EP4258884A1 - Composition liquide antimicrobienne et son utilisation comme activateur de conservateur de produits cosmetiques - Google Patents
Composition liquide antimicrobienne et son utilisation comme activateur de conservateur de produits cosmetiquesInfo
- Publication number
- EP4258884A1 EP4258884A1 EP21824287.3A EP21824287A EP4258884A1 EP 4258884 A1 EP4258884 A1 EP 4258884A1 EP 21824287 A EP21824287 A EP 21824287A EP 4258884 A1 EP4258884 A1 EP 4258884A1
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- European Patent Office
- Prior art keywords
- acid
- antimicrobial
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- weight
- salts
- 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.)
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Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
- A01N65/40—Liliopsida [monocotyledons]
- A01N65/44—Poaceae or Gramineae [Grass family], e.g. bamboo, lemon grass or citronella grass
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P3/00—Fungicides
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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
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
- A61K8/062—Oil-in-water emulsions
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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
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/34—Alcohols
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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
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/36—Carboxylic acids; Salts or anhydrides thereof
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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
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/36—Carboxylic acids; Salts or anhydrides thereof
- A61K8/365—Hydroxycarboxylic acids; Ketocarboxylic acids
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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
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/36—Carboxylic acids; Salts or anhydrides thereof
- A61K8/368—Carboxylic acids; Salts or anhydrides thereof with carboxyl groups directly bound to carbon atoms of aromatic rings
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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
- A61K8/602—Glycosides, e.g. rutin
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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
- A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
- A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
- A61K8/9783—Angiosperms [Magnoliophyta]
- A61K8/9794—Liliopsida [monocotyledons]
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
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- 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
- A61K2800/52—Stabilizers
- A61K2800/524—Preservatives
Definitions
- the invention relates to the field of the preservation of cosmetic products, and more specifically to the field of activators of preservatives for cosmetic products.
- preservative activator In order to obtain a preservative effect.
- preservative activators are not preservatives listed as such, but have activities, in particular antimicrobial, which supplement or increase the antimicrobial activity of the preservatives.
- Lonza patent WO 2014/014416 teaches antimicrobial compositions composed of a preservative active ingredient and a potentiator of said active ingredient.
- the preservative active can be chosen from a multitude of compounds, ranging from cinnamaldehyde to sorbic acid or benzoic acid, and essential oils of wintergreen or lemongrass.
- the potentiator can be chosen from erythorbic acid or gluconic acid, or their salts. Regarding gluconic acid, its cyclic form, known as gluconolactone, is preferred.
- Lemongrass oil is cited in this application, and the antibacterial activity data presented show that this essential oil does not have sufficient activity to act as a preservative or preservative activator. Many additives are mentioned in this application, including solubilizers, without any indication being given as to their nature or their usefulness for the composition or for the cosmetic formulation.
- the CleanWell patent US6346281 proposes combining citronella essential oil with metal ions, such as copper sulphate, and with a “biosurfactant” and a solvent.
- the "biosurfactant” can be either "BOD” or Tween-80 which is a polyethoxylated sorbitan.
- the solvent can be chosen from organic solvents such as ethanol.
- the combination of thyme oil with copper ions Cu2+ and an alkylpolyglucoside makes it possible to obtain a composition capable of foaming, useful for the treatment and prevention of bacterial infections resistant to antibiotics, in particular methicillin-resistant strains of Staphylococcus aureus.
- the Reckitt Benckiser patent US5403587 combines an essential oil of thyme or lemongrass with an ethoxylated fatty acid, a “nonoxynol-10” carboxylic acid, or a coconut fatty acid sodium salt, and with a surfactant and an organic solvent.
- the surfactant and the organic solvent are essential to provide a composition in liquid form capable of being dispersed or solubilized.
- the surfactant can be chosen from anionic or amphoteric surfactants. These combinations exhibit antibacterial activity on S. Aureus and on P. Aeruginosa.
- the Procter & Gamble patent W02008/126057 discloses antimicrobial compositions for the care of the mouth. They include a mixture of essential oils containing acyclic compounds and cyclic compounds. The addition of gluconic acid is recommended for its chelating power of the calcium ions located on the walls of the bacteria, which contributes to improving the bactericidal power of the composition.
- the composition can include all surfactants, but anionic surfactants, cationic surfactants, or zwitterionic surfactants are preferred.
- Nonionic surfactants are also cited, and the patent emphasizes nonionic surfactants prepared by condensation of alkylene oxide, i.e. polyethoxylated nonionic surfactants.
- Indusco US9687002 proposes putting lemongrass essential oil in a microemulsion in water with citric acid, lactic acid or acetic acid added as a pH buffer.
- the microemulsion is obtained thanks to at least two surfactants having an HLB between 9 and 18, and these surfactants can be nonionic surfactants.
- the microemulsion makes it possible to obtain a stable composition, i.e. remaining macroscopically homogeneous, and transparent.
- L'Oreal FR3061010 discloses essential oil nanoemulsions obtained by emulsification of these essential oils in a mixture of water and water-soluble organic solvent with surfactants chosen from anionic, nonionic, amphoteric, zwitterionic or cationic surfactants. These nanoemulsions are prepared for their topical use for the treatment of bacterial or fungal infections. Lemongrass essential oil is presented although no antimicrobial activity is attributed to it.
- nonionic surfactants alkyl polyglucosides are preferred, and particularly caprylyl/capryl glucoside, such as OramixTM CG110 from Seppic.
- OramixTM CG110 is formulated with ten essential oils, ethanol and water.
- the amount of OramixTM CG110 used therein is 0.05% by weight relative to the total weight of the formulation.
- L'Oréal FR3061010 recommends using an amount of nonionic surfactant of less than 1% by weight relative to the total weight of the nanoemulsion. It is the combination of a nonionic surfactant and ethanol which makes it possible to obtain a nanoemulsion. This state of nanoemulsion has advantages in terms of texture, softness to the touch, and transparency.
- essential oils are natural extracts insoluble in water, known since antiquity for their antiseptic activities, but also for their potential allergenicity, which requires finding, for their use in cosmetics, a dose balanced between the need to increase this dose, to increase the antiseptic activity, and the need to reduce this dose, so as not to cause an allergy.
- the antiseptic activity has the widest possible spectrum, in order to be able to inhibit the growth or kill all microorganisms, namely bacteria, fungi, yeasts, and viruses.
- composition of a cosmetic product is very different from that of an in-vitro test culture medium.
- interactions between the constituents of the antimicrobial composition and the ingredients of the cosmetic product may occur, resulting in the alteration or suppression of the antimicrobial activity. It may then be necessary to increase the dose of antimicrobial composition to regain the antimicrobial activity in situ.
- a preservative activator composed of natural products or products of natural origin, biodegradable, devoid of ethoxylated or silicone compounds, transparent and which can be integrated into a cosmetic product without altering the physical properties -chemicals of the product, that is to say without altering or destabilizing the cosmetic product, or causing a phase shift or the formation of solid particles, and this for the majority of dosage forms. It is also necessary to develop a formulation that preserves the antimicrobial properties of the activator.
- FIG. 1 shows the results of antimicrobial activity testing of the antimicrobial liquid composition on Escherichia coli ATCC® 8739.
- Fig. 2 [0021][Fig. 2] shows the results of antimicrobial activity testing of the antimicrobial liquid composition against Candida albicans ATCC® 10231.
- FIG. 3 shows the results of antimicrobial activity testing of the antimicrobial liquid composition against Aspergillus brasiliensis ATCC® 16404.
- FIG. 4 shows the results of antimicrobial activity testing of the antimicrobial liquid composition against Staphylococcus aureus ATCC® 6538.
- FIG. 5 shows the results of antimicrobial activity testing of the antimicrobial liquid composition against Pseudomonas aeruginosa ATCC® 9027.
- antimicrobial compositions according to the invention make it possible to activate preservatives and increase their antimicrobial protection.
- strong logarithmic reductions in the number of colony-forming units of Pseudomonas Aeruginosa, Escherichia Coli, Aspergillus brasiliensis, Candida albicans and Staphylococcus Aureus are measured when the antimicrobial compositions are introduced into the cosmetic composition, in combination with a preservative, and this compared to a cosmetic composition comprising only a preservative usually used.
- the present invention relates to the use of an antimicrobial liquid composition for activating the preservatives of cosmetic products, said antimicrobial liquid composition comprising:
- At least one essential oil chosen from the essential oils of species of the genus Cymbopogon, the essential oils of clove, Bourbon geranium, noble laurel, lemony litsea, lemon balm, pepper, crown pepper, oregano, tea tree, thyme, lemongrass;
- At least one nonionic surfactant chosen from alkyl(poly)glycosides, alkylglycosides, esters of vegetable oils, non-ethoxylated fatty esters of polyols, heteropolymers of C8-C10 alkylglycosides and sorbitan fatty esters, or mixtures thereof,
- At least one carboxylic acid in free form At least one carboxylic acid in free form.
- the present invention also relates to antimicrobial compositions comprising
- compositions advantageously make it possible to stabilize the cosmetic products in which they are incorporated, without altering or destabilizing the cosmetic product, or causing a phase shift or the formation of solid particles.
- the antimicrobial compositions according to the invention keep their antimicrobial activity once formulated in a cosmetic product.
- the present invention also relates to cosmetic products comprising antimicrobial compositions according to the invention and at least one preservative.
- the constituents other than water of the antimicrobial composition that is the subject of the present application are sometimes marketed in the form of aqueous solutions, composed of water and one of said constituents.
- the mass percentages of said constituents other than water in the antimicrobial composition expressed in% by dry weight, are the mass percentages of the dry masses into said constituents, in other words the mass percentages of said dry constituents, water being excluded.
- the liquid antimicrobial composition which is the subject of the present application is an aqueous composition.
- the quantities of liquid antimicrobial composition used are expressed in gross mass percentages, denoted as % by gross weight, accounting for the antimicrobial liquid composition in its entirety, in other words taking into account all of its constituents, including water.
- the present invention relates to the use of an antimicrobial liquid composition for activating the preservatives of cosmetic products, said antimicrobial liquid composition comprising:
- At least one essential oil chosen from the essential oils of species of the genus Cymbopogon, the essential oils of clove, Bourbon geranium, noble laurel, lemony litsea, lemon balm, pepper, crown pepper, oregano, tea tree, thyme, lemongrass or a mixture of these oils;
- At least one non-ionic surfactant chosen from alkyl (poly) glycosides, alkyl glycosides, alkyl glycosides, esters of vegetable oils, non-ethoxylated fatty esters of polyols, heteropolymers of C8-C10 alkylglycosides and sorbitan fatty esters, or mixtures thereof,
- the present invention relates to the use of an antimicrobial liquid composition to activate the preservatives of cosmetic products, said antimicrobial liquid composition comprising:
- At least one essential oil chosen from the essential oils of species of the genus Cymbopogon, the essential oils of clove, Bourbon geranium, noble laurel, lemony litsea, lemon balm, pepper, crown pepper, oregano, tea tree, thyme, lemongrass or a mixture of these oils;
- At least one nonionic surfactant chosen from alkyl(poly)glycosides,
- an antimicrobial composition is a composition which exhibits antimicrobial activity, that is to say that the composition is capable of slowing down the growth of at least certain bacteria, fungi or yeasts, better at inhibiting the growth and lowering the presence in number of at least some of them by preventing them from developing and multiplying, and even better at make their presence undetectable and make them completely disappear by killing them. Therefore, the definition encompasses growth retardation, growth inhibition under the known terms bacteriostatic and fungistatic, and also lethal activity, known as bactericidal or fungicidal.
- the antimicrobial composition according to the invention proves by itself insufficiently effective in preserving a cosmetic product (i.e. it does not significantly slow down or inhibit the growth of bacteria or fungi and does not have bactericidal or fungicidal activity).
- the antimicrobial composition according to the invention combines its antimicrobial activity with the activity of said preservative, and potentiates the activity of said preservative. It will then be possible to use a reduced dose of preservative, in combination with an appropriate dose of antimicrobial composition, to successfully reduce the load of microorganisms in the cosmetic product, that is to say reduce the number of colony-forming unit, or even preferentially to stabilize the microbiology of the cosmetic product according to the ISO 11930:2019 standard.
- the antimicrobial composition thus effectively makes it possible to reduce the quantity of preservative necessary to preserve the cosmetic product, and this over periods equivalent to the usual preservatives used at the recommended doses, which are generally equal to the maximum concentrations permitted in ready-to-use cosmetic products.
- Preservatives in cosmetic products are present in the cosmetic composition, either alone or in combination, in a content of approximately 1% by weight, relative to the total weight of the composition.
- the antimicrobial compositions according to the invention make it possible to reduce the preservative content (for example 0.4% for potassium sorbate and sodium benzoate), and to use only one preservative.
- a preservative activator is a compound which has insufficient antimicrobial activity by itself in the cosmetic product, but which is capable of increasing the antimicrobial activity of a preservative in the cosmetic product.
- the term “insufficient antimicrobial activity” means a compound which does not make it possible, in a significant manner, to slow down the growth of bacteria, fungi or yeasts, and even less to inhibit their growth or kill them.
- the preservative activator cannot therefore microbiologically stabilize a medium by itself, and therefore cannot be qualified as a preservative within the meaning of the regulations.
- a preservative with a preservative activator therefore makes it possible to at least increase the antimicrobial activity of the preservative and preferably to stabilize a cosmetic product microbiologically. It is generally desired that this stabilization or increase occur at a dose of preservative lower than the dose required when the preservative is used alone.
- the antimicrobial activity can be evaluated by any method known to those skilled in the art.
- the classification can be made by monitoring the reduction in the number of colony-forming units (denoted cfu/mL) at seven, fourteen and twenty-eight days after the cosmetic product has been inoculated with a microorganism.
- the reduction in the number of colony forming units is expressed in logarithm base 10, for example one log of reduction corresponds to a reduction of 10 A 1 , i.e. 10, cfu/mL, or two logs of reduction correspond to a reduction of 10 At 2, i.e. 100, cfu/mL.
- the antimicrobial activity is evaluated according to the international standard ISO 11930:2019 entitled "ISO11930 Cosmetics - Microbiology - Evaluation of the antimicrobial protection of a cosmetic product” which specifies a procedure for the interpretation of the data resulting from the test of the effectiveness of the antimicrobial protection and/or the assessment of the microbiological risk during the overall evaluation of the antimicrobial protection of a cosmetic product.
- a composition will be considered as a preservative activator when, combined with the preservative, it makes it possible to increase by at least 1 log the reduction in the number of colony-forming units of microorganisms present in the medium, preferably at least two logs, preferably at least 3 logs, compared to the number of colony forming units when the preservative alone is used.
- a composition will be considered as a preservative activator when combined with the preservative, it makes it possible to increase by at least 1 log the reduction in the number of units forming colonies of microorganisms present in the medium, preferentially to the at least two logs, preferably at least 3 logs, compared to the number of colony-forming units of microorganisms when the preservative alone is used, over a period of at least 7 days, preferably 14 days and even more preferably over a period of at least 28 days.
- the antimicrobial liquid composition that is the subject of the present application can be qualified as a liquid composition with a preservative-activating effect because it satisfies the preceding definition of preservative-activating agent.
- the antimicrobial liquid composition is therefore a liquid composition with a preservative-activating effect.
- the antimicrobial composition according to the invention makes it possible to activate a preservative and, combined with said preservative, to reduce by at least one log, preferably at least two logs, preferably at least three logs, the number of colony forming units of Pseudomonas Aeruginosa, Escherichia Coli, Aspergillus brasiliensis, Candida albicans and Staphylococcus aureus.
- the antimicrobial composition according to the invention makes it possible to activate a preservative and, combined with said preservative, to reduce by at least one log, preferentially by at least two logs, preferentially by at least 3 logs, the number of colony-forming units of Pseudomonas Aeruginosa, Escherichia Coli, Aspergillus brasiliensis, Candida albicans and Staphylococcus aureus, over a period of at least 7 days, preferably at least 14 days and preferably at least 28 days.
- the antimicrobial composition comprises an essential oil chosen from essential oils of species of the genus Cymbopogon, essential oils of clove, Bourbon geranium, noble laurel, lemon-litsea, lemon balm , chili, crown pepper, oregano, tea tree, thyme, lemongrass or a mixture of these oils.
- the essential oil is chosen from essential oils of species of the genus Cymbopogon.
- Cymbopogon is a genus of monocotyledonous plants of the Poaceae family, Panicoideae subfamily, which comprises about fifty species originating from the tropical and subtropical regions of Africa, Asia and Australia. They are herbaceous plants, generally perennial, rarely annual, cespitose or rhizomatous, whose stems (culms) can reach 15 to 300 cm in length.
- the essential oil of species of the genus Cymbopogon is chosen from oils of species of the genus Cymbopogon rich in citral, neral, geranial and geraniol.
- the essential oil of species of the genus Cymbopogon is chosen from essential oils of species of the genus Cymbopogon having approximately 30% by weight in neral, approximately 40% by weight in geranial, and 5% by weight in geraniol. These mass percentages are usually determined by chromatography.
- Cymbopogon nardus also called Ceylon lemongrass or Sri Lankan lemongrass
- Cymbopogon schoenanthus also called Camel grass or geranium grass
- Cymbopogon winterianus Jowitt also called Java Lemongrass - Cymbopogon martinii var. sofia, also called gingergrass
- the Cymbopogon essential oil is chosen from the essential oils of the Cymbopogon flexuosus Stapf species. and Cymbopogon citratus (DC.) Stapf.
- the essential oil is an essential oil of citronella of the species Cymbopogon citratus (DC.) Stapf.
- essential oils of Cymbopogon flexuosus Stapf. and Cymbopogon citratus (DC.) Stapf. have about 30% by weight neral, about 40% by weight geranial, and 5% by weight geraniol
- the essential oil can also be advantageously chosen from other oils rich in citral, neral, geranial and geraniol.
- It may be, for example, essential oil of lemon bedsea which contains approximately 40% by weight of geranial and approximately 30% by weight of neral or essential oil of lemon balm of the species Melissa officinalis, compared to the total weight of essential oil.
- an essential oil rich in geraniol and geraniol such as in particular the essential oil of palmarosa (Cymbopogon martini) which usually contains between 80% and 85% by weight of geraniol relative to the total weight of essential oil.
- the essential oil will comprise at least one active molecule chosen from the active molecules that make up the essential oil lemongrass of the species Cymbopogon flexuosus and Cymbopogon citratus: the trans isomer of citral, known as geranial or citral A, with the name IIICPA (E)-3,7-Dimethylocta-2,6-dienal; the cis isomer of citral, known as neral, or citral B, of the name IIICPA (Z)-3,7-Dimethylocta-2,6-dienal; geraniol, named IIICPA (2E)-3,7-dimethylocta-2,6-dien-1-ol.
- the trans isomer of citral known as geranial or citral A, with the name IIICPA (E)-3,7-Dimethylocta-2,6-dienal
- the cis isomer of citral known as neral, or citral B, of the
- the essential oil is chosen from the essential oils of Cymbopogon, lemon-litsea, lemon balm.
- the essential oil useful for the antimicrobial composition that is the subject of the present application can be chosen from the essential oils of ajwain (also called Indian thyme), star anise (also called star anise ), basil, Chinese or Ceylon cinnamon, cardamom, cypress from governing, lemon eucalyptus, eucalyptus globulus, eucalyptus radiata, black spruce, tarragon, fennel, wintergreen , Virginia juniper, grass geranium, rose geranium, Bourbon geranium, gingergrass, clove (clove), fragrant inula, noble laurel, reydovan lavandin, fine lavender, cineole aspic lavender, true lavender, lavandin, super lavandin, garden marjoram, shell marjoram, linear-leaved tea tree, field mint, peppermint, lemon balm, red myrtle, neroli, niaouli, petit grain big
- the essential oil may also be an oil rich in phenols, in particular in carvacrol (present for example in the essential oil of savory), in thymol (present for example in the essential oil of thyme with thymol) and in eugenol (present for example in clove essential oil). These phenols are responsible for the fungicidal and bactericidal activities of the essential oils that contain them.
- Mention may more particularly be made, as oils rich in phenols, of the essential oils of thyme (Thymus mastichina, Thymus vulgaris, Thymus zygis, Thymus thymi), pepper (Pimenta racemosa, Pimenta acris), ajowan (Trachyspermum ammi), clove (Eugenia caryophyllus), mountain savory (Satureja montana), oregano (Origanum heracleoticum (Greek oregano), Origanum majorana, Origanum vulgare, Origanum compactum (Oregano compact), Spanish oregano (Corydothymus capitatus), Ceylon cinnamon (Cinnamomum verum).
- the essential oil will comprise at least one active molecule chosen from monoterpenols, which are alcohols with 10 carbon atoms, preferably geraniol, linalool, thujanol, myrcenol, terpineol, menthol and piperitol.
- Essential oils that include these active molecules are palmarosa Cymbopogon martinii, spike lavender Lavandula spica, peppermint Mentha piperita, marjoram Origanum majorana, and tea tree essential oils. species Melaleuca alternifolia.
- another essential oil poor in at least one phenol, monoterpenol, terpene oxide, aromatic aldehyde, terpene aldehyde, phenylpropene, monoterpene hydrocarbon, and sesquiterpene hydrocarbon can be added to the composition object of the present application, for example to perfume it, change its smell or act on its antimicrobial activity. It can be chosen from essential oil of cedar, essential oil of sweet orange, essential oil of lemon, essential oil of green or red mandarin, or essential oil of wintergreen.
- the total quantity of essential oils present in the antimicrobial liquid composition can range from 0.1% to 10% by dry weight, preferentially from 0.5% to 7% by dry weight, more preferentially from 1% to 5 % by dry weight, and most preferably from 1.5% to 3% by dry weight, relative to the total weight of the antimicrobial liquid composition.
- the ratio of the total dry mass of nonionic surfactants to the total dry mass of essential oils may also be greater than or equal to 2, preferably greater than or equal to 3, more preferably greater than or equal to 4, and any preferably greater than or equal to 5.
- the essential oil(s) are advantageously present in the antimicrobial composition in a quantity which is lacking with respect to the quantity of nonionic surfactant(s). The selection of this default situation makes it possible to best solubilize the essential oil or oils in the water of the antimicrobial liquid composition, and also contributes to maintaining this solubilization in the water of the cosmetic product when the said liquid composition antimicrobial is diluted in said cosmetic product, and in particular in the water of said cosmetic product.
- This ratio advantageously makes it possible to obtain a stable antimicrobial liquid composition, without phase shift or precipitation over time, while being transparent or opalescent, in the concentrated state or even after high dilution in water.
- the nonionic surfactant is chosen from:
- alpha-diols and (C1-C20)alkylphenols these compounds being polyethoxylated and/or polypropoxylated and/or polyglycerolated, the number of ethylene oxide and/or propylene oxide groups possibly ranging from 1 to 100, and the number of glycerol groups possibly ranging from 2 to 30; or alternatively these compounds comprising at least one fatty chain comprising from 8 to 40 carbon atoms, in particular from 16 to 30 carbon atoms; in particular alcohols comprising at least one C8 to C40 alkyl chain, saturated or not, linear or branched, oxyethylenated comprising from 1 to 100 moles of ethylene oxide, preferably from 2 to 50, more particularly from 2 to 40 moles of ethylene oxide and comprising one or two fatty chains;
- polyethoxylated fatty amides preferably having from 2 to 30 ethylene oxide units, polyglycerolated fatty amides comprising on average from 1 to 5 glycerol groups and in particular from 1.5 to 4;
- polyoxyalkylenated fatty acid esters preferably polyoxyethylenated, having from 2 to 150 moles of ethylene oxide, including oxyethylenated vegetable oils;
- amine oxides such as (C10-C14 alkyl)amine oxides or N-(C10-C14 acyl)-aminopropylmorpholine oxides; - non-ethoxylated fatty esters of polyols, and in particular from non-ethoxylated fatty esters of glycerol, polyglycerols, sorbitol, sorbitan, androdrohexitols such as in particular isosorbide, mannitol, xylitol, erythritol, maltitol, sucrose, glucose, polydextrose, hydrogenated glucose syrups, dextrins and hydrolyzed starches,
- esters of polyglycerol and saturated or unsaturated C4-C20 fatty acids preferably C8-C18, and more preferably C18, for example polyglyceryl-2 dipolyhydroxystearate and polyglyceryl-3 diisostearate,
- - vegetable oil esters in particular from coconut oil esters, for example coco-caprylate, and mixtures thereof.
- the nonionic surfactant is chosen from alkyl(poly)glycosides, which are represented by the following general formula:
- Ri represents: a linear or branched alkyl or alkenyl radical containing 6 to 24 carbon atoms, or 6 to 18 carbon atoms, or 6 to 12 carbon atoms; or an alkylphenyl radical whose linear or branched alkyl radical contains 6 to 24 carbon atoms, or 6 to 18 carbon atoms, or 6 to 12 carbon atoms,
- R 2 represents an alkylene radical containing 2 to 4 carbon atoms
- - G represents a sugar unit comprising 5 to 6 carbon atoms
- - 1 denotes a value ranging from 0 to 10, preferably from 0 to 4,
- - v denotes a value ranging from 1 to 15, preferably from 1 to 4.
- alkyl(poly)glycoside surfactants are compounds of the formula described above in which:
- Ri denotes a saturated or unsaturated, linear or branched alkyl radical comprising from 6 to 18 carbon atoms, or from 6 to 12 carbon atoms,
- R 2 represents an alkylene radical containing 2 to 4 carbon atoms
- - 1 denotes a value ranging from 0 to 3, preferably equal to 0,
- G denotes glucose, fructose or galactose, preferably glucose
- the degree of polymerization that is to say the value of v, which can range from 1 to 15, preferably from 1 to 4; the average degree of polymerization being more particularly between 1 and 2.
- the glucosidic bonds between the sugar units are generally of the 1-6 or 1-4 type, preferably of the 1-4 type.
- the alkyl(poly)glycoside surfactant is an alkyl(poly)glucoside surfactant, that is to say an alkyl(poly)glycoside surfactant where G is glucose.
- G is glucose.
- the surfactant is chosen from capryl/capryl glucosides.
- the nonionic surfactant can also be chosen from alkyl(poly)glycosides, preferably alkyl(poly)glucosides, with an HLB greater than or equal to 10, or greater than or equal to 12, or greater than or equal to 14.
- Alkyl(poly)glycosides preferably alkyl(poly)glucosides, can also be combined with fatty alcohols.
- the nonionic surfactant can also be chosen from heteropolymers of C8-C10 alkylglycosides and fatty esters of sorbitan, preferably from heteropolymers of C8-C10 alkylglycosides and C4-C20 fatty esters of sorbitan, and more preferably from heteropolymers of C10 alkylglycosides and of C18 fatty esters of sorbitan.
- An example of such a heteropolymer is Poly Suga® Mulse D9 from Colonial Chemical Inc.
- the total amount of nonionic surfactants in the antimicrobial liquid composition is greater than or equal to 1% by weight, preferably greater than or equal to 5% by weight, more preferably greater than or equal to 7.5% by weight, and any preferably greater than or equal to 10% by weight, relative to the total weight of said liquid antimicrobial composition.
- the total quantity of nonionic surfactants present in the liquid antimicrobial composition can range from 1% to 50% by weight, preferentially from 1% to 40%, preferentially from 5% to 40% by weight, preferentially 5% to 30% by weight, more preferably from 7.5% to 30% by weight, more preferably 7.5 to 20% by weight, and most preferably from 10% to 20% by weight, relative to the total weight of the composition antimicrobial liquid.
- the ratio of the total dry mass of nonionic surfactants to the total dry mass of essential oils may also be greater than or equal to 2, preferably greater than or equal to 3, more preferably greater than or equal to 4, and any preferably greater than or equal to 5.
- the nonionic surfactant(s) are advantageously present in the antimicrobial composition in an amount which is in excess relative to the amount of the essential oil(s). The selection of this excess situation makes it possible to best solubilize the essential oil or oils in the water of the antimicrobial liquid composition, and also contributes to maintaining this solubilization in the water of the cosmetic product when the said antimicrobial liquid composition is diluted in said cosmetic product, and in particular in the water of said cosmetic product.
- a value of the ratio of the mass of caprylyl/capryl glucoside to the mass of essential oil greater than or equal to 2, preferably greater than or equal to 3, more preferably greater than or equal to 4, most preferably greater than or equal to 5, makes it possible to obtain a completely transparent and stable antimicrobial liquid composition over time in the concentrated state and in the diluted state in the water.
- Cosmetic product formulators generally prefer to employ transparent ingredients to formulate their products.
- the selection of nonionic surfactants according to the invention makes the liquid antimicrobial composition compatible with ionic surfactants and zwitterionic surfactants. It is therefore possible to add the composition antimicrobial to a cosmetic product comprising another type of surfactant while maintaining good physical stability of the state of the cosmetic product, and retaining the effects of ionic or zwitterionic surfactants, that is to say without masking or neutralizing the effects of these surfactants.
- the antimicrobial composition according to the invention can be added to shampoos or shower gels, which comprise anionic surfactants, often in high quantities, while retaining the detergent power of the anionic surfactants, and retaining the monophasic state liquid or gel.
- the liquid antimicrobial composition can also be added to a coloring solution or hair conditioner, generally comprising cationic surfactants or cationic polymers, while retaining the coloring ability and conditioning ability of the hair.
- the free carboxylic acid useful for the antimicrobial composition which is the subject of the present application is chosen from monocarboxylic acids and polycarboxylic acids, linear or branched, preferentially from monocarboxylic acids, dicarboxylic acids, and tricarboxylic acids, very preferentially among monocarboxylic acids and dicarboxylic acids.
- free it is meant that the carboxylic acid function is either in its protonated form COOH, or in its ionized form COO- associated with a counter ion H+ or H3O+, and this in proportions dependent on the value of the pH. of the aqueous solution of acid and the strength of the acid characterized by its pKa.
- the carboxylic acid is chosen from monocarboxylic acids whose carbon chain consists of 2 to 12 carbon atoms, or 3 to 8 carbon atoms.
- monocarboxylic acids whose carbon chain consists of 2 to 12 carbon atoms, or 3 to 8 carbon atoms.
- lactic acid glycolic acid
- glucuronic acid maltobionic acid
- lactobionic acid malic acid
- tartaric acid mandelic acid
- fatty acids (or aliphatic chain carboxylic acids) having a carbon chain of 4 to 12 atoms preferably natural fatty acids such as in particular propionic, butyric, caproic, caprylic, capric and lauric acids.
- the carboxylic acid is chosen from gluconic acid, glucuronic acid, maltobionic acid, preferentially the carboxylic acid is gluconic acid.
- the monocarboxylic acid is the cyclic form of gluconic acid, called gluconolactone.
- the carboxylic acid is chosen from polycarboxylic acids, and preferably from dicarboxylic acids and tricarboxylic acids, and most preferably from aspartic acid, adipic acid, malonic, pimelic acid, succinic acid, glucaric acid, and glutaric acid, and even more preferably is succinic acid.
- carboxylic acid(s) or polycarboxylic acid(s) useful for the antimicrobial liquid composition which is the subject of the present application are further characterized by a pKa value ranging from 3 to 6, preferably from 4 to 6.
- the total amount of free carboxylic acid(s) present in the liquid antimicrobial composition can range from 10% to 70% by dry weight, preferably from 20% to 60% by dry weight, more preferably from 25% to 50% by dry weight. dry weight, and most preferably from 27.5% to 40% by dry weight, relative to the total weight of the antimicrobial liquid composition.
- the carboxylic acid salt useful for the antimicrobial composition which is the subject of the present application is chosen from salts of monocarboxylic acids or salts of linear or branched polycarboxylic acids.
- the carboxylic acid function is either in the protonated form COOH, or in the ionized form COO- associated with a metallic counter ion M+, and this in proportions dependent on the pH value of the aqueous acid solution , the acidity constant pKa of the corresponding free acid, and the dissociation constant of the salt pKd.
- the carboxylic acid salt or salts is or are chosen from sodium, magnesium, zinc, calcium, potassium, iron, lithium, carboxylic acid salts chosen from the carboxylic acids of "free carboxylic acid" part of the present application.
- the carboxylic acid salt is a salt of the free carboxylic acid useful for the composition that is the subject of the present application.
- said carboxylic acid is distributed in at most 35% by dry weight in salt of said carboxylic acid and in at least 65% by dry weight in said free carboxylic acid.
- gluconic acid distributed at 35% by dry weight as sodium gluconate and 65% by dry weight as free gluconic acid.
- such a mixture of acid and its salt has a pH that is better tolerated by the skin and is less irritating than the acid alone can be.
- the carboxylic acid salt or salts is or are chosen from sodium, magnesium, zinc, calcium, potassium, iron or lithium salts of gluconic acid or succinic acid, and preferably the carboxylic acid salt or salts are chosen from sodium gluconate and sodium succinate, and most preferably the carboxylic acid salt is sodium gluconate.
- the total quantity of carboxylic acid salts present in the liquid antimicrobial composition can range from 1% to 50% by dry weight, preferentially from 5% to 30% by dry weight, more preferentially from 10% to 20% by dry weight. dry weight, and most preferably from 15% to 17.5% by dry weight, relative to the total weight of the antimicrobial liquid composition.
- the water present in the antimicrobial liquid composition can be decarbonated water, or demineralized water.
- the amount of water present in the antimicrobial liquid composition can range from 20% to 75% by weight, preferably from 30% to 65% by weight, more preferably from 35% to 55% by weight, relative to the weight total antimicrobial liquid composition.
- the pH of the antimicrobial liquid composition that is the subject of the present application can range from 2 to 9, preferably from 3 to 8, more preferably from 4 to 7, and even more preferably from 4.5 to 6.5, and even more more preferably from 5.5 to 6.2.
- the preservative can be chosen from propionic acid, calcium propionate, formaldehyde, paraformaldehyde, o-phenylphenol or its salts, zinc pyrithione, sodium sulphites, bisulphites or metabisulphites, d ammonium, potassium, chlorobutanol, methylparaben, ethylparaben, propylparaben, butylparaben, formic acid and its salts such as sodium formate, benzoic acid and its salts such as sodium benzoate, sorbic acid and its salts, such as calcium sorbate, sodium sorbate, potassium sorbate, salicylic acid and its salts, dehydroacetic acid and its salts such as sodium dehydroacetate, undecylenic acid and its salts such as calcium undecylenate, potassium undecylenate, sodium undecylenate, phenoxyethanol, 1,2-dimethylol-5,6-dimethylhydantoin,
- the antimicrobial composition is a preservative activator for the following preservatives: benzoic acid, sodium benzoate, salicylic acid and its salts, sorbic acid, calcium sorbate, sodium sorbate, potassium sorbate, dehydroacetic acid, sodium dehydroacetate, undecylenic acid, calcium undecylenate, potassium undecylenate, sodium undecylenate, phenoxyethanol, 1,2-Dimethylol-5,6-dimethylhydantoin, benzyl alcohol, chlorhexidine, chlorhexidine diacetate, chlorhexidine digluconate, dihydrochloride chlorhexidine, behentrimonium chloride, cetrimonium chloride, cetrimonium bromide, laurtrimonium chloride, laurtrimonium bromide, steartrimonium chloride, steartrimonium bromide, hexamidine, hexamidine diisethionate, chlorphenesin
- the preservative is chosen from formic acid and its salts, dehydroacetic acid and its salts, benzoic acid and its salts, sorbic acid and its salts, phenoxyethanol, benzyl alcohol and its salts. More preferably, the preservative activated by the liquid antimicrobial composition is chosen from benzoic acid, sorbic acid, phenoxyethanol, benzyl alcohol, sodium benzoate, potassium sorbate. Even more preferably, the preservative is chosen from phenoxyethanol, benzyl alcohol, sodium benzoate and potassium sorbate.
- the preservative activated by the liquid antimicrobial composition is chosen from sorbic acid and its calcium, sodium, potassium, magnesium or zinc salts, or a mixture of these. this. Even more preferably, the preservative is chosen from sorbic acid, calcium sorbate, sodium sorbate, potassium sorbate. Most preferably, the preservative is potassium sorbate.
- the antimicrobial composition according to the invention makes it possible to activate the preservative power of phenoxyethanol against Pseudomonas Aeruginosa, Escherichia Coli, Staphylococcus aureus and Aspergillus brasiliensis.
- the antimicrobial composition according to the invention makes it possible to activate phenoxyethanol and, combined with said phenoxyethanol, to reduce by at least two logs the number of colony-forming units of Pseudomonas Aeruginosa, Staphylococcus aureus , Aspergillus brasiliensis and Escherichia Coli.
- the antimicrobial composition according to the invention makes it possible to activate phenoxyethanol and thus allows a reduction in the number of colony-forming units compared to phenoxyethanol alone, greater:
- the antimicrobial composition according to the invention makes it possible to activate the preservative power of benzyl alcohol against Pseudomonas Aeruginosa, Staphylococcus aureus, and Escherichia Coli.
- the antimicrobial composition according to the invention makes it possible to activate benzyl alcohol and thus allows a reduction in the number of colony-forming units compared to benzyl alcohol alone, greater:
- the antimicrobial composition according to the invention makes it possible to activate the preservative power of sodium benzoate against Pseudomonas Aeruginosa, Staphylococcus Aureus, Escherichia Coli, Aspergillus brasiliensis, and Candida albicans.
- the antimicrobial composition according to the invention makes it possible to activate sodium benzoate and thus allows a reduction in the number of colony-forming units compared to sodium benzoate alone, greater than:
- the antimicrobial composition according to the invention makes it possible to activate the preservative power of potassium sorbate against Pseudomonas Aeruginosa, Staphylococcus aureus, Escherichia Coli, Candida Albicans and 'Aspergillus brasiliensis.
- the antimicrobial composition according to the invention makes it possible to activate potassium sorbate and thus makes it possible to reduce the number of colony-forming units compared to potassium sorbate alone, greater than:
- an antimicrobial liquid composition to activate a cosmetic product preservative in a cosmetic product can be made with:
- an amount of antimicrobial liquid composition which can range from at least 0.1% by gross weight, preferably at least 0.5% by gross weight, more preferably at least 0.75% by gross weight, preferably at least 1 % by gross weight, and even more preferably at least 1.5% by gross weight,
- preservative which can be up to 2.5% by gross weight, preferably up to 1.5% by gross weight, more preferably up to 1% by gross weight, preferably up to 0 7% by gross weight, and even more preferably up to 0.6% by gross weight, relative to the total weight of the cosmetic product.
- an antimicrobial liquid composition to activate a cosmetic product preservative in a cosmetic product can be made with:
- an amount of antimicrobial liquid composition which can range from 0.1% to 5% by gross weight, preferably from 0.5% to 3% by gross weight, more preferably from 0.75% to 2% by gross weight, and most preferably from 1% to 1.5% by gross weight, of said at least one antimicrobial liquid composition,
- an amount of usual preservative which can be from 0.1% to 2.5% by gross weight, preferably from 0.2% to 1.5% by gross weight, more preferably from 0.3% to 1 % by gross weight, and most preferably from 0.4% to 0.7% by gross weight, relative to the total weight of the cosmetic product.
- the antimicrobial composition makes it possible to reduce by at least 35%, or even by at least 50%, or even better still by at least 60%, the quantity of usual preservative used in the cosmetic formulations. Thus it is generally possible to use them only at very low levels not exceeding 0.5% by gross weight, or even 0.4% by gross weight, relative to the total weight of the cosmetic product.
- the microbiological stability may be equal or even better than with the usual preservative used alone and at the recommended dose.
- the antimicrobial composition that is the subject of the present application comprises, or consists of:
- an essential oil consisting of citral and geraniol preferably a lemongrass oil consisting of citral and geraniol
- alkylglucoside carrying fatty chains with 6 to 12 carbon atoms preferably caprylyl/capryl glucoside
- carboxylic acid salt preferably sodium gluconate or sodium succinate, most preferably sodium gluconate
- the antimicrobial composition comprises, or consists of:
- an essential oil preferably lemongrass comprising at least 50% by weight of citral and geraniol relative to the weight of said essential oil, at a mass percentage of 0.1% to 10% by dry weight, preferably 0, 5% to 7% by dry weight, more preferably from 1% to 5% by dry weight, and most preferably from 1.5% to 3% by dry weight,
- alkylglucoside carrying fatty chains containing 6 to 12 carbon atoms preferably caprylyl/capryl glucoside, preferably from 5% to 30% by dry weight, more preferably 7, 5% to 20% by dry weight,
- gluconic acid from 10% to 70% by dry weight of gluconic acid, succinic acid, sodium gluconate or sodium succinate, preferably from 20% to 60% by dry weight, more preferably from 25% to 50% by dry weight, and most preferably from 27.5% to 40% by dry weight,
- the embodiments with terpene aldehydes, and without benzene aldehydes, have the advantage of being generally considered to be less irritating and less allergenic for the skin than the embodiments with benzene aldehydes.
- the present invention relates to an antimicrobial liquid composition
- an antimicrobial liquid composition comprising, preferably consisting of:
- an essential oil chosen from the essential oils of clove, lemongrass, Bourbon geranium, geranium grass, gingergrass, noble laurel, lemongrass, West Indian lemongrass, Indian lemongrass, East Indian, Lemon Bed, Lemon Balm, Palmarose, Chilli, Crown Pepper, Oregano, Tea Tree, Thyme, Lemongrass,
- nonionic surfactant chosen from alkyl(poly)glycosides, preferably from alkyl(poly)glucosides,
- the antimicrobial liquid composition comprises, preferably consists of:
- an essential oil chosen from essential oils of citronella, and essential oils of lemongrass from western India, lemongrass from eastern India, and preferably from essential oils of species of the genus Cymbopogon ,
- nonionic surfactant chosen from alkyl(poly)glycosides, preferably from alkyl(poly)glucosides,
- the antimicrobial liquid composition comprises, preferably consists of:
- the antimicrobial liquid composition comprises
- - caprylyl/capryl glucoside present at a mass percentage ranging from 1% to 40% by dry weight, preferably from 5% to 30% by dry weight, more preferably from 7.5% to 20% by dry weight,
- - free gluconic acid present at a mass percentage ranging from 10% to 70% by dry weight, preferably from 20% to 60% by dry weight, more preferably from 25% to 50% by dry weight, and most preferably from 27.5% to 40% by dry weight,
- the antimicrobial liquid composition consists of
- - caprylyl/capryl glucoside present at a mass percentage ranging from 1% to 40% by dry weight, preferably from 5% to 30% by dry weight, and more preferably from 7.5% to 20% by dry weight,
- - free gluconic acid present at a mass percentage ranging from 10% to 70% by dry weight, preferably from 20% to 60% by dry weight, more preferably from 25% to 50% by dry weight, and most preferably from 27.5% to 40% by dry weight,
- an essential oil chosen from the essential oils of clove, lemongrass, Bourbon geranium, geranium grass, gingergrass, noble laurel, lemongrass, West Indian lemongrass, Indian lemongrass, East Indian, Lemon Bed, Lemon Balm, Palmarose, Chilli, Crown Pepper, Oregano, Tea Tree, Thyme, Lemongrass,
- nonionic surfactant chosen from alkyl(poly)glycosides, preferably from alkyl(poly)glucosides,
- a salt of said carboxylic acid chosen from calcium, sodium, potassium, calcium, magnesium, zinc salts,
- the object antimicrobial liquid composition comprises, preferably consists of:
- an essential oil chosen from essential oils of citronella, and essential oils of lemongrass from western India, lemongrass from eastern India, and preferably from essential oils of species of the genus Cymbopogon ,
- nonionic surfactant chosen from alkyl(poly)glycosides, preferably from alkyl(poly)glucosides,
- the object antimicrobial liquid composition comprises, preferably consists of:
- the antimicrobial liquid composition comprises:
- - caprylyl/capryl glucoside present at a mass percentage ranging from 1% to 40% by dry weight, preferably from 5% to 30% by dry weight, more preferably from 7.5% to 20% by dry weight,
- - free gluconic acid present at a mass percentage ranging from 10% to 70% by dry weight, preferably from 20% to 60% by dry weight, more preferably from 25% to 50% by dry weight, and most preferably from 27.5% to 40% by dry weight,
- - sodium gluconate present at a mass percentage ranging from 1% to 50% by dry weight, preferably from 5% to 30% by dry weight, more preferably from 10% to 20% by dry weight, and most preferably 15% at 17.5% by dry weight,
- the antimicrobial liquid composition consists of:
- - caprylyl/capryl glucoside present at a mass percentage ranging from 1% to 40% by dry weight, preferably from 5% to 30% by dry weight, and more preferably from 7.5% to 20% by dry weight,
- - free gluconic acid present at a mass percentage ranging from 10% to 70% by dry weight, preferably from 20% to 60% by dry weight, more preferably from 25% to 50% by dry weight, and most preferably from 27.5% to 40% by dry weight,
- - sodium gluconate present at a mass percentage ranging from 1% to 50% by dry weight, preferably from 5% to 30% by dry weight, more preferably from 10% to 20% by dry weight, and most preferably 15% at 17.5% by dry weight,
- the choice of the constituents of the antimicrobial liquid composition which is the subject of the present application also has the advantage of giving it a content index of natural origin, denoted CNO, of 100%, the alkyl(poly)glucosides being obtained only from from plant resources.
- the antimicrobial composition that is the subject of the present application is in the form of a liquid, which is a dispersion of an oily phase in an aqueous phase.
- This dispersion can be either an oil-in-water emulsion, or an oil-in-water microemulsion, or an oil-in-water nanoemulsion, or a micellar solution, depending on the nature and the amounts of the constituents of the composition and its process. of production.
- the antimicrobial composition is an oil-in-water emulsion, and has oil phase droplet sizes ranging from 0.3 micrometers to 10 micrometers.
- the antimicrobial composition is an oil-in-water microemulsion or an oil-in-water micellar composition, and has droplet sizes ranging from 0.001 micrometers to 0.3 micrometers. Smaller droplet sizes, or microdroplets, or micelles, of the antimicrobial liquid composition make it opalescent or transparent. In addition, they also contribute to improving the stability of the oil in water, and to improving its antimicrobial activity and its effectiveness as a preservative activator.
- the oily dispersed phase comprises the essential oil; the aqueous phase comprises the carboxylic acid and/or the carboxylic acid salt; and the surfactant is located at the interface between the two phases.
- the oily phase may include a "non-essential" oil, such as triglycerides, in order to adjust the concentration of essential oil in the oily phase, and also to reduce the potential allergenicity of the essential oil.
- the oily phase can also include oils such as methyl esters of vegetable oils, or triglycerides of short fatty acids.
- the oily phase and the aqueous phase can also comprise additives without antimicrobial activity such as rheology agents, soluble dyes, pigments, perfumes, humectants, bulking agents.
- the oily dispersed phase consists of the essential oil; the aqueous phase consists of water, free carboxylic acid and/or carboxylic acid salt; and the nonionic surfactant is distributed between the two phases.
- the aqueous phase contains water as the sole and unique solvent, and is therefore free of any other solvent, in particular of any organic solvent.
- the transparency of the antimicrobial liquid composition and the compatibility with ionic surfactants allow this antimicrobial composition to be added to cosmetic products that are themselves transparent, such as micellar waters or gels, while retaining the transparency.
- the antimicrobial liquid composition is in the form of a macroscopically homogeneous liquid, which allows easy use during the production of cosmetic products. Handling a liquid requires less personal or collective protective equipment than handling a pulverulent powder. The transfer between container and the precise dosage are also much simpler and more reliable than for a pulverulent powder.
- the antimicrobial liquid composition can easily be incorporated into a cosmetic product in order to activate the preservative present, without destabilizing the cosmetic product.
- This composition according to the invention offers good stability and compatibility with cosmetic products, allowing transparency without problem of crystallization or precipitation.
- the present application also relates to a cosmetic product containing, as a preservative activator, an antimicrobial liquid composition according to the invention, and at least one usual cosmetic product preservative as described above.
- the cosmetic product comprises:
- the cosmetic product comprises:
- the cosmetic product comprises:
- the cosmetic product comprises a single and single antimicrobial liquid composition according to the present application, and a single and single preservative.
- the cosmetic product can be in any known form or physical state, namely an oil-in-water emulsion, a water-in-oil emulsion, a suspension, a foam, a true solution, a micellar solution , a hydroalcoholic solution, a paste, a gel, a powder, a tablet, a wipe.
- the product is in a form chosen from an oil-in-water emulsion, a water-in-oil emulsion, a suspension, a foam, a true solution, a micellar solution, a hydroalcoholic solution, a paste, a freeze.
- the product is in a form chosen from an oil-in-water emulsion, a water-in-oil emulsion, a suspension, a foam, a true solution, a micellar solution, a paste, a gel.
- the cosmetic product due to the neutrality of the composition according to the invention and its high compatibility with the vast majority of oils and fatty substances, alcohols, surfactants, emulsifiers, solubilizers, conditioners, film-forming agents, thickeners, gelling agents , neutralizing agents, or even active agents, can be formulated without particular difficulty and in a very broad manner with the ingredients usually selected.
- the following protocol describes the preparation of an antimicrobial composition consisting of essential oil(s), gluconic acid, sodium gluconate and a solubilizing surfactant.
- solubilizing surfactant When the solubilizing surfactant is in the form of a powder, it is dissolved in a minimum quantity of water.
- This aqueous solution of essential oil(s) and solubilizer is added to an aqueous solution of gluconic acid composed of the required quantity of free gluconic acid and sodium gluconate, with gentle stirring (for example 500- 1000 rpm using a Rayneri motor fitted with a propeller) and at ambient temperature (22° C.), until a homogeneous solution is obtained.
- the antimicrobial composition Used as a preservative activator, can be added to the cosmetic product at the end of preparation, in other words after the latter has been prepared, when the preparation of said cosmetic product includes high-temperature heating steps. temperature 60-80°C for periods exceeding a few minutes.
- the antimicrobial composition can be added from the first stages of preparation, but it is preferable to add it at the end of the preparation of the cosmetic product.
- the antimicrobial composition according to the invention can also find non-cosmetic uses and can in particular be suitable for microbiologically stabilizing pharmaceutical, food or industrial compositions such as, for example, liquid detergent compositions, liquid washing compositions, starch adhesives.
- Another object of the present application is the use of an antimicrobial composition according to the present application for killing microorganisms, or pathogenic microorganisms, or inhibiting the growth of microorganisms or pathogenic microorganisms, on or in a substrate not living or artificial.
- an antimicrobial composition for killing microorganisms, or pathogenic microorganisms, or inhibiting the growth of microorganisms or pathogenic microorganisms, on or in a substrate not living or artificial.
- Such an application concerns, for example, the disinfection of surfaces (floors, walls, doors, door handles), disinfection/conservation of industrial liquid products such as aqueous solutions of starches, proteins, or fibers.
- Example 1 selection of a solubilizing surfactant to achieve the transparency criteria
- This example presents the selection of a solubilizing surfactant and the ratio of the gross mass of surfactant to the gross mass of essential oil, to obtain a aqueous solution of essential oil of lemongrass Cymbopogon flexuosus which is transparent both in the concentrated state and in the state diluted in water.
- a solubilizing surfactant will be acceptable if both transparency criteria are met. Only the main surfactants tested which gave results are presented here.
- the ratio of the gross mass of surfactant to the gross mass of essential oil is denoted “raw TA/HE ratio” below.
- the protocol for preparing a liquid composition is as follows:
- a first premix is prepared by dissolving the gluconic acid in the mass of water with gentle stirring at 20-22°C,
- a second premix is prepared by adding to the mass of essential oil, the required mass of solubilizing surfactant, and stirring to allow the essential oil to be well dispersed and to obtain a homogeneous liquid,
- the second pre-mixture is then added to the first pre-mixture, and the mixture is maintained under gentle non-shearing agitation for about 20 minutes, to allow time for the pre-mixture of surfactant and essential oil to disperse, and thus the liquid composition to stabilize.
- the state of the liquid composition prepared is observed with the naked eye in order to evaluate its transparency and its homogeneity, in particular over the entire height of the sample, and in order to search for the possible presence of several phases or solid particles (which would have formed by instantaneous precipitation, or by slower crystallization).
- This state is denoted by “concentrated liquid composition”.
- Concentrated liquid composition On half of the volume of liquid composition, these observations are continued during storage at a temperature of 20-22° C. for 1 month.
- uccess almost imperceptible opalescence; homogeneous and almost perfect transparency to the naked eye; no turbidity visible to the naked eye.
- the surfactants A, E and F make it possible to provide a concentrated liquid composition which is transparent.
- Surfactants B, C and G fail to provide a concentrated liquid composition which is transparent, but allow transparency after dilution in water.
- Surfactant F provides transparency after dilution in water.
- the surfactants A, B, C, E, F and G may be suitable for the liquid antimicrobial composition which is the subject of the present application.
- the solubilizing surfactant F that is to say caprylyl/capryl glucoside
- the solubilizing surfactant F makes it possible to satisfy both the criterion of transparency and homogeneity of the concentrated liquid composition, and the same criterion after dilution in water, and this for values of the crude TA/HE ratio ranging from 8 to 10.
- the values of the crude TA/HE ratio ranging from 8 to 10 are equivalent to values of a ratio of the dry mass of surfactant to the dry mass of essential oil ranging from 4 to 5 (because this surfactant comprises 50% water and 50% caprylyl/dry capryl glucoside).
- Example 2 preparations of antimicrobial compositions
- compositions of the antimicrobial compositions that are the subject of the present application are shown in Table 5.
- the antimicrobial compositions 40 and 43 are prepared according to the following protocol:
- the required quantity of essential oil is slowly added to the required quantity of solubilizing surfactant solution, with gentle stirring, for example 500-1000 rpm using a Rayneri motor equipped with a propeller, and at temperature room temperature of 22°C, until a homogeneous solution is obtained.
- This aqueous solution of essential oil and solubilizer is added to an aqueous solution of gluconic acid and sodium gluconate.
- the antibacterial and antifungal activities of the compositions prepared in Example 2 are demonstrated through in vitro growth tests on standard culture media for the following microorganisms: Escherichia coli ATCC® 8739, Pseudomonas Aeruginosa ATCC® 9027, Staphylococcus Aureus ATCC® 6538, Candida Albicans ATCC® 10231, and Aspergillus Brasiliensis ATCC® 16404. These tests include comparisons with the constituents of the compositions taken in isolation, and taken in combination of two constituents, in order to identify the synergies of antimicrobial activity on these microorganisms.
- test tubes are prepared as there are products to be tested, that is to say the antimicrobial composition, the constituents alone, or the combinations of two constituents, as well as a control, with the culture medium adapted to the microorganism: “potato dextrose broth” for Aspergillus Brasiliensis; “Yeast Molds” for Candida Albicans; “tryptone soy broth” for Escherichia Coli; “medium” for Staphylococcus Aureus; and “middle” for Pseudomonas Aeruginosa.
- a dose of product to be tested according to Table 6 below, expressed as a weight/volume percentage is then added to each test tube. For example, a percentage of 1.5% weight/volume means that for 100 mL of culture medium, 1.5 g of product to be tested are added. Then we homogenize carefully by suction-repression.
- Each test tube is inoculated with a known quantity of microorganisms : 10 to 3 colony-forming units per milliliter of agar (denoted cfu/mL) for Aspergillus brasiliensis; 10 A 4 cfu/mL for Escherichia coli and Candida Albicans; 10 to 5 cfu /mL for Staphylococcus aureus and Pseudomonas aeruginosa. At the end of the inoculation, the inoculated media are again carefully homogenized by aspiration-discharge.
- the samples inoculated with Aspergillus brasiliensis are incubated at 30° C. (+/- 2.5° C.) for 48 hours.
- the samples inoculated with the other strains are incubated at 37°C (+/-2.5°C) for 48 hours.
- Samples and counts of the microorganisms are carried out at 30 minutes, 24 hours and 48 hours for each microorganism.
- the inoculated samples are taken, serially diluted in diluent (casein peptone 1 g/L, sodium chloride 8.5 g/L, pH 7) and deposited respectively on potato and dextrose agars for Aspergillus brasiliensis, tryptocasein-soya agars for Escherichia coli and Sabouraud dextrose agars for Candida albicans.
- the agars are incubated for 24 to 72 hours before counting the colonies present.
- the measurements of populations of microorganisms carried out at each sampling time are expressed in cfu/mL.
- the detection limit of the test is 100 cfu/mL.
- compositions 40 and 43 have antibacterial and antifungal properties under in vitro culture conditions on agar-type medium, because they make it possible to microbiologically stabilize culture media inoculated with bacteria and fungi. reference for periods of up to 48 hours.
- the antimicrobial compositions retain their antifungal and antibacterial properties once incorporated into cosmetic compositions.
- Example 4 activation of preservatives at pH 6 in an oil-in-water emulsion
- composition 43 prepared in Example 3 to activate the bactericidal and fungicidal activity of preservatives at pH 6 in an oil-in-water emulsion is demonstrated.
- the preservatives are phenoxyethanol, benzyl alcohol, sodium benzoate, and potassium sorbate. They are listed in appendix 5 of regulation no. 1223/2009.
- the cosmetic product used for this demonstration is a cream of the oil-in-water emulsion type, called “cotton cream”.
- Creams are prepared according to the composition of table 12, by adding sufficient quantities, denoted "Qs", of composition 43 and preservative according to the values of table 10.
- phase A is mixed separately and heated to 75°C. While maintaining at 75° C., phase B is added to phase A with gentle stirring (500-750 rpm; marine propeller), and the mixture is waited for to be homogeneous. Then phase A+B is added to phase C with emulsifying stirring (3000 rpm; deflocculating) for 10 minutes, maintaining at 75°C. The mixture is allowed to cool to 45° C., and phase D is added with moderate stirring (1500 rpm; marine propeller). The mixture is cooled to 25° C. with gentle stirring (500-750 rpm; marine propeller), then the pH is finally adjusted to 6 with phase E.
- Each antimicrobial protection efficacy test is conducted according to the guidelines of the ISO 11930:2019 standard. The results are provided in Tables 14 to 19. They are expressed as the logarithmic reduction in the number of colony forming units per mL. A positive value corresponds to a decrease in the number of colony forming units. A negative value corresponds to an increase in the number of colony forming units.
- cream 1 which is a cream without any preservative and without preservative activator, shows that cream 1 is not protected against Pseudomonas Aeruginosa, Escherichia Coli, and Candida Albicans, but is protected against Staphylococcus Aureus and Aspergillus Brasiliensis (we speak of self-protection) beyond 14 days. This measurement is our negative control.
- composition 43 contains 1% and 1.5% of composition 43 respectively, and no preservative, show that none of these creams is protected against Pseudomonas Aeruginosa and Candida Albicans. Self-protection against Staphylococcus Aureus and Aspergillus Brasiliensis is maintained. Concerning Escherichia Coli, protection is observed from 28 days. Composition 43 does not make it possible to protect the cream against microbial development. It is however notable that composition 43 does not degrade the self-protection of the cream against Staphylococcus Aureus and Aspergillus Brasiliensis.
- cream 6 which contains 0.4% by weight of phenoxyethanol and 1% by weight of composition 43
- the microbial protection against Pseudomonas Aeruginosa, Escherichia Coli, and Aspergillus brasiliensis is much better than that of the cream 5, and equivalent to the positive control. Indeed, from 7 days, or 14 days for Aspergillus Brasiliensis, strong logarithmic reductions are measured, and are greater than the reductions measured on cream 5 by at least 2 log.
- composition 43 therefore makes it possible to activate the preservative power of phenoxyethanol against Pseudomonas Aeruginosa, Escherichia Coli, Aspergillus brasiliensis and Staphylococcus aureus.
- cream 8 which contains 0.4% by weight of benzyl alcohol and 1% by weight of composition 43, it is found that the microbial protection against Pseudomonas Aeruginosa, Escherichia Coli, and Staphylococcus Aureus is well better than that of cream 7, and equivalent to the positive control. Indeed, from 7 days, or 14 days, significant or strong logarithmic reductions are measured, and are greater than the reductions measured on cream 7, by at least 2 log for Pseudomonas Aeruginosa and Escherichia Coli and Staphylococcus Aureus. These reductions continue or are maintained at 14 days and 28 days. However, Cream 8 is not protected against Candida albicans, which continues to grow there.
- composition 43 therefore makes it possible to activate the preservative power of benzyl alcohol against Pseudomonas Aeruginosa, Escherichia Coli, and Staphylococcus Aureus.
- cream 10 which contains 0.4% by weight of sodium benzoate and 1% by weight of composition 43
- the microbial protection against Pseudomonas Aeruginosa, Staphylococcus Aureus, Escherichia Coli, Aspergillus brasiliensis and Candida albicans is much better than that of cream 9, and equivalent to the positive control. Indeed, from 7 days, or 14 days for A. brasiliensis, significant or strong logarithmic reductions are measured, and are greater than the reductions measured on cream 7 by at least 1 or 2 log. These reductions continue or are maintained at 14 days and 28 days. Self-protection against Staphylococcus aureus is maintained. It is noteworthy that the cream 10 here presents sufficient protection against Candida albicans.
- Composition 43 therefore makes it possible to activate the preservative power of sodium benzoate against Pseudomonas Aeruginosa, Staphylococcus Aureus, Escherichia Coli, Aspergillus brasiliensis, and Candida albicans.
- the combination of 1% (by weight) of composition 43 and 0.4% (by weight) of the sodium benzoate makes it possible to stabilize the cream according to criterion B of standard ISO 11930:2019.
- cream 12 which contains 0.4% by weight of potassium sorbate and 1% by weight of composition 43
- the microbial protection against Pseudomonas Aeruginosa, Staphylococcus Aureus, Escherichia Coli, Candida Albicans and Aspergillus brasiliensis is much better than that of cream 11 , and even better than that of positive control cream 2 (containing 1% of Microcare® PM4).
- positive control cream 2 containing 1% of Microcare® PM4
- strong logarithmic reductions are measured, and are greater than the reductions measured on cream 11 by at least 2 log. These reductions are maintained or continue at 14 days and 28 days.
- composition 43 therefore makes it possible to activate the preservative power of potassium sorbate against Pseudomonas Aeruginosa, Escherichia Coli, Candida Albicans, Staphylococcus Aureus and Aspergillus brasiliensis.
- the combination of 1% (by weight) of composition 43 and 0.4% (by weight) of potassium sorbate makes it possible to stabilize the cream according to criterion A of standard ISO 11930:2019.
- Example 5 cosmetic products comprising the “preservative activator” composition and a preservative
- a shampoo is prepared according to the composition of table 22:
- Antimicrobial protection efficacy tests are carried out on each shampoo in table 23 for the five microorganisms of the ISO 11930:2019 standard Pseudomonas Aeruginosa, Staphylococcus Aureus, Escherichia Coli, Candida Albicans, Aspergillus Brasiliensis. The results are shown in Table 24.
- potassium sorbate which is a listed preservative, exerts a protective effect against three microorganisms Pseudomonas Aeruginosa, Candida Albicans and Aspergillus Brasiliensis, but destroys the self-protection of the formula against Escherichia Coli, making it non protected against this last bacterium.
- composition 43 makes it possible to exert an antibacterial activity targeted on the Escherichia Coli strain effective from seven days and up to 28 days.
- composition 43 thus makes it possible to protect the shampoo against the development of bacteria of the genus Escherichia Coli, and this without reducing or disturbing the antimicrobial activity of the preservative which is potassium sorbate, but on the contrary by activating the antimicrobial activity of potassium sorbate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR2013020A FR3117310B1 (fr) | 2020-12-10 | 2020-12-10 | composition liquide antimicrobienne et son utilisation comme activateur de conservateur de produits cosmétiques |
| FR2103219 | 2021-03-29 | ||
| PCT/EP2021/025490 WO2022122187A1 (fr) | 2020-12-10 | 2021-12-10 | Composition liquide antimicrobienne et son utilisation comme activateur de conservateur de produits cosmetiques |
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| EP4258884A1 true EP4258884A1 (fr) | 2023-10-18 |
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| EP21824287.3A Pending EP4258884A1 (fr) | 2020-12-10 | 2021-12-10 | Composition liquide antimicrobienne et son utilisation comme activateur de conservateur de produits cosmetiques |
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| US (1) | US20240023559A1 (fr) |
| EP (1) | EP4258884A1 (fr) |
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| CN115428883A (zh) * | 2022-09-13 | 2022-12-06 | 宁波市农业科学研究院 | 一种米制品糕点保鲜剂及其应用 |
| CN117338664A (zh) * | 2023-11-07 | 2024-01-05 | 广州唯我美日用品有限公司 | 一种调节头皮生态平衡的组合物及含有组合物的洗发水 |
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| US5403587A (en) | 1993-04-22 | 1995-04-04 | Eastman Kodak Company | Disinfectant and sanitizing compositions based on essential oils |
| US6346281B1 (en) | 2000-05-05 | 2002-02-12 | Scentsible Life Products, A Division Of Laid Back Designs Ltd. | Antimicrobial composition formulated with essential oils |
| US20080253976A1 (en) | 2007-04-16 | 2008-10-16 | Douglas Craig Scott | Personal Care Compositions Comprising An Antimicrobial Blend of Essential Oils or Constituents Thereof |
| US20100114146A1 (en) | 2008-10-30 | 2010-05-06 | Albrecht Thomas E | Methods and devices for predicting intra-gastric satiety and satiation creation device system performance |
| EP2460409A1 (fr) | 2010-12-03 | 2012-06-06 | Nestec S.A. | Support pour relargage d'huiles essentielles antimicrobiennes |
| JP2015521161A (ja) * | 2012-04-25 | 2015-07-27 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングMerck Patent Gesellschaft mit beschraenkter Haftung | 抗微生物特性を有するジシクロヘキシルメタノール誘導体の使用 |
| TWI707483B (zh) | 2012-07-17 | 2020-10-11 | 新加坡商新加坡恒立私人有限公司 | 發射可變強度分布的光線的光電模組 |
| CN104994878A (zh) * | 2012-12-13 | 2015-10-21 | 纽约市哥伦比亚大学理事会 | 植物抗微生物组合物 |
| CA2982869C (fr) * | 2015-04-09 | 2021-06-15 | Isp Investments Llc | Compositions de conservateurs synergiques |
| US9687002B2 (en) | 2015-05-21 | 2017-06-27 | IndusCo, Ltd. | Botanical antimicrobial microemulsions (BAMM) |
| FR3061010B1 (fr) | 2016-12-23 | 2019-05-24 | L'oreal | Nanoemulsions a base d'huile polaire |
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- 2021-12-10 US US18/256,365 patent/US20240023559A1/en active Pending
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| US20240023559A1 (en) | 2024-01-25 |
| WO2022122187A1 (fr) | 2022-06-16 |
| CN116829124A (zh) | 2023-09-29 |
| CN116829124B (zh) | 2026-03-13 |
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