to the preparation of the aqueous phase, an emulsifying combination may be prepared according to the process for preparing the emulsifying combination herein. before described.
- the hydroxy acid ester and fatty acid mono- and di-glycerides is present in the oily phase.
- an emulsifying combination may be prepared according to the process for preparing the emulsifying combination herein. before described.
- MEL may be present in the aqueous phase and / or the oily phase.
- the process for preparing an oil-in-water emulsion according to the invention may comprise an additional step of homogenization under high pressure. This additional step has the effect of further reducing the size of the dispersed phase particles (oily phase).
- the volume-weighted average particle diameter of the emulsion thus obtained is less than 500 nm, preferably less than 300 nm, more preferably still less than 200 nm.
- the emulsion obtained is an oil-in-water nanoemulsion.
- the emulsifying combinations and compositions according to the invention, and in particular the compositions in the form of an oil-in-water emulsion, can be used for the preparation of products in various applications.
- the invention also relates to the use of an emulsifying combination according to the invention, or a composition according to the invention, in particular in emulsion form, in cosmetic products, phytopharmaceutical products, lubricants or products. food.
- a fine-droplet emulsion indeed makes it possible to deposit it uniformly on a surface, to improve the spreading of this emulsion and to allow the active ingredients contained in the small droplets to penetrate more easily the surface on which they have been deposited.
- the invention also relates to a cosmetic, plant protection, lubricant or food product comprising a composition according to the invention, in particular a composition in the form of an emulsion.
- cosmetic product it is more particularly targeted solar or UV products or lotions, self-tanning products, makeup removers, tonics, care products, including mousses and serums, for skin or hair , moisturizing mists, deodorant wipes and cleansing or cleansing wipes.
- the cosmetic product according to the invention may also comprise one or more cosmetic active (s), perfume (s), pigment (s), dye (s), preservative (s), antioxidant (s), modifier (s) ) rheology, stabilizer (s) and / or agent (s) adjusters () pH.
- plant protection product refers more particularly to insect repellents, insecticides, fungicides and herbicides.
- the phytopharmaceutical product according to the invention may also comprise one or more phytopharmaceutical active (s), such as an insect repellent active, an insecticidal active agent, a fungicidal active agent, a herbicidal active agent.
- s phytopharmaceutical active
- Lubricating product is intended more particularly for cooling fluids.
- the lubricant product according to the invention may also comprise one or more antioxidant (s) and / or anti-wear (s) used in the field of lubricants.
- the term "food product” refers more particularly to cooking oils and margarines with a reduced fat content.
- the food product according to the invention may also comprise one or more food preservative (s).
- An emulsion comprising at least one MEL and a fatty acid mono- and di-glyceride hydroxyacid ester, said hydroxy acid having at least 4 carbon atoms, has the advantage that it can be sprayed in the form of fine droplets of average diameter (Dv50) advantageously less than 500 nm.
- Dv50 average diameter
- the emulsion obtained according to the invention can be used in sprayable products or impregnated wipes.
- the invention finally relates to a sprayable product comprising a reservoir and a system for propelling an emulsion, said emulsion comprising an emulsifying combination of the invention, or a composition according to the invention.
- the sprayable product may be in the form of an aerosol.
- the propulsion system is then constituted of a propellant gas.
- the propellant is selected from air, ethane, propane, butane, isobutane, isopentane, pentane, nitrogen, nitrous oxide and dimethyl ether.
- the sprayable product may be in the form of a frothing bottle.
- the propulsion system then consists of a foam pump.
- Example 1 Materials and Methods Implemented in the Examples
- MOT Oleon Radia 7104
- the MELs were obtained by a fermentation process comprising the following steps:
- a first mixture of MELs (mixture of MELs 1A) is obtained, which has the following characteristics:
- ⁇ MEL content at least 98% by weight, based on the total weight of the mixture of MELs obtained.
- each of the mixtures of MELs 1A and 1B comprise MELs-A at a content of 48% by weight, MELs-B at a content of 24% by weight, and MELs-C at a content of 27% by weight. weight, and MELs-D at a content of 1% by weight, the percentages by weight being given relative to the weight of the total amount of MELs.
- glycerol monolaurate (Jolee 7908 Oleon) are introduced and heated to 1 10 ° C. With stirring at 450 rpm, the pressure is reduced to 50 mbar for 30 minutes, then the temperature is lowered to 85 ° C. The citric acid, 123.5 g, and Dow Corning DC200 antifoam, 0.08 g, are then added. The pressure is again reduced to 150 mbar and the reaction medium heated at 130 ° C for about 8 hours. The acid number of CITREM L thus obtained is 33.
- the mixture of MELs 1B and a fatty acid mono- and di-glyceride hydroxyacid ester are heated to 60 ° C and then mixed with mechanical stirring at a rate of 500 rpm. min until a homogeneous mixture is obtained.
- the emulsifying combinations 1 to 5 have a liquid appearance.
- the emulsifying combinations 6 to 8 have a solid appearance.
- compositions were prepared in the amounts described in Table 2 below. The procedures are those described in points 1.1 and 1.2 below.
- Table 2 Compositions prepared in Example 3 1 .1. Preparation process at room temperature
- An emulsifying combination according to the invention or an emulsifier, and the hydrophilic substances of the aqueous phase are mixed with mechanical stirring at room temperature, ie approximately 25 ° C. +/- 5 ° C., until a mixture is obtained. homogeneous to obtain respectively a composition according to the invention or a comparative composition.
- This method can be implemented if the emulsifying combination or the emulsifier is liquid at ambient temperature and atmospheric pressure. This is the case of emulsifying combinations 1 to 5 and CO emulsifier.
- An emulsifying combination according to the invention or an emulsifier, and the hydrophilic substances of the aqueous phase are mixed with mechanical stirring at 80 ° C., until a homogeneous mixture is obtained to obtain a composition according to the invention or a comparative composition.
- an oily phase consisting of one or more hydrophobic substance (s) is added (27 g in 205 sec) with mechanical stirring at 600 rpm. Once the addition is complete, the composition is stirred for 2 minutes at 10,000 rpm using the homogenizer to obtain a composition in the form of an oil-in-water emulsion (hereinafter referred to as "emulsion" in the Examples).
- Example 4 Evaluation of the properties of the emulsions prepared in Example 3 1. Size of scattered particles
- the particle size of the oily phase dispersed in the aqueous phase as well as the specific surface area are measured using the granulometer one day after the preparation of said emulsions. Particle diameters are weighted in volume and are given in the following terms: "Dv10" represents the highest particle diameter of all the smaller particles representing 10% of the particle volume,
- Dv50 represents the average diameter of all the particles representing 50% of the volume of the particles.
- Dv90 represents the smallest particle diameter of all the larger particles representing 10% of the particle volume.
- Table 4 Size of the particles dispersed in emulsions 3, 6 to 8 according to the invention and comparative emulsions 1 to 4 prepared in Example 3 Regardless of the hydroxyacid and mono- and di-glyceride ester fatty acid, the replacement of 33% of the content thereof by MEL, reduces the size of the dispersed particles. 1 .3. According to the constituents of the oily and aqueous phases
- Table 5 Size of the particles dispersed in emulsions 3, 9 and 10 according to the invention prepared in Example 3
- the isoamyl laurate more polar than the MCT, makes it possible to obtain an emulsion with a mean diameter of particles Dv50 which is smaller (88 nm compared to 340 nm).
- the presence of glycerol in the aqueous phase makes it possible to overcome the higher viscosity of the oily phase (the dynamic viscosity of the pentaerythritol tetrahexanoate at 25 ° C. is 89%, 47 mPa.s, that of MCT is 23.74 mPa.s and that of isoamyl laurate of 4.72 mPa.s).
- the emulsion obtained is effectively as liquid as emulsions 3 and 9. These emulsions all have a dynamic viscosity at 25 ° C. of between 10 and 20 mPa ⁇ s.
- the emulsion 3 according to the invention was subjected to 1 minute of additional homogenization, ie 3 minutes of homogenization at 10,000 rpm after the end of the addition of the hydrophobic substance in the composition.
- Table 6 Size of the particles dispersed in the emulsion 3 according to the invention after three minutes of homogenization at 10,000 rpm.
- a Panda Plus 2000 high pressure homogenizer is used in this test.
- the emulsion 3 according to the invention is subjected to two successive passes at a pressure of 500 bar and then a passage at a pressure of 1000 bar.
- the emulsion remains stable after each pass.
- the emulsion After 6 months at 25 ° C., the emulsion remains stable with particles having a diameter of less than 200 nm.
- the stability is observed over time by measuring the volume of the less dense lower phase which can appear at the lower part of the emulsion. Indeed, the phenomenon of creaming that can appear, causes a phase separation with a creamy phase more dense in oily droplets at the top of the emulsion, and a less dense phase in oily droplets at the bottom of the emulsion. 2.1. Depending on the amount of MELs and CO
- Table 8 Stability of emulsions 1 to 3 according to the invention and comparative emulsion 1 prepared in Example 3
- Table 9 Stability at room temperature of emulsions 6 to 8 and comparative emulsions 2 to 4 prepared in Example 3
- the dynamic viscosity of the emulsions 1 to 5 according to the invention and of the comparative emulsion 1 was evaluated one day after their preparation, using the Brookfield viscometer at a temperature of 25 ° C. and at a speed of 10 tr / min for 1 minute.
- Table 10 Dynamic viscosity of emulsions 1 to 5 according to the invention and comparative emulsion 1 prepared in Example 3 plus the amount of hydroxyacid ester and fatty acid mono- and di-glycerides substituted by as MELs increase, the viscosity of the emulsion increases.
- the emulsions however remain very liquid, even with a quantity of MELs of 60% by weight relative to the weight of the emulsifying combination. This observation makes it possible to envisage applications requiring a very liquid emulsion that can be vaporized easily.
- An emulsion was prepared according to the amounts, in% by weight relative to the total weight of the emulsion, described in Table 1 1 below.
- Water, glycerol and the preservative are mixed to form the aqueous phase, to which the emulsifying combination 3 is added at ambient temperature and with stirring.
- the oily phase is prepared by mixing the three esters. This oily phase is then added at a flow rate of 1 g / 8 sec to the above mixture under mechanical stirring of 1500 rpm.
- the whole is then stirred for 2 minutes at 10,000 rpm using the homogenizer.
- Table 12 Size of the particles dispersed in the cosmetic emulsion The particles occupying 50% of the volume of the dispersed particles of the emulsion have an average diameter of 197 nm.
- Table 13 Cosmetic Emulsion Properties The cosmetic emulsion obtained is very white, very liquid and stable at least 45 days at room temperature.
- This cosmetic emulsion can serve as a basis for the development of low-viscosity cosmetic products, such as sprayable lotions (solar lotions and after-sprayable lotions) or impregnated wipes.
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- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Epidemiology (AREA)
- Birds (AREA)
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Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1758352A FR3070860B1 (fr) | 2017-09-11 | 2017-09-11 | Combinaison emulsifiante pour l'obtention d'emulsions de faible viscosite |
PCT/EP2018/074269 WO2019048664A1 (fr) | 2017-09-11 | 2018-09-10 | COMBINAISON EMULSIFIANTE POUR l'OBTENTION D'EMULSIONS DE FAIBLE VISCOSITE |
Publications (1)
Publication Number | Publication Date |
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EP3681465A1 true EP3681465A1 (fr) | 2020-07-22 |
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ID=60515560
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP18765124.5A Withdrawn EP3681465A1 (fr) | 2017-09-11 | 2018-09-10 | COMBINAISON EMULSIFIANTE POUR l'OBTENTION D'EMULSIONS DE FAIBLE VISCOSITE |
Country Status (3)
Country | Link |
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EP (1) | EP3681465A1 (fr) |
FR (1) | FR3070860B1 (fr) |
WO (1) | WO2019048664A1 (fr) |
Family Cites Families (5)
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DE19802206A1 (de) * | 1998-01-22 | 1999-07-29 | Beiersdorf Ag | Lipidreduzierte, fließfähige Zubereitungen |
DE102004003435A1 (de) * | 2004-01-21 | 2005-08-11 | Beiersdorf Ag | Dünnflüssige O/W-Emulsion |
DE102006004353A1 (de) | 2006-01-30 | 2007-08-02 | Goldschmidt Gmbh | Kaltherstellbare, niedrigviskose und langzeitstabile kosmetische Emulsionen |
JP5826171B2 (ja) * | 2010-05-27 | 2015-12-02 | 花王株式会社 | 水中油型乳化組成物 |
SG11201709383UA (en) * | 2015-12-18 | 2017-12-28 | Pola Chem Ind Inc | Oil-in-water type emulsion composition and method for producing same |
-
2017
- 2017-09-11 FR FR1758352A patent/FR3070860B1/fr not_active Expired - Fee Related
-
2018
- 2018-09-10 WO PCT/EP2018/074269 patent/WO2019048664A1/fr unknown
- 2018-09-10 EP EP18765124.5A patent/EP3681465A1/fr not_active Withdrawn
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WO2019048664A1 (fr) | 2019-03-14 |
FR3070860A1 (fr) | 2019-03-15 |
FR3070860B1 (fr) | 2019-09-20 |
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