WO1999038945A1 - Water dispersible granulates comprising a perfume in a water soluble or water dispersible matrix and preparation method - Google Patents

Water dispersible granulates comprising a perfume in a water soluble or water dispersible matrix and preparation method Download PDF

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Publication number
WO1999038945A1
WO1999038945A1 PCT/FR1999/000132 FR9900132W WO9938945A1 WO 1999038945 A1 WO1999038945 A1 WO 1999038945A1 FR 9900132 W FR9900132 W FR 9900132W WO 9938945 A1 WO9938945 A1 WO 9938945A1
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WO
WIPO (PCT)
Prior art keywords
water
weight
perfume
dispersible
granules
Prior art date
Application number
PCT/FR1999/000132
Other languages
French (fr)
Inventor
Gilles Guerin
Mikel Morvan
Daniel Joubert
Original Assignee
Rhodia Chimie
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Rhodia Chimie filed Critical Rhodia Chimie
Priority to JP2000529406A priority Critical patent/JP2002501976A/en
Priority to EP99900988A priority patent/EP1051472A1/en
Priority to AU20621/99A priority patent/AU2062199A/en
Priority to CA002318383A priority patent/CA2318383A1/en
Publication of WO1999038945A1 publication Critical patent/WO1999038945A1/en

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q13/00—Formulations or additives for perfume preparations
    • 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
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A61K8/0283—Matrix particles
    • A61K8/0287—Matrix particles the particulate containing a solid-in-solid dispersion
    • 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
    • A61K8/64—Proteins; Peptides; Derivatives or degradation products thereof
    • A61K8/645—Proteins of vegetable origin; Derivatives or degradation products thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/221—Mono, di- or trisaccharides or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/382—Vegetable products, e.g. soya meal, wood flour, sawdust
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • C11D3/502—Protected perfumes
    • C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay

Definitions

  • the subject of the present invention is water-dispersible granules comprising at least one perfume in a water-soluble or water-dispersible organic polymer matrix, their process of preparation, their use as a perfuming agent in detergent or cosmetic compositions and detergent compositions for linen or cosmetics comprising said particles.
  • the perfuming of detergent compositions for washing, in particular for washing clothes requires a certain number of constraints, more or less important depending on the technical-economic and marketing objectives of the formulator.
  • One of the first problems posed is to find a suitable method of addition and distribution of the liquid perfume on the detergent powder.
  • the perfume is sprayed finely, continuously, on the formulated powder, complete, which transits in any conveyor, between the place of manufacture and the place of packaging. Pneumatic transport can be used for this operation, or "air lift" systems.
  • the formulated detergent is sufficiently cooled, especially when the manufacturing process is an atomization process, and that the mixing system allows a minimum loss of the perfumed substance, which is the most expensive components of the formulation. .
  • Compliance with the dosage is one of the elements which is difficult to control and which must be sought to improve both for cost problems and for problems of consistency of quality.
  • the solid-particulate shaping of the composition may represent a first improvement in this level of the method of manufacturing detergents.
  • the alkalinity of the compositions is also a factor in degrading the perfume.
  • Very absorbent products such as silicas, clays, zeolites can selectively and more or less strongly absorb the perfume or one of its components and this material contribute to modify or alter it.
  • a third problem, or a third requirement, encountered in the field of perfuming detergents, is the fact that the perception of the chosen odor, which is one of the modes of recognition of detergent by the buyer, must be effective for all laundry life cycles, and beyond.
  • the odor of the perfume must be perceptible in the store where the detergent is presented for purchase, during the lifetime of the package (even when opened), during washing himself, from the washing machine, during the operations of drying, ironing and storing the washed articles, in the storage cupboard, and finally during the carrying or the use of the linen.
  • One of the first ways is to use the absorbent properties of certain porous supports, such as silicas, clays, natural or synthetic zeolites, starches, carboxymethylcellulose, urea, soluble mineral phosphates ...
  • porous supports such as silicas, clays, natural or synthetic zeolites, starches, carboxymethylcellulose, urea, soluble mineral phosphates ...
  • disadvantages of these modes of shaping in particular the fact of dividing and spreading the perfume over very large contact surfaces, thereby increasing the risks of oxidation at the same time as the exchange surface between the perfume and air, and also the risk of making a selective retention of one or more components, with restitution of a modified odor.
  • Simple absorption allows solid shaping, but is often insufficient for the protection of the perfume during storage.
  • a coating of the perfume / support assembly must also be used.
  • Another mode of shaping is the use of products with a particular molecular structure making it possible to create a reception cavity for perfumes, for example products such as cyclodextrins.
  • the downside, besides the cost, is the difficulty in introducing complex compositions based on very different and dissimilar steric molecular weight and bulk products.
  • Organic matrices composed of PEG or paraffins of sufficient molecular mass to be solid at ordinary temperature have also been proposed for solidifying the perfumed compositions, with advantages but also disadvantages, in particular that of only partially releasing the perfume or else the having to use molten phases of the coating products.
  • microcapsules either mineral or polymeric, possibly mechanically friable
  • the Applicant has found a solid form dispersible in water, liquid perfumes, by encapsulation by a protective matrix which is localized outside the droplets of finely divided perfume; in this way, said matrix coats the perfume, protects it at the same time as it allows the transition to the solid state.
  • a first object of the invention consists of water dispersible granules, comprising
  • hydrophobic perfume in the form of droplets, finely divided into and encapsulated by a water-soluble or water-dispersible (MO) solid organic matrix, chosen from
  • AE emulsifying agent
  • said water-dispersible granules comprise
  • AE emulsifying agent
  • Said droplets can have an average particle size of the order of 0.1 to 10 ⁇ m, preferably of the order of 0.2 to 5 ⁇ m.
  • the term “perfume” is intended to mean either a perfumed essence or more generally a complex composition obtained using numerous odorous products in mixture and excipient products which ensure their homogeneity.
  • Said perfumes according to the invention are isotropic and hydrophobic compounds. Their solubility in water at pH 7 does not exceed 10% by weight.
  • the mixture of odorous products can comprise a large number of constituents, chosen so as to obtain the desired fragrant notes for the intended use, the public and the market.
  • constituents for example vegetable or animal essences obtained by steam extraction or by alcoholic extraction, which are themselves already mixtures
  • synthetic products which can be aliphatic or aromatic ketones, aliphatic aldehydes or aromatics, condensation products of aldehydes and amines, aromatic or aliphatic lactones, aromatic or aliphatic ethers or esters, aliphatic alcohols of various molecular weights, saturated or unsaturated hydrocarbons, linear, cyclic or aromatic, terpenic, polynuclear or not .
  • the most sophisticated perfume compositions can contain up to a hundred ingredients.
  • an odorous compound there may be mentioned: cinnamic hexyl aldehyde, 2-methyl-3 (para-tert-butylphenyl) -propionaldehyde 7-acetyl-1, 2,3,4,5,6 , 7,8-octahydro-1, 1, 6,7-tetramethyl naphthalene benzyl salicylate; 7-acetyl-1, 1, 3,4,4,6,6-hexamethyl tetraline para-tert-butyl cyclohexyl acetate methyl dihydro jasmonate; beta-naphthol methyl ether methyl beta-naphthyl ketone; 2-methyl-2- (para-iso-propylphenyl) -propionaldehyde 1, 3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-gamma-2 -benzopyran dodecahydro
  • water-soluble or water-dispersible synthetic polypeptides which may constitute the matrix
  • These polymers can be homopolymers derived from aspartic or glutamic acid as well as copolymers derived from aspartic acid and glutamic acid in any proportions, or copolymers derived from aspartic acid and / or glutamic acid and d other amino acids.
  • copolymerizable amino acids there may be mentioned glycine, alanine, leucine, isoleucine, phenyl alanine, methionine, histidine, proline, lysine, serine, threonine, cysteine ...
  • polypeptides (PP) of plant origin mention may be made of proteins of plant origin which are water-soluble or water-dispersible. They are preferably hydrolyzed; their degree of hydrolysis is preferably less than or equal to 40%, for example from 5 to less than 40%.
  • proteins of vegetable origin mention may be made, by way of indication, of the proteins originating from protein seeds, in particular those of peas, faba beans, lupins, beans, and lentils; proteins from cereal grains, especially those from wheat, barley, rye, corn, rice, oats, and millet; proteins from oil seeds, especially those from soybeans, peanuts, sunflowers, rapeseed, and coconuts; proteins from the leaves, especially alfalfa, and nettles; and proteins from plant organs from buried reserves, notably that of potatoes and beets.
  • the vegetable protein comes more particularly from soybeans or wheat.
  • the polyelectrolyte (PE) can be chosen from those resulting from the polymerization of monomers which have the general formula
  • R represents a hydrocarbon residue containing from 1 to 4 carbon atoms, preferably an alkylene residue containing 1 or 2 carbon atoms, methylene in particular.
  • acrylic, methacrylic, maleic, fumaric, itaconic and crotonic acids By way of nonlimiting examples, mention may be made of acrylic, methacrylic, maleic, fumaric, itaconic and crotonic acids.
  • copolymers obtained from the monomers corresponding to the preceding general formula and those obtained using these monomers and other monomers in particular vinyl derivatives such as vinyl alcohols and copolymerizable amides such as acrylamide or methacrylamide.
  • vinyl derivatives such as vinyl alcohols
  • copolymerizable amides such as acrylamide or methacrylamide.
  • alkyl vinyl ether and maleic acid as well as those obtained from vinyl styrene and maleic acid which are in particular described in the KIRK-OTHMER encyclopedia entitled "ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY" - Volume 18 - 3rd edition - Wiley interscience publication - 1982.
  • the preferred polyelectrolytes have a low degree of polymerization.
  • the molecular weight by weight of the polyelectrolytes is more particularly less than 20,000 g / mole. Preferably, it is between 1000 and 5000 g / mole.
  • the emulsifying agents (AE) which may be present are non-ionic, ionic or amphoteric emulsifiers.
  • said matrix (MO) is made of a polypeptide (PP)
  • said emulsifying agent (AE) is chosen from ionic or amphoteric emulsifiers.
  • said matrix (MO) is made of a polyelectrolyte (PE)
  • said emulsifying agent (AE) is chosen from nonionic or amphoteric emulsifiers.
  • nonionic emulsifiers mention may be made in particular of polyoxyalkylenated derivatives such as
  • the number of oxyethylene (OE) and / or oxypropylene (OP) units of these nonionic surfactants usually varies from 2 to 100 depending on the HLB (hydrophilic / lipophilic balance) desired. More particularly, the number of OE and / or OP units is between 2 and 50. Preferably, the number of OE and / or OP units is between 10 and 50.
  • Ethoxylated or ethoxy-propoxylated fatty alcohols generally contain from 6 to 22 carbon atoms, the OE and OP units being excluded from these numbers. Preferably, these units are ethoxylated units.
  • the ethoxylated or ethoxy-propoxylated triglycerides can be triglycerides of plant or animal origin (such as lard, tallow, peanut oil, butter oil, cottonseed oil, oil flaxseed, olive oil, fish oil, palm oil, grape seed oil, soybean oil, castor oil, rapeseed oil, coconut oil, coconut oil and are preferably ethoxylated.
  • the ethoxylated or ethoxy-propoxylated fatty acids are fatty acid esters (such as for example oleic acid, stearic acid), and are preferably ethoxylated.
  • the ethoxylated or ethoxy-propoxylated sorbitan esters are cyclized fatty acid sorbitol esters comprising from 10 to 20 carbon atoms such as lauric acid, stearic acid or oleic acid, and are preferably ethoxylated.
  • ethoxylated triglyceride is intended in the present invention, both the products obtained by ethoxylation of a triglyceride with ethylene oxide as those obtained by transesterification of a triglyceride with a polyethylene glycol.
  • ethoxylated fatty acid includes both the products obtained by ethoxylation of a fatty acid with ethylene oxide and those obtained by transesterification of a fatty acid with a polyethylene glycol.
  • Ethoxylated or ethoxy-propoxylated fatty amines generally have from 10 to 22 carbon atoms, the OE and OP units being excluded from these numbers, and are preferably ethoxylated.
  • the ethoxylated or ethoxy-propoxylated alkylphenols are generally 1 or 2 alkyl groups, linear or branched, having 4 to 12 carbon atoms. By way of example, mention may in particular be made of octyl, nonyl or dodecyl groups.
  • nonionic surfactants from the group of ethoxy or ethoxy-propoxylated alkylphenols ethoxylated di (phenyl-1 ethyl) phenols and ethoxy or ethoxy-propoxy tri (phenyl-ethyl) phenols
  • anionic emulsifiers mention may be made of the water-soluble salts of alkylsuifates, of alkylethersulfates, alkylisethionates and alkyltaurates or their salts, alkylcarboxylates, alkylsulfosuccinates or alkylsuccinamates, alkylsarcosinates, alkyl derivatives of protein hydrolysates, acylaspartates, phosphates, alkyl esters and / or alkyl ether and / or alkylaryl ether.
  • the cation is generally an alkali or alkaline earth metal, such as sodium, potassium, lithium, magnesium, or an ammonium group NR 4 + with R, identical or different, representing an alkyl radical substituted or not by a oxygen or nitrogen atom. 8
  • alkyldimethylbenzylammonium halides examples include alkyldimethylethylammonium halides, etc.
  • amphoteric emulsifiers mention may be made of alkyl betaines, alkyldimethyl betaines, alkylamidopropyl betaines, alkylamidopropyl dimet betaines, alkyltrimethyl sulfobetaines, imidazoline derivatives such as alkylamphoacetates, alkylamphodiacetates, alkylampho-amphionates, alkylampho-propylates alkylsultaines or alkylamidopropyl-hydroxysultaines, condensation products of fatty acids and protein hydrolysates, amphoteric derivatives of alkylpolyamines such as Amphionic XL® marketed by Rhône-Poulenc, Ampholac 7T / X® and Ampholac 7C / X® marketed by Berol Nobel, proteins or protein hydrolysates.
  • alkyl betaines such as Amphionic XL® marketed by Rhône-Poulenc, Am
  • up to 50% of the weight of the matrix (MO) can be made up of a water-soluble or water-dispersible ose, oside or poiyholoside (O).
  • ose oside
  • O poiyholoside
  • aldoses such as glucose, mannose, galactose, ribose, and ketoses such as fructose.
  • Osides are compounds which result from the condensation, with elimination of water, of daring molecules between them or even of daring molecules with non-carbohydrate molecules.
  • the holosides which are formed by the combination of exclusively carbohydrate units are preferred, and more particularly the oligoholosides (or oligosaccharides) which contain only a limited number of these units, that is to say a number generally lower. or equal to 10.
  • oligoholosides mention may be made of sucrose, lactose, cellobiose, maltose and trehalose.
  • the water-soluble or water-dispersible poiyholosides are highly depolymerized; they are described for example in the work of P. ARNAUD entitled “organic chemistry course", Gaultier-Villars editors, 1987. More particularly, these poiyholosides have a molecular weight by weight of less than 20,000 g / mole.
  • dextran By way of nonlimiting example of highly depolymerized poiyholosides, mention may be made of dextran, starch, xanthan gum and galactomannans such as guar or carob, these polysaccharides preferably having a melting point above 100 ° C. and a solubility in water of between 50 and 500 g / l.
  • a second subject of the invention consists of a two-step process for the preparation of water-dispersible granules, comprising
  • hydrophobic perfume in the form of droplets, finely divided into and encapsulated by a water-soluble or water-dispersible (MO) solid organic matrix, chosen from
  • the first step consisting in preparing an emulsion in water comprising at least one hydrophobic perfume (P), at least one emulsifying agent (AE) and said water-soluble or water-dispersible (MO) organic matrix
  • the second step consisting in drying said emulsion until a granule is formed.
  • hydrophobic is synonymous with solubility in water at pH 7 not exceeding 10% by weight.
  • perfume (P), of emulsifying agent (AE) and of water-soluble or water-dispersible organic matrix (MO) used are such that said emulsion, expressed in dry form, comprises
  • hydrophobic perfume (P) from 5 to 90%, preferably from 25 to 70% by weight, of hydrophobic perfume (P),
  • AE emulsifying agent
  • the amount of dry matter of the emulsion is generally between 10 and 70% by weight and preferably between 20 and 60% by weight. It is possible to use all the methods for preparing emulsions known to a person skilled in the art and which are described in "ENCYCLOPEDIA of EMULSIONS TECHNOLOGY", volumes 1 to 3 by Paul BECHER edited by MARCEL DEKKER INC., 1983.
  • the so-called direct phase emulsification method is suitable for the preparation of the granules according to the invention. It is recalled briefly that this method consists in preparing a mixture containing the water, the emulsifier (s), the water-soluble or water-dispersible matrix (MO), then in introducing the perfume in liquid form, with stirring.
  • the emulsion can also be prepared by using colloid mills such as MENTON GAULIN and MICROFLUIDIZER (MICROFLUIDICS).
  • the average particle size of the emulsion is generally between 0.1 and 10 micrometers and preferably between 0.2 and 5 micrometers.
  • the emulsification can be carried out at a temperature close to room temperature, although lower or higher temperatures can be envisaged.
  • the second step of the preparation process according to the invention consists in drying the emulsion thus formulated to obtain granules.
  • the method used to remove water from the emulsion and obtain granules can be carried out by any means known to those skilled in the art. 10
  • lyophilization which corresponds to a freezing step, followed by a sublimation step, or even spray drying.
  • drying modes and more particularly that by atomization, are particularly indicated because they make it possible to keep the emulsion in the state and to obtain granules directly.
  • Water-soluble or water-dispersible proteins of plant origin are particularly well suited to spray drying, because they are particularly stable.
  • Spray drying can be carried out in the usual manner in any known device such as for example an atomization tower associating a spraying carried out by a nozzle or a turbine with a stream of hot gas.
  • any known device such as for example an atomization tower associating a spraying carried out by a nozzle or a turbine with a stream of hot gas.
  • the conditions of implementation depend on the nature of the matrix, the thermosensitivity of the perfume and the atomizer used; these conditions are generally such that the temperature of the entire product during drying does not exceed 150 ° C., preferably does not exceed 110 ° C.
  • additives such as anti-caking agents can be incorporated into the granules at the time of this second drying step.
  • a filler chosen in particular from calcium carbonate, kaolin, silica, bentonite ...
  • the composite particles obtained are redispersible in water.
  • the release of the perfume, during the re-dispersion can be controlled by the choice of the organic matrix (OM), by choosing a matrix with progressive or slow solubility.
  • OM organic matrix
  • Another subject of the invention consists in the use of said dispersible granules as a perfuming agent in cosmetic compositions and in particular in detergent compositions for washing clothes (industrial or household washing).
  • said granules can be used in an amount of about 0.01 to 0.5%, preferably from 0.05 to 0.2% by weight relative to the detergent composition.
  • a final object of the invention consists of cosmetic compositions and in particular detergent compositions for washing clothes (industrial or household washing), comprising said dispersible granules based on perfume.
  • the detergent compositions may contain approximately 0.01 to 0.5%, preferably 0.05 to 0.2%, by weight of dispersible granules based on perfume. 11
  • the detergent compositions according to the invention comprise at least one surfactant, in an amount generally of the order of 5 to 60% by weight, preferably from 8 to 50% by weight.
  • the detergent compositions which are the subject of the invention can also comprise usual additives, such as mineral or organic detergency builders, in an amount such that the total amount of detergency builder is from 5 to 80% by weight of the said composition, preferably from 8 to 40% by weight, of the anti-fouling agents, the anti-redeposition agents, the bleaching agents, the fluorescent agents, the foam-suppressing agents, the agents softeners, enzymes and other additives.
  • mineral or organic detergency builders in an amount such that the total amount of detergency builder is from 5 to 80% by weight of the said composition, preferably from 8 to 40% by weight, of the anti-fouling agents, the anti-redeposition agents, the bleaching agents, the fluorescent agents, the foam-suppressing agents, the agents softeners, enzymes and other additives.
  • FP940 (soy protein hydrolyzate of degree of hydrolysis 0.6 part by weight less than 5%, from Protein Technologies International) (dry) fragrance 29.6 parts by weight Deionized water 69.8 parts by weight by adding perfume to a 5% by weight aqueous solution of FP940.
  • the dry matter rate is 30.2%.
  • the mixture is first pre-emulsified using one of the Ultra Turrax T25 devices for
  • the emulsion itself is produced using a microfluidizer (M110T from M110T from M110T from M110T.
  • Microfluidics under the following conditions: Pressure: 600 bars - 3 passages in the micro-fluidizer - Cold water bath at the output of the micro-fluidizer.
  • the emulsion obtained has a tight particle size with a median diameter
  • the same vegetable protein (FP940 from Protein Technologies International) is incorporated into the emulsion prepared as a polypeptide matrix.
  • the composition of the emulsion formulated is as follows:
  • This formulated emulsion has 45.9% dry matter and a median diameter (d50) of 1.3 ⁇ m.
  • composition of this emulsion corresponds to a dry weight ratio A B of 51/49, ratio in which A and B have the following meaning:
  • the emulsion obtained has a poiydisperse particle size with a median diameter (d50) of 0.7 mm.
  • the matrix incorporated into the emulsion is a polyacrylic acid with a molar mass of 2000 g / mol of Bevaloid.
  • composition of the emulsion formulated is as follows: 18.6% Perfume
  • composition of the emulsion thus formulated corresponds to a weight ratio in sec
  • silica in the following proportions:

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Abstract

The invention concerns water dispersible granulates comprising: at least a hydrophobic perfume (P), in the form of droplets, finely divided in and encapsulated by a water soluble or water dispersible solid organic matrix (MO) selected among: polypeptides (PP) of plant or synthetic origin; polyelectrolytes (PE) belonging to the family of weak polyacids; or their mixtures; and at least an emulsifying agent (AE) at the droplet/matrix interface. The invention also concerns a method, in two steps, for preparing said granulates, the first step consisting in preparing an emulsion in water comprising at least a hydrophobic perfume (P), at least an emulsifying agent (AE); and said water soluble or water dispersible organic matrix (MO), the second step consisting in drying said emulsion until a granulate is formed.

Description

1 1
GRANULES DISPERSABLES DANS LΕAU COMPRENANT UN PARFUMWATER DISPERSABLE GRANULES COMPRISING A PERFUME
DANS UNE MATRICE HYDROSOLUBLE OU HYDRODISPERSABLEIN A WATER-SOLUBLE OR WATER-DISPERSABLE MATRIX
ET LEUR PROCEDE DE PREPARATIONAND THEIR PREPARATION PROCESS
La présente invention a pour objet des granulés dispersables dans l'eau, comprenant au moins un parfum dans une matrice polymère organique hydrosoluble ou hydrodispersable, leur procédé de préparation, leur utilisation comme agent parfumant dans les compositions détergentes ou cosmétiques et les compositions détergentes pour le linge ou cosmétiques comprenant lesdites particules. Le parfumage des compositions détergentes de lavage, notamment de lavage du linge, requiert un certain nombre de contraintes, plus ou moins importantes selon les objectifs technico-économiques et de marketing du formulateur.The subject of the present invention is water-dispersible granules comprising at least one perfume in a water-soluble or water-dispersible organic polymer matrix, their process of preparation, their use as a perfuming agent in detergent or cosmetic compositions and detergent compositions for linen or cosmetics comprising said particles. The perfuming of detergent compositions for washing, in particular for washing clothes, requires a certain number of constraints, more or less important depending on the technical-economic and marketing objectives of the formulator.
Un des premiers problèmes posés est de trouver un mode d'addition et de répartition adéquat du parfum liquide sur la poudre détergente. Généralement le parfum est pulvérisé finement, en continu, sur la poudre formulée, complète, qui transite dans un transporteur quelconque, entre le lieu de fabrication et le lieu de conditionnement. Les transports pneumatiques peuvent être mis à profit pour cette opération, ou bien les systèmes "air lift". Il est nécessaire que la lessive formulée soit suffisamment refroidie, en particulier quand le procédé de fabrication est un procédé par atomisation, et que le système de mélange permette un minimum de perte de la substance parfumée, qui est des composants les plus onéreux de la formulation. Le respect du dosage (% de parfum par rapport à la poudre ) est un des éléments difficile à maîtriser et qu'il faut chercher à améliorer aussi bien pour des problèmes de coût que pour des problèmes de constance de qualité. La mise en forme solide-particulaire de la composition peut représenter une première amélioration à ce niveau deu procédé de fabrication des lessives.One of the first problems posed is to find a suitable method of addition and distribution of the liquid perfume on the detergent powder. Generally the perfume is sprayed finely, continuously, on the formulated powder, complete, which transits in any conveyor, between the place of manufacture and the place of packaging. Pneumatic transport can be used for this operation, or "air lift" systems. It is necessary that the formulated detergent is sufficiently cooled, especially when the manufacturing process is an atomization process, and that the mixing system allows a minimum loss of the perfumed substance, which is the most expensive components of the formulation. . Compliance with the dosage (% of perfume relative to the powder) is one of the elements which is difficult to control and which must be sought to improve both for cost problems and for problems of consistency of quality. The solid-particulate shaping of the composition may represent a first improvement in this level of the method of manufacturing detergents.
Un autre problème du parfumage des lessives est celui de la stabilité du parfum (et de l'ensemble des "notes" qu'il libère) au cours du stockage de la lessive dans son emballage. En effet, les composants des lessives sont eux-mêmes très variés et leurs natures chimiques sont très différentes et peuvent être agressives, voire incompatibles avec la composition parfumée, qui renferme des composants chimiquement fragiles. Les lessives modernes contiennent souvent des systèmes de blanchiment basés sur des produits libérant de l'eau oxygénée, puis de l'oxygène actif. C'est là l'élément le plus déstabilisant pour les parfums.Another problem with the perfuming of detergents is that of the stability of the perfume (and of all of the "notes" that it releases) during the storage of the detergent in its packaging. In fact, the components of the detergents are themselves very varied and their chemical natures are very different and can be aggressive, or even incompatible with the perfumed composition, which contains chemically fragile components. Modern detergents often contain bleaching systems based on products releasing oxygenated water, then active oxygen. This is the most destabilizing element for perfumes.
L'alcalinité des compositions est également un facteur de dégradation du parfum. Des produits très absorbants comme le silices, les argiles, les zeolithes peuvent absorber sélectivement et plus ou moins fortement le parfum ou l'un de ses composants et de cette matière contribuer à le modifier ou à l'altérer.The alkalinity of the compositions is also a factor in degrading the perfume. Very absorbent products such as silicas, clays, zeolites can selectively and more or less strongly absorb the perfume or one of its components and this material contribute to modify or alter it.
De même, l'eau de cristallisation, l'eau libre, les surfactants, les séquestrants, qui sont toujours présents dans les compositions détergentes peuvent interférer négativement avec les compositions parfumées.Likewise, water of crystallization, free water, surfactants, sequestrants, which are always present in the detergent compositions can negatively interfere with the perfumed compositions.
Un troisième problème, ou une troisième exigence, rencontré dans le domaine du parfumage des lessives, est le fait que la perception de l'odeur choisie, qui est un des modes de reconnaissance de la lessive par l'acheteur, doit être effective à tous les cycles de vie de la lessive, et même au delà.A third problem, or a third requirement, encountered in the field of perfuming detergents, is the fact that the perception of the chosen odor, which is one of the modes of recognition of detergent by the buyer, must be effective for all laundry life cycles, and beyond.
En particulier, l'odeur du parfum, ou tout au moins une fraction de cette odeur, doit être perceptible dans le magasin où est présentée la lessive à l'achat, durant la durée de vie du paquet (même ouvert), durant le lavage lui même, à partir de la machine à laver, durant les opérations de séchage , de repassage et de rangement des articles lavés, dans l'armoire de rangement, et enfin au cours du porté ou de l'usage du linge.In particular, the odor of the perfume, or at least a fraction of this odor, must be perceptible in the store where the detergent is presented for purchase, during the lifetime of the package (even when opened), during washing himself, from the washing machine, during the operations of drying, ironing and storing the washed articles, in the storage cupboard, and finally during the carrying or the use of the linen.
Une telle série d'exigence n'est évidemment pas facile à satisfaire, mais parmi les moyens qu'il faut déployer pour tendre à cette satisfaction, l'enrobage et l'encapsulation , qui améliorent la stabilité au stockage et peuvent permettre dans certaines conditions, un relargage du parfum pendant le lavage, sont un des moyens les plus importants et les plus efficaces.Such a series of requirements is obviously not easy to satisfy, but among the means that must be deployed to achieve this satisfaction, coating and encapsulation, which improve storage stability and can allow under certain conditions , a release of the perfume during washing, are one of the most important and effective means.
Plusieurs modes de mise en forme solide des parfums ont été tentés dans le passé ou très récemment par les fabricants de parfums ou les fabricants de lessives pour résoudre tout ou partie de ces problèmes.Several methods of solid shaping of perfumes have been tried in the past or very recently by the perfume manufacturers or the detergent manufacturers to solve all or some of these problems.
L'un des premiers moyens est d'utiliser les propriétés absorbantes de certains supports poreux, tels les silices, les argiles, les zeolithes naturelles ou synthétiques, les amidons, la carboxyméthylcellulose, l'urée, les phosphates minéraux solubles ... Mais les inconvénients de ces modes de mise en forme sont nombreux, notamment le fait de diviser et d'étaler le parfum sur des très grandes surfaces de contact, d'augmenter ainsi les risques d'oxydation en même temps que la surface d'échange entre le parfum et l'air, et aussi le risque de faire une rétention sélective d'un ou plusieurs composants, avec restitution d'une odeur modifiée.One of the first ways is to use the absorbent properties of certain porous supports, such as silicas, clays, natural or synthetic zeolites, starches, carboxymethylcellulose, urea, soluble mineral phosphates ... But the There are many disadvantages of these modes of shaping, in particular the fact of dividing and spreading the perfume over very large contact surfaces, thereby increasing the risks of oxidation at the same time as the exchange surface between the perfume and air, and also the risk of making a selective retention of one or more components, with restitution of a modified odor.
La simple absorbtion permet la mise en forme solide, mais est souvent insuffisante pour la protection du parfum pendant les stockages. On doit avoir recours en outre à un enrobage de l'ensemble parfum/support. Un autre mode de mise en forme est l'usage de produits à structure moléculaire particulière permettant de créer une cavité d'accueil pour les parfums, par exemple les produits tels les cyclodextrines. L'inconvénient, outre le coût, est la difficulté à introduire des compositions complexes basées sur des produits de masse molaire et d'encombrement stériques très différents et dissemblables.Simple absorption allows solid shaping, but is often insufficient for the protection of the perfume during storage. A coating of the perfume / support assembly must also be used. Another mode of shaping is the use of products with a particular molecular structure making it possible to create a reception cavity for perfumes, for example products such as cyclodextrins. The downside, besides the cost, is the difficulty in introducing complex compositions based on very different and dissimilar steric molecular weight and bulk products.
Des matrices organiques composées de PEG ou de paraffines de masse moléculaire suffisante pour être solides à température ordinaire, ont aussi été proposées pour solidifier les compositions parfumées, avec des avantages mais aussi des inconvénients, notamment celui de ne relâcher que partiellement le parfum ou encore le fait de devoir utiliser des phases fondues des produits enrobants.Organic matrices composed of PEG or paraffins of sufficient molecular mass to be solid at ordinary temperature have also been proposed for solidifying the perfumed compositions, with advantages but also disadvantages, in particular that of only partially releasing the perfume or else the having to use molten phases of the coating products.
Egalement des méthodes sophistiquées et difficile à contrôler comme les techniques de micro encapsulation par polycondensation interfaciale ont été avancées pour obtenir des parfums encapsulés, mais leur coût et leur complexité n'a pas facilité leur développement.Also sophisticated and difficult to control methods such as microencapsulation techniques by interfacial polycondensation have been advanced to obtain encapsulated perfumes, but their cost and their complexity have not facilitated their development.
Enfin, l'usage de microcapsules préformées, soit minérales soit polymériques, éventuellement mécaniquement friables a aussi été envisagé, sans grande réussite commerciale, probablement pour des raisons économiques. La Demanderesse a trouvé une mise en forme solide dispersable dans l'eau, des parfums liquides, par encapsulation par une matrice protectrice qui se localise à l'extérieur des goutellettes de parfum finement divisé ; de cette manière, ladite matrice enrobe le parfum, le protège en même temps qu'elle permet le passage à l'état solide.Finally, the use of preformed microcapsules, either mineral or polymeric, possibly mechanically friable, has also been considered, without great commercial success, probably for economic reasons. The Applicant has found a solid form dispersible in water, liquid perfumes, by encapsulation by a protective matrix which is localized outside the droplets of finely divided perfume; in this way, said matrix coats the perfume, protects it at the same time as it allows the transition to the solid state.
Un premier objet de l'invention consiste en des granulés dispersables dans l'eau, comprenantA first object of the invention consists of water dispersible granules, comprising
- au moins un parfum hydrophobe (P), sous forme de gouttelettes, finement divisé dans et encapsulé par une matrice organique solide hydrosoluble ou hydrodispersable (MO), choisie parmi- at least one hydrophobic perfume (P), in the form of droplets, finely divided into and encapsulated by a water-soluble or water-dispersible (MO) solid organic matrix, chosen from
* les polypeptides (PP) d'origine végétale ou synthétique hydrosolubles ou hydrodispersables* water-soluble or water-dispersible polypeptides (PP) of plant or synthetic origin
* les polyelectrolytes (PE) appartenant à la famille des polyacides faibles * polyelectrolytes (PE) belonging to the family of weak polyacids
* ou leurs mélanges.* or their mixtures.
- et au moins un agent émulsifiant (AE) à l'interface gouttelette/matrice.- And at least one emulsifying agent (AE) at the droplet / matrix interface.
Pour une bonne réalisation de l'invention, lesdits granulés dispersables dans l'eau, comprennentFor a good implementation of the invention, said water-dispersible granules comprise
- de 5 à 90 %, de préférence de 25 à 70 % de leur poids, de parfum (P),- from 5 to 90%, preferably from 25 to 70% by weight, of perfume (P),
- de 5 à 90 %, de préférence de 25 à 70 % de leur poids, de matrice organique hydrosoluble ou hydrodispersable (MO),- from 5 to 90%, preferably from 25 to 70% by weight, of water-soluble or water-dispersible (MO) organic matrix,
- de 0,02 à 20 %, de préférence de 0,1 à 10 % de leur poids, d'agent émulsifiant (AE), lesdits pourcentages étant exprimés en poids de matière sèche.- from 0.02 to 20%, preferably from 0.1 to 10% by weight, of emulsifying agent (AE), said percentages being expressed by weight of dry matter.
Lesdites gouttelettes peuvent présenter une granulométrie moyenne de l'ordre de 0,1 à 10μm, de préférence de l'ordre de 0,2 à 5 μm. On entend par "parfum", soit une essence parfumée, soit plus généralement une composition complexe obtenue à l'aide de nombreux produits odorants en mélange et de produits excipients qui en assurent l'homogénéité.Said droplets can have an average particle size of the order of 0.1 to 10 μm, preferably of the order of 0.2 to 5 μm. The term “perfume” is intended to mean either a perfumed essence or more generally a complex composition obtained using numerous odorous products in mixture and excipient products which ensure their homogeneity.
Lesdits parfums selon l'invention sont des composés isotropes et hydrophobes. Leur solubilité dans l'eau à pH 7 ne dépasse pas 10% en poids.Said perfumes according to the invention are isotropic and hydrophobic compounds. Their solubility in water at pH 7 does not exceed 10% by weight.
Le mélange de produits odorants peut comprendre un grand nombre de constituants, choisis de façon à obtenir les notes parfumées désirées pour l'utilisation, le public et le marché visés. On trouve généralement des produits naturels (par exemple essences végétales ou animales obtenues par extraction à la vapeur ou par extraction alcoolique, qui sont eux-mêmes déjà des mélanges) ou des produits synthétiques qui peuvent être des cétones aliphatiques ou aromatiques, des aldéhydes aliphatiques ou aromatiques, des produits de condensation des aldéhydes et des aminés, des lactones aromatiques ou aliphatiques, des éthers ou esters aromatiques ou aliphatiques, des alcools aliphatiques de masse moléculaires variées, des hydrocarbures saturés ou insaturés linéaires, cycliques ou aromatiques, terpéniques, polynucléaires ou non.The mixture of odorous products can comprise a large number of constituents, chosen so as to obtain the desired fragrant notes for the intended use, the public and the market. There are generally natural products (for example vegetable or animal essences obtained by steam extraction or by alcoholic extraction, which are themselves already mixtures) or synthetic products which can be aliphatic or aromatic ketones, aliphatic aldehydes or aromatics, condensation products of aldehydes and amines, aromatic or aliphatic lactones, aromatic or aliphatic ethers or esters, aliphatic alcohols of various molecular weights, saturated or unsaturated hydrocarbons, linear, cyclic or aromatic, terpenic, polynuclear or not .
Les compositions de parfums les plus sophistiquées peuvent renfermer jusqu'à une centaine d'ingrédients.The most sophisticated perfume compositions can contain up to a hundred ingredients.
A titre d'exemple de composé odorant, on peut citer : l'aldéhyde hexyl cinnamique, le 2-méthyl-3(para-tert-butylphényl)-propionaldéhyde le 7-acétyl-1 ,2,3,4,5,6,7,8-octahydro-1 ,1 ,6,7-tetraméthyl naphtalène le benzyl salicylate ; la 7-acétyl-1 ,1 ,3,4,4,6-hexaméthyl tetraline le para-tert-butyl cyclohexyl acétate le méthyl dihydro jasmonate ; le beta-naphtol méthyl ether la méthyl beta-naphtyl cétone ; le 2-méthyl-2-(para-iso-propylphényl)-propionaldéhyde le 1 ,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexaméthyl-cyclopenta-gamma-2-benzopyrane le dodecahydro-3a,6,6,9a-tetraméthylnaphto[2,1b]bifurane ; l'anisaldéhyde la coumarine ; le cédrol ; la vanilline ; le cyclopentadecanolide le tricyclodécényi acétate ; le tricyclodécénylpropionate ; le phénylethylalcool le terpinéol ; le linalool ; le linalyl acétate ; le géraniol ; le nérol le 2-(1 ,1-diméthyléthyl)cyclohexanol acétate ; le benzyl acétate ; les terpenes (orange) l'eugénol ; le diéthylphtalate les huiles essentielles, résines ou résinoïdes (huile d'orange, citron, patchouli, beaume du Pérou, Olibanum résinoïde, styrax, coriandre, lavandin, lavande ...) D'autres exemples de composés odorants sont décrits dans H 1468 (United States Statutory Invention Registration).As an example of an odorous compound, there may be mentioned: cinnamic hexyl aldehyde, 2-methyl-3 (para-tert-butylphenyl) -propionaldehyde 7-acetyl-1, 2,3,4,5,6 , 7,8-octahydro-1, 1, 6,7-tetramethyl naphthalene benzyl salicylate; 7-acetyl-1, 1, 3,4,4,6,6-hexamethyl tetraline para-tert-butyl cyclohexyl acetate methyl dihydro jasmonate; beta-naphthol methyl ether methyl beta-naphthyl ketone; 2-methyl-2- (para-iso-propylphenyl) -propionaldehyde 1, 3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-gamma-2 -benzopyran dodecahydro-3a, 6,6,9a-tetramethylnaphto [2,1b] bifuran; anisaldehyde coumarin; cedrol; vanillin; cyclopentadecanolide tricyclodecenyi acetate; tricyclodecenylpropionate; phenylethyl alcohol terpineol; the linalool; linalyl acetate; geraniol; nerol 2- (1,1-dimethylethyl) cyclohexanol acetate; benzyl acetate; terpenes (orange) eugenol; diethylphthalate essential oils, resins or resinoids (orange oil, lemon, patchouli, Peruvian beaume, resinoid olibanum, styrax, coriander, lavandin, lavender ...) Other examples of odorous compounds are described in H 1468 ( United States Statutory Invention Registration).
Parmi les polypeptides (PP) de synthèse hydrosolubles ou hydrodispersables pouvant constituer la matrice, on peut mentionner les homopolymères et copolymères dérivés de la polycondensation d'acides aminés, notamment de l'acide aspartique et glutamique ou des précurseurs desdits aminodiacides, et hydrolyse. Ces polymères peuvent être aussi bien des homopolymères dérivés de l'acide aspartique ou glutamique que des copolymères dérivés de l'acide aspartique et de l'acide glutamique en proportions quelconques, ou des copolymères dérivés de l'acide aspartique et / ou glutamique et d'aminoacides autres. Parmi les aminoacides copolymérisables, on peut citer la glycine, l'alanine, la leucine, l'isoleucine, la phényl alanine, la méthionine, l'histidine, la proline, la lysine, la serine, la thréonine, la cystéine ...Among the water-soluble or water-dispersible synthetic polypeptides (PP) which may constitute the matrix, mention may be made of homopolymers and copolymers derived from the polycondensation of amino acids, in particular aspartic acid and glutamic acid or precursors of said aminodiacides, and hydrolysis. These polymers can be homopolymers derived from aspartic or glutamic acid as well as copolymers derived from aspartic acid and glutamic acid in any proportions, or copolymers derived from aspartic acid and / or glutamic acid and d other amino acids. Among the copolymerizable amino acids, there may be mentioned glycine, alanine, leucine, isoleucine, phenyl alanine, methionine, histidine, proline, lysine, serine, threonine, cysteine ...
Parmi les polypeptides (PP) d'origine végétale, on peut mentionner les protéines d'origine végétale hydrosolubles ou hydrodispersables. Elles sont de préférence hydrolysées ; leur degré d'hydrolyse est preferentiellement inférieur ou égal à 40%, par exemple de 5 à moins de 40%.Among the polypeptides (PP) of plant origin, mention may be made of proteins of plant origin which are water-soluble or water-dispersible. They are preferably hydrolyzed; their degree of hydrolysis is preferably less than or equal to 40%, for example from 5 to less than 40%.
Parmi les protéines d'origine végétale, on peut citer à titre indicatif les protéines provenant des graines protéagineuses notamment celles de pois, de féverole, de lupin, de haricot, et de lentille ; les protéines provenant de grains de céréales notamment celles du blé, de l'orge, du seigle, du maïs, du riz, de l'avoine, et du millet ; les protéines provenant des graines oléagineuses notamment celles du soja, de l'arachide, du tournesol, du colza, et de la noix de coco ; les protéines provenant des feuilles notamment de luzerne, et d'orties ; et les protéines provenant d'organes végétaux de réserves enterrées notamment celle de pomme de terre, et de betterave. La protéine d'origine végétale provient plus particulièrement du soja ou du blé.Among the proteins of vegetable origin, mention may be made, by way of indication, of the proteins originating from protein seeds, in particular those of peas, faba beans, lupins, beans, and lentils; proteins from cereal grains, especially those from wheat, barley, rye, corn, rice, oats, and millet; proteins from oil seeds, especially those from soybeans, peanuts, sunflowers, rapeseed, and coconuts; proteins from the leaves, especially alfalfa, and nettles; and proteins from plant organs from buried reserves, notably that of potatoes and beets. The vegetable protein comes more particularly from soybeans or wheat.
Le polyélectrolyte (PE) peut être choisi parmi ceux issus de la polymérisation de monomères qui ont la formule généraleThe polyelectrolyte (PE) can be chosen from those resulting from the polymerization of monomers which have the general formula
(R1)(R2)C=C (R3) COOH formule dans laquelle R1, R2, et R3 sont identiques ou différents et représentent . un atome d'hydrogène,(R 1 ) (R 2 ) C = C (R 3 ) COOH formula in which R 1 , R 2 , and R 3 are identical or different and represent. a hydrogen atom,
. un radical hydrocarboné contenant de 1 à 4 atomes de carbone, méthyle de préférence. a hydrocarbon radical containing from 1 to 4 carbon atoms, preferably methyl
. une fonction -COOH. a -COOH function
. un radical -R-COOH, où R représente un reste hydrocarboné contenant de 1 à 4 atomes de carbone, de préférence un reste alkylène contenant 1 ou 2 atomes de carbone, méthylène tout particulièrement.. a radical -R-COOH, where R represents a hydrocarbon residue containing from 1 to 4 carbon atoms, preferably an alkylene residue containing 1 or 2 carbon atoms, methylene in particular.
A titre d'exemples non limitatifs, on peut citer les acides acrylique, méthacrylique, maléique, fumarique, itaconique, crotonique.By way of nonlimiting examples, mention may be made of acrylic, methacrylic, maleic, fumaric, itaconic and crotonic acids.
Conviennent également les copolymères obtenus à partir des monomères répondant à la formule générale précédente et ceux obtenus à l'aide de ces monomères et d'autres monomères, en particulier les dérivés vinyliques comme les alcools vinyliques et les amides copolymérisables comme l'acrylamide ou le méthacrylamide. On peut également citer les copolymères obtenus à partir d'alkyle vinyl éther et d'acide maléique ainsi que ceux obtenus à partir de vinyl styrène et d'acide maléique qui sont notamment décrits dans l'encyclopédie KIRK-OTHMER intitulé "ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY" - Volume 18 - 3 ème édition - Wiley interscience publication - 1982. Les polyelectrolytes préférés présentent un degré de polymérisation faible. La masse moléculaire en poids des polyelectrolytes est plus particulièrement inférieure à 20000 g/mole. De préférence, elle est comprise entre 1000 et 5000 g/mole.Also suitable are the copolymers obtained from the monomers corresponding to the preceding general formula and those obtained using these monomers and other monomers, in particular vinyl derivatives such as vinyl alcohols and copolymerizable amides such as acrylamide or methacrylamide. We can also mention the copolymers obtained from alkyl vinyl ether and maleic acid as well as those obtained from vinyl styrene and maleic acid which are in particular described in the KIRK-OTHMER encyclopedia entitled "ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY" - Volume 18 - 3rd edition - Wiley interscience publication - 1982. The preferred polyelectrolytes have a low degree of polymerization. The molecular weight by weight of the polyelectrolytes is more particularly less than 20,000 g / mole. Preferably, it is between 1000 and 5000 g / mole.
Les agents émuisifiants (AE) pouvant être présents, sont des émulsifiants non- ioniques, ioniques ou amphotères. Lorsque ladite matrice (MO) est en un polypeptide (PP), ledit agent émulsifiant (AE) est choisi parmi les émuisifiants ioniques ou amphotères. Lorsque ladite matrice (MO) est en un polyélectrolyte (PE), ledit agent émulsifiant (AE) est choisi parmi les émuisifiants non-ioniques ou amphotères.The emulsifying agents (AE) which may be present are non-ionic, ionic or amphoteric emulsifiers. When said matrix (MO) is made of a polypeptide (PP), said emulsifying agent (AE) is chosen from ionic or amphoteric emulsifiers. When said matrix (MO) is made of a polyelectrolyte (PE), said emulsifying agent (AE) is chosen from nonionic or amphoteric emulsifiers.
Parmi les émuisifiants non-ioniques, on peut citer notamment les dérivés polyoxyalkylénés commeAmong the nonionic emulsifiers, mention may be made in particular of polyoxyalkylenated derivatives such as
- les alcools gras éthoxylés ou éthoxy-propoxylés- ethoxylated or ethoxy-propoxylated fatty alcohols
- les triglycérides éthoxylés ou éthoxy-propoxylés- ethoxylated or ethoxy-propoxylated triglycerides
- les acides gras éthoxylés ou éthoxy-propoxylés- ethoxylated or ethoxy-propoxylated fatty acids
- les esters de sorbitan éthoxylés ou éthoxy-propoxylés - les aminés grasses éthoxylées ou éthoxy-propoxylées- ethoxylated or ethoxy-propoxylated sorbitan esters - fatty ethoxylated or ethoxy-propoxylated amines
- les di(phényl-1 éthyl) phénols éthoxylés ou éthoxy-propoxylés- ethoxylated or ethoxy-propoxylated di (phenyl-1 ethyl) phenols
- les tri(phényl-1 éthyl) phénols éthoxylés ou éthoxy-propoxylés- tri (1-phenylethyl) ethoxylated or ethoxy-propoxylated phenols
- les alkyls phénols éthoxylés ou éthoxy-propoxylés- ethoxylated or ethoxy-propoxylated alkyl phenols
Le nombre de motifs oxyéthylène (OE) et/ou oxypropylène (OP) de ces tensio-actifs non ioniques varie habituellement de 2 à 100 selon la HLB (balance hydrophilie/lipophilie) souhaitée. Plus particulièrement, le nombre de motifs OE et/ou OP se situe entre 2 et 50. De préférence, le nombre de motifs OE et/ou OP est compris entre 10 et 50.The number of oxyethylene (OE) and / or oxypropylene (OP) units of these nonionic surfactants usually varies from 2 to 100 depending on the HLB (hydrophilic / lipophilic balance) desired. More particularly, the number of OE and / or OP units is between 2 and 50. Preferably, the number of OE and / or OP units is between 10 and 50.
Les alcools gras éthoxylés ou éthoxy-propoxylés comprennent généralement de 6 à 22 atomes de carbone, les motifs OE et OP étant exclus de ces nombres. De préférence, ces motifs sont des motifs éthoxylés.Ethoxylated or ethoxy-propoxylated fatty alcohols generally contain from 6 to 22 carbon atoms, the OE and OP units being excluded from these numbers. Preferably, these units are ethoxylated units.
Les triglycérides éthoxylés ou éthoxy-propoxylés peuvent être des triglycérides d'origine végétale ou animale (tels que le saindoux, le suif, l'huile d'arachide, l'huile de beurre, l'huile de graine de coton, l'huile de lin, l'huile d'olive, l'huile de poisson, l'huile de palme, l'huile de pépin de raisin, l'huile de soja, l'huile de ricin, l'huile de colza, l'huile de coprah, l'huile de noix de coco et sont de préférence éthoxylés.The ethoxylated or ethoxy-propoxylated triglycerides can be triglycerides of plant or animal origin (such as lard, tallow, peanut oil, butter oil, cottonseed oil, oil flaxseed, olive oil, fish oil, palm oil, grape seed oil, soybean oil, castor oil, rapeseed oil, coconut oil, coconut oil and are preferably ethoxylated.
Les acides gras éthoxylés ou éthoxy-propoxylés sont des esters d'acide gras (tels que par exemple l'acide oléïque, l'acide stéarique), et sont de préférence éthoxylés. Les esters de sorbitan éthoxylés ou éthoxy-propoxylés sont des esters du sorbitol cyclisés d'acide gras comprenant de 10 à 20 atomes de carbone comme l'acide laurique, l'acide stéarique ou l'acide oléïque, et sont de préférence éthoxylés.The ethoxylated or ethoxy-propoxylated fatty acids are fatty acid esters (such as for example oleic acid, stearic acid), and are preferably ethoxylated. The ethoxylated or ethoxy-propoxylated sorbitan esters are cyclized fatty acid sorbitol esters comprising from 10 to 20 carbon atoms such as lauric acid, stearic acid or oleic acid, and are preferably ethoxylated.
Le terme triglycéride éthoxylé vise dans la présente invention, aussi bien les produits obtenus par éthoxylation d'un triglycéride par l'oxyde d'éthylène que ceux obtenus par transestérification d'un triglycéride par un polyéthyièneglycol.The term ethoxylated triglyceride is intended in the present invention, both the products obtained by ethoxylation of a triglyceride with ethylene oxide as those obtained by transesterification of a triglyceride with a polyethylene glycol.
De même, le terme acide gras éthoxylé inclue aussi bien les produits obtenus pas éthoxylation d'un acide gras par l'oxyde d'éthylène que ceux obtenus par transestérification d'un acide gras par un polyéthyièneglycol. Les aminés grasses éthoxylés ou éthoxy-propoxylés ont généralement de 10 à 22 atomes de carbone, les motifs OE et OP étant exclus de ces nombres, et sont de préférence éthoxylés.Likewise, the term ethoxylated fatty acid includes both the products obtained by ethoxylation of a fatty acid with ethylene oxide and those obtained by transesterification of a fatty acid with a polyethylene glycol. Ethoxylated or ethoxy-propoxylated fatty amines generally have from 10 to 22 carbon atoms, the OE and OP units being excluded from these numbers, and are preferably ethoxylated.
Les alkylphénols éthoxylés ou éthoxy-propoxylé sont généralement 1 ou 2 groupes alkyies, linéaires ou ramifiés, ayant 4 à 12 atomes de carbone. A titre d'exemple on peut citer notamment les groupes octyles, nonyles ou dodécyles.The ethoxylated or ethoxy-propoxylated alkylphenols are generally 1 or 2 alkyl groups, linear or branched, having 4 to 12 carbon atoms. By way of example, mention may in particular be made of octyl, nonyl or dodecyl groups.
A titre d'exemples de tensio-actifs non ioniques du groupe des alkylphénols éthoxy ou éthoxy-propoxylés, des di(phényl-1 éthyl) phénols éthoxylés et des tri(phényl-1 éthyl) phénols éthoxy ou éthoxy-propoxyiés, on peut citer notamment le di(phényl-1 éthyl)phénol éthoxylé avec 5 motifs OE, le di(phényl-1 éthyl)phénol éthoxylé avec 10 motifs OE, le tri(phényl-1 éthyl)phénoi éthoxylé avec 16 motifs OE, le tri(phényl-1 éthyl)phénol éthoxylé avec 20 motifs OE, le tri(phényl-1 éthyl)phénol éthoxylé avec 25 motifs OE, le tri(phényl-1 éthyl)phénol éthoxylé avec 40 motifs OE, les tri(phényl-1 éthyl)phénols éthoxy-propoxylés avec 25 motifs OE + OP, le nonylphenol éthoxylé avec 2 motifs OE, le nonylphenol éthoxylé avec 4 motifs OE, le nonylphenol éthoxylé avec 6 motifs OE, le nonylphenol éthoxylé avec 9 motifs OE, les nonylphenols éthoxy-propoxylés avec 25 motifs OE + OP, les nonylphenols éthoxy-propoxylés avec 30 motifs OE + OP, les nonylphenols éthoxy-propoxylés avec 40 motifs OE + OP, les nonylphenols éthoxy- propoxylés avec 55 motifs OE + OP, les nonylphenols éthoxy-propoxylés avec 80 motifs OE + OP. Parmi les émuisifiants anioniques, on peut citer les sels hydrosolubles d'alkylsuifates, d'alkyléthersulfates, les alkyliséthionates et les alkyltaurates ou leurs sels, les alkylcarboxylates, les alkylsulfosuccinates ou les alkylsuccinamates, les alkylsarcosinates, les dérivés alkylés d'hydrolysats de protéines, les acylaspartates, les phosphates esters d'alkyle et/ou d'alkyléther et/ou d'alkylaryléther. Le cation est en général un métal alcalin ou alcalino-terreux, tels que le sodium, le potassium, le lithium, le magnésium, ou un groupement ammonium NR4 + avec R, identiques ou différents, représentant un radical alkyle substitué ou non par un atome d'oxygène ou d'azote. 8As examples of nonionic surfactants from the group of ethoxy or ethoxy-propoxylated alkylphenols, ethoxylated di (phenyl-1 ethyl) phenols and ethoxy or ethoxy-propoxy tri (phenyl-ethyl) phenols, mention may be made in particular ethoxylated di (phenyl-ethyl) phenol with 5 EO units, ethoxylated di (phenyl-ethyl) phenol with 10 EO units, tri (1-ethylphenyl) phenox ethoxylated with 16 EO units, tri (phenyl -1 ethyl) ethoxylated phenol with 20 EO units, tri (1-phenyl ethyl) ethoxylated phenol with 25 EO units, tri (1-phenylethyl) ethoxylated phenol with 40 EO units, tri (1-phenyl ethyl) phenols ethoxy-propoxylated with 25 EO + OP units, ethoxylated nonylphenol with 2 EO units, ethoxylated nonylphenol with 4 EO units, ethoxylated nonylphenol with 6 EO units, ethoxylated nonylphenol with 9 EO units, ethoxy-propoxylated nonylphenols with 25 units OE + OP, ethoxy-propoxylated nonylphenols with 30 OE + OP units, no ethoxy-propoxylated nylphenols with 40 OE + OP units, ethoxy-propoxylated nonylphenols with 55 OE + OP units, ethoxy-propoxylated nonylphenols with 80 OE + OP units. Among the anionic emulsifiers, mention may be made of the water-soluble salts of alkylsuifates, of alkylethersulfates, alkylisethionates and alkyltaurates or their salts, alkylcarboxylates, alkylsulfosuccinates or alkylsuccinamates, alkylsarcosinates, alkyl derivatives of protein hydrolysates, acylaspartates, phosphates, alkyl esters and / or alkyl ether and / or alkylaryl ether. The cation is generally an alkali or alkaline earth metal, such as sodium, potassium, lithium, magnesium, or an ammonium group NR 4 + with R, identical or different, representing an alkyl radical substituted or not by a oxygen or nitrogen atom. 8
Parmi les émuisifiants cationiques, on peut citer les halogénures d'alkyldiméthyl- benzylammonium, les halogénures d'alkyldiméthyléthylammonium ...Among the cationic emulsifiers, mention may be made of alkyldimethylbenzylammonium halides, alkyldimethylethylammonium halides, etc.
Parmi les émuisifiants amphotères, on peut citer les alkyl-bétaïnes, les alkyldiméthylbétaïnes, les alkylamidopropylbétaines, les alkylamido- propyldiméthylbétaïnes, les alkyltriméthyl-sulfobétaïnes, les dérivés d'imidazoline tels que les alkylamphoacétates, alkylamphodiacétates, alkylampho-propionates, alkyl- amphodipropionates, les alkylsultaïnes ou les alkylamidopropyl-hydroxysultaïnes, les produits de condensation d'acides gras et d'hydrolysats de protéines, les dérivés amphotères des alkylpolyamines comme l'Amphionic XL® commercialisé par Rhône- Poulenc, Ampholac 7T/X® et Ampholac 7C/X® commercialisés par Berol Nobel, les protéines ou hydrolysats de protéines.Among the amphoteric emulsifiers, mention may be made of alkyl betaines, alkyldimethyl betaines, alkylamidopropyl betaines, alkylamidopropyl dimet betaines, alkyltrimethyl sulfobetaines, imidazoline derivatives such as alkylamphoacetates, alkylamphodiacetates, alkylampho-amphionates, alkylampho-propylates alkylsultaines or alkylamidopropyl-hydroxysultaines, condensation products of fatty acids and protein hydrolysates, amphoteric derivatives of alkylpolyamines such as Amphionic XL® marketed by Rhône-Poulenc, Ampholac 7T / X® and Ampholac 7C / X® marketed by Berol Nobel, proteins or protein hydrolysates.
Selon une variante de réalisation, jusqu'à 50% du poids de la matrice (MO) peut être constituée en un ose, oside ou poiyholoside hydrosoluble ou hydrodispersable (O). Parmi les oses on peut mentionner les aldoses tels que le glucose, le mannose, le galactose, le ribose, et les cétoses tels que le fructose.According to an alternative embodiment, up to 50% of the weight of the matrix (MO) can be made up of a water-soluble or water-dispersible ose, oside or poiyholoside (O). Among the dares, there may be mentioned aldoses such as glucose, mannose, galactose, ribose, and ketoses such as fructose.
Les osides sont des composés qui résultent de la condensation, avec élimination d'eau, de molécules d'osés entre elles ou encore de molécules d'osés avec des molécules non glucidiques. Parmi les osides on préfère les holosides qui sont formés par la réunion de motifs exclusivement glucidiques et plus particulièrement les oligoholosides (ou oligosaccharides) qui ne comportent qu'un nombre restreint de ces motifs, c'est-à-dire un nombre en général inférieur ou égal à 10. A titre d'exemples d'oligoholosides, on peut mentionner le saccharose, le lactose, la cellobiose, le maltose et la tréhalose.Osides are compounds which result from the condensation, with elimination of water, of daring molecules between them or even of daring molecules with non-carbohydrate molecules. Among the osides, the holosides which are formed by the combination of exclusively carbohydrate units are preferred, and more particularly the oligoholosides (or oligosaccharides) which contain only a limited number of these units, that is to say a number generally lower. or equal to 10. As examples of oligoholosides, mention may be made of sucrose, lactose, cellobiose, maltose and trehalose.
Les poiyholosides (ou polysaccharides) hydrosolubles ou hydrodispersables sont fortement dépolymérisés ; ils sont décrits par exemple dans l'ouvrage de P. ARNAUD intitulé "cours de chimie organique", Gaultier-Villars éditeurs, 1987. Plus particulièrement, ces poiyholosides ont une masse moléculaire en poids inférieure à 20000 g/mole.The water-soluble or water-dispersible poiyholosides (or polysaccharides) are highly depolymerized; they are described for example in the work of P. ARNAUD entitled "organic chemistry course", Gaultier-Villars editors, 1987. More particularly, these poiyholosides have a molecular weight by weight of less than 20,000 g / mole.
A titre d'exemple non limitatif de poiyholosides fortement dépolymérisés, on peut citer le dextran, l'amidon, la gomme xanthane et les galactomannanes tels que le guar ou la caroube, ces polysaccharides présentant de préférence un point de fusion supérieur à 100°C et une solubilité dans l'eau comprise entre 50 et 500g/l.By way of nonlimiting example of highly depolymerized poiyholosides, mention may be made of dextran, starch, xanthan gum and galactomannans such as guar or carob, these polysaccharides preferably having a melting point above 100 ° C. and a solubility in water of between 50 and 500 g / l.
Un deuxième objet de l'invention consiste en un procédé de préparation en deux étapes, de granulés dispersables dans l'eau, comprenantA second subject of the invention consists of a two-step process for the preparation of water-dispersible granules, comprising
- au moins un parfum hydrophobe (P), sous forme de gouttelettes, finement divisé dans et encapsulé par une matrice organique solide hydrosoluble ou hydrodispersable (MO), choisie parmi- at least one hydrophobic perfume (P), in the form of droplets, finely divided into and encapsulated by a water-soluble or water-dispersible (MO) solid organic matrix, chosen from
* les polypeptides (PP) d'origine végétale ou synthétique hydrosolubles ou hydrodispersables * les polyelectrolytes (PE) appartenant à la famille des polyacides faibles* water-soluble or water-dispersible polypeptides (PP) of plant or synthetic origin * polyelectrolytes (PE) belonging to the family of weak polyacids
* ou leurs mélanges.* or their mixtures.
- et au moins un agent émulsifiant (AE) à l'interface gouttelette/matrice, la première étape consistant à préparer une emulsion dans l'eau comprenant au moins un parfum hydrophobe (P), au moins un agent émulsifiant (AE) et ladite matrice organique hydrosoluble ou hydrodispersable (MO), la deuxième étape consistant à sécher ladite emulsion jusqu'à formation d'un granulé.- And at least one emulsifying agent (AE) at the droplet / matrix interface, the first step consisting in preparing an emulsion in water comprising at least one hydrophobic perfume (P), at least one emulsifying agent (AE) and said water-soluble or water-dispersible (MO) organic matrix, the second step consisting in drying said emulsion until a granule is formed.
Le terme "hydrophobe" est synonyme de solubilité dans l'eau à pH 7 ne dépassant pas 10% en poids. Les quantités relatives de parfum (P), d'agent émulsifiant (AE) et de matrice organique hydrosoluble ou hydrodispersable (MO) mises en oeuvre sont telles que ladite emulsion, exprimée en sec, comprenneThe term "hydrophobic" is synonymous with solubility in water at pH 7 not exceeding 10% by weight. The relative amounts of perfume (P), of emulsifying agent (AE) and of water-soluble or water-dispersible organic matrix (MO) used are such that said emulsion, expressed in dry form, comprises
- de 5 à 90 %, de préférence de 25 à 70 % de leur poids, de parfum hydrophobe (P),- from 5 to 90%, preferably from 25 to 70% by weight, of hydrophobic perfume (P),
- de 5 à 90 %, de préférence de 25 à 70 % de leur poids, de matrice organique hydrosoluble ou hydrodispersable (MO),- from 5 to 90%, preferably from 25 to 70% by weight, of water-soluble or water-dispersible (MO) organic matrix,
- de 0,02 à 20 %, de préférence de 0,1 à 10 % de leur poids, d'agent émulsifiant (AE), lesdits pourcentages étant exprimés en poids de matière sèche.- from 0.02 to 20%, preferably from 0.1 to 10% by weight, of emulsifying agent (AE), said percentages being expressed by weight of dry matter.
La quantité de matière sèche de l'émulsion est généralement comprise entre 10 et 70 % en poids et preferentiellement entre 20 et 60% en poids. On peut mettre en oeuvre toutes les méthodes de préparation d'émulsions connues de l'homme du métier et qui sont décrites dans "ENCYCLOPEDIA of EMULSIONS TECHNOLOGY", volumes 1 à 3 de Paul BECHER édités par MARCEL DEKKER INC., 1983.The amount of dry matter of the emulsion is generally between 10 and 70% by weight and preferably between 20 and 60% by weight. It is possible to use all the methods for preparing emulsions known to a person skilled in the art and which are described in "ENCYCLOPEDIA of EMULSIONS TECHNOLOGY", volumes 1 to 3 by Paul BECHER edited by MARCEL DEKKER INC., 1983.
Ainsi, la méthode dite d'émulsification en phase directe convient à la préparation des granulés selon l'invention. Il est rappelé brièvement que cette méthode consiste à préparer un mélange contenant l'eau, le ou les émuisifiants, la matrice (MO) hydrosoluble ou hydrodispersable, puis à introduire le parfum sous forme liquide, sous agitation.Thus, the so-called direct phase emulsification method is suitable for the preparation of the granules according to the invention. It is recalled briefly that this method consists in preparing a mixture containing the water, the emulsifier (s), the water-soluble or water-dispersible matrix (MO), then in introducing the perfume in liquid form, with stirring.
On peut aussi préparer l'émulsion en mettant en oeuvre des broyeurs colloïdaux tels que MENTON GAULIN et MICROFLUIDIZER (MICROFLUIDICS). La granulométrie moyenne de l'émulsion est en général comprise entre 0,1 et 10 micromètres et preferentiellement entre 0,2 et 5 micromètres.The emulsion can also be prepared by using colloid mills such as MENTON GAULIN and MICROFLUIDIZER (MICROFLUIDICS). The average particle size of the emulsion is generally between 0.1 and 10 micrometers and preferably between 0.2 and 5 micrometers.
L'émulsification peut être réalisée à une température voisine de la température ambiante, bien que des températures plus faibles ou plus élevées soient envisageables. La seconde étape du procédé de préparation selon l'invention consiste à sécher l'émulsion ainsi formulée pour obtenir des granulés.The emulsification can be carried out at a temperature close to room temperature, although lower or higher temperatures can be envisaged. The second step of the preparation process according to the invention consists in drying the emulsion thus formulated to obtain granules.
La méthode mise en oeuvre pour éliminer l'eau de l'émulsion et obtenir des granulés peut être effectuée par tout moyen connu de l'homme du métier. 10The method used to remove water from the emulsion and obtain granules can be carried out by any means known to those skilled in the art. 10
Conviennent par exemple la lyophilisation, qui correspond à une étape de congélation, suivie d'une étape de sublimation, ou bien encore le séchage par atomisation.For example, lyophilization, which corresponds to a freezing step, followed by a sublimation step, or even spray drying.
Ces modes de séchage, et plus particulièrement celui par atomisation, sont particulièrement indiqués car ils permettent de conserver l'émulsion en l'état et d'obtenir directement des granulés. Les protéines d'origine végétale hydrosolubles ou hydrodispersables sont particulièrement bien adaptées au séchage par atomisation, car elles particulièrement stables.These drying modes, and more particularly that by atomization, are particularly indicated because they make it possible to keep the emulsion in the state and to obtain granules directly. Water-soluble or water-dispersible proteins of plant origin are particularly well suited to spray drying, because they are particularly stable.
Le séchage par atomisation peut s'effectuer de manière habituelle dans tout appareil connu tel que par exemple une tour d'atomisation associant une pulvérisation réalisée par une buse ou une turbine avec un courant de gaz chaud. Les conditions de mise en oeuvre sont fonction de la nature de la matrice, de la thermosensibilité du parfum et de l'atomiseur utilisé ; ces conditions sont généralement telles que la température de l'ensemble du produit au cours du séchage ne dépasse pas 150°C, de préférence ne dépasse pas 110°C.Spray drying can be carried out in the usual manner in any known device such as for example an atomization tower associating a spraying carried out by a nozzle or a turbine with a stream of hot gas. The conditions of implementation depend on the nature of the matrix, the thermosensitivity of the perfume and the atomizer used; these conditions are generally such that the temperature of the entire product during drying does not exceed 150 ° C., preferably does not exceed 110 ° C.
D'une façon inattendue, le séchage par atomisation dans un courant de gaz chaud se fait sans altération du parfum.Unexpectedly, spray drying in a stream of hot gas takes place without altering the fragrance.
Il est à noter que des additifs, tels que les agents antimottants peuvent être incorporés aux granulés au moment de cette seconde étape de séchage. On recommande d'utiliser une charge choisie notamment parmi le carbonate de calcium, le kaolin, la silice, la bentonite ...It should be noted that additives, such as anti-caking agents can be incorporated into the granules at the time of this second drying step. We recommend using a filler chosen in particular from calcium carbonate, kaolin, silica, bentonite ...
Les particules composites obtenues sont redispersables dans l'eau.The composite particles obtained are redispersible in water.
La libération du parfum, lors de la remise en dispersion peut être contrôlée par le choix de la matrice organique (MO), en choisissant une matrice à solubilité progressive ou lente.The release of the perfume, during the re-dispersion can be controlled by the choice of the organic matrix (OM), by choosing a matrix with progressive or slow solubility.
Un autre objet de l'invention consiste en l'utilisation desdits granulés dispersables comme agent parfumant dans les compositions cosmétiques et notamment dans les compositions détergentes pour le lavage du linge (lavage industriel ou ménager). Selon l'invention, lesdits granulés peuvent être utilisés à raison d'environ 0,01 à 0,5% de préférence de 0,05 à 0,2% en poids par rapport à la composition détergente.Another subject of the invention consists in the use of said dispersible granules as a perfuming agent in cosmetic compositions and in particular in detergent compositions for washing clothes (industrial or household washing). According to the invention, said granules can be used in an amount of about 0.01 to 0.5%, preferably from 0.05 to 0.2% by weight relative to the detergent composition.
Un dernier objet de l'invention consiste en des compositions cosmétiques et notamment en des compositions détergentes pour le lavage du linge (lavage industriel ou ménager), comprenant lesdits granulés dispersables à base de parfum.A final object of the invention consists of cosmetic compositions and in particular detergent compositions for washing clothes (industrial or household washing), comprising said dispersible granules based on perfume.
Selon l'invention, les compositions détergentes peuvent contenir environ 0,01 à 0,5% de préférence de 0,05 à 0,2% de leur poids de granulés dispersables à base parfum. 11According to the invention, the detergent compositions may contain approximately 0.01 to 0.5%, preferably 0.05 to 0.2%, by weight of dispersible granules based on perfume. 11
Les compositions détergentes selon l'invention, comprennent au moins un agent tensioactif, en quantité généralement de l'ordre de 5 à 60% en poids, de préférence de 8 à 50% en poids.The detergent compositions according to the invention comprise at least one surfactant, in an amount generally of the order of 5 to 60% by weight, preferably from 8 to 50% by weight.
Parmi ceux-ci, on peut citer les agents tensioactifs anioniques ou non-ioniques habituellement utilisés dans le domaine de la détergence pour le lavage du linge. Les compositions détergentes faisant l'objet de l'invention, peuvent en outre comprendre des additifs usuels, comme des adjuvants de détergence ("builders") minéraux ou organiques, en quantité telle que la quantité totale d'adjuvant de détergence soit de l'ordre de 5 à 80% du poids de ladite composition, de préférence de 8 à 40% en poids, des agents anti- salissures, des agents antiredéposition, des agents de blanchiment, des agents de fluorescence, des agents suppresseurs de mousses, des agents adoucissants, des enzymes et autres additifs.Among these, there may be mentioned the anionic or nonionic surfactants usually used in the field of detergents for washing clothes. The detergent compositions which are the subject of the invention can also comprise usual additives, such as mineral or organic detergency builders, in an amount such that the total amount of detergency builder is from 5 to 80% by weight of the said composition, preferably from 8 to 40% by weight, of the anti-fouling agents, the anti-redeposition agents, the bleaching agents, the fluorescent agents, the foam-suppressing agents, the agents softeners, enzymes and other additives.
Les exemples suivants sont donnés à titre illustratif.The following examples are given by way of illustration.
Exemple 1 :Example 1:
- Réalisation d'une emulsion de parfum dans une solution aqueuse de protéine de soia- Realization of a perfume emulsion in an aqueous solution of soy protein
On prépare un mélange de composition suivanteA mixture of the following composition is prepared
FP940 (hydrolysat de protéine de soja de degré d'hydrolyse 0,6 partie en poids inférieur à 5%, de Protein Technologies International ) (en sec) parfum 29,6 parties en poids
Figure imgf000013_0001
Eau permutée 69,8 parties en poids par addition de parfum à une solution aqueuse à 5% en poids de FP940. Le taux de matière sèche est de 30,2%.FP940 (soy protein hydrolyzate of degree of hydrolysis 0.6 part by weight less than 5%, from Protein Technologies International) (dry) fragrance 29.6 parts by weight
Figure imgf000013_0001
Deionized water 69.8 parts by weight by adding perfume to a 5% by weight aqueous solution of FP940. The dry matter rate is 30.2%.
Le mélange est d'abord pré-émulsionné à l'aide d'un de l'appareil Ultra Turrax T25 durantThe mixture is first pre-emulsified using one of the Ultra Turrax T25 devices for
1 minute à 9500 t/mn.1 minute at 9500 rpm.
L'émulsion proprement dite est réalisée au moyen d'un microfiuidiseur (M110T deThe emulsion itself is produced using a microfluidizer (M110T from
Microfluidics) dans les conditions suivantes : Pression : 600 bars - 3 passages dans le microfiuidiseur - Bain d'eau froide en sortie du microfiuidiseur.Microfluidics) under the following conditions: Pressure: 600 bars - 3 passages in the micro-fluidizer - Cold water bath at the output of the micro-fluidizer.
L'émulsion obtenue présente une granulométrie resserrée avec un diamètre médianThe emulsion obtained has a tight particle size with a median diameter
(d50) de 1 ,3 μm.(d50) of 1, 3 μm.
- Incorporation de la matrice de protéine de soia - 12- Incorporation of the soy protein matrix - 12
On incorpore à l'émulsion préparée la même protéine végétale (FP940 de Protein Technologies International) comme matrice polypeptidique. La composition de l'émulsion formulée est la suivante :The same vegetable protein (FP940 from Protein Technologies International) is incorporated into the emulsion prepared as a polypeptide matrix. The composition of the emulsion formulated is as follows:
FP940 (hydrolysat de protéine de soja de degré d'hydrolyse 0,47 partie en poids inférieur à 5%, de Protein Technologies International ) (en sec) (émulsifiant) parfum 22,95 parties en poidsFP940 (soy protein hydrolyzate of degree of hydrolysis 0.47 part by weight less than 5%, from Protein Technologies International) (dry) (emulsifier) perfume 22.95 parts by weight
FP940 (hydrolysat de protéine de soja de degré d'hydrolyse 22,48 parties en poids inférieur à 5%, de Protein Technologies International ) (en sec) (matrice)
Figure imgf000014_0001
Eau permutée 54,10 parties en poidsFP940 (soy protein hydrolyzate of degree of hydrolysis 22.48 parts by weight less than 5%, from Protein Technologies International) (in dry) (matrix)
Figure imgf000014_0001
Deionized water 54.10 parts by weight
Cette emulsion formulée présente 45,9 % de matière sèche et un diamètre médian (d50) de 1 ,3 μm.This formulated emulsion has 45.9% dry matter and a median diameter (d50) of 1.3 μm.
La composition de cette emulsion correspond à un rapport pondéral en sec A B de 51/49, rapport dans lequel A et B ont la signification suivante :The composition of this emulsion corresponds to a dry weight ratio A B of 51/49, ratio in which A and B have the following meaning:
A = (parfum+proteine FP940 émulsifiant) / % total matière sèche X 100A = (perfume + FP940 emulsifier protein) /% total dry matter X 100
B = protéine FP940 matrice/ % total matière sèche X100B = FP940 matrix protein /% total dry matter X100
- Séchage de l'émulsion formulée :- Drying of the formulated emulsion:
Cette emulsion est ensuite séchée par lyophilisation. Les granulés issus de ce traitement ont la composition suivante :This emulsion is then dried by lyophilization. The granules resulting from this treatment have the following composition:
FP940 (hydrolysat de protéine de soja de degré d'hydrolyse 1 partie en poids inférieur à 5%, de Protein Technologies International ) (émulsifiant) parfum 50 parties en poidsFP940 (soy protein hydrolyzate of degree of hydrolysis 1 part by weight less than 5%, from Protein Technologies International) (emulsifier) perfume 50 parts by weight
FP940 (hydrolysat de protéine de soja de degré d'hydrolyse 49 parties en poids inférieur à 5%, de Protein Technologies International )
Figure imgf000014_0002
(matrice)FP940 (soy protein hydrolyzate of degree of hydrolysis 49 parts by weight less than 5%, from Protein Technologies International)
Figure imgf000014_0002
(matrix)
La redispersion des granulés dans l'eau donne à nouveau une emulsion de parfum de distribution granulométrique assez homogène et de diamètre médian (d50) de 2,5 μm.The redispersion of the granules in water again gives a perfume emulsion with a fairly uniform particle size distribution and a median diameter (d50) of 2.5 μm.
Exemple 2 :Example 2:
- Réalisation d'une emulsion de parfum dans un alcool aras éthoxylé On prépare un mélange de composition suivante : 13- Production of a perfume emulsion in an ethoxylated macaw alcohol A mixture of the following composition is prepared: 13
20,0 % Parfum20.0% Perfume
1 ,2 % Synperonic A11 (alcool gras éthoxylé Ci 3-C15 contenant en moyennel 10E)1, 2% Synperonic A11 (Ci 3-C15 ethoxylated fatty alcohol containing on average 10E)
78.8 % Eau permutée présentant un extrait sec de 21 ,2%. Le mélange est d'abord pré-émulsionné à l'ultra turrax T25 durant 1 minute à 9500 t/mn. L'émulsion proprement dite est réalisée au moyen d'un microfiuidiseur (M110T de Microfluidics) dans les conditions suivantes : Pression : 500 bars - 3 passages dans le microfiuidiseur - Bain d'eau froide en sortie du microfiuidiseur.78.8% Deionized water with a dry extract of 21.2%. The mixture is first pre-emulsified with ultra turrax T25 for 1 minute at 9500 rpm. The actual emulsion is produced by means of a microfluidizer (M110T from Microfluidics) under the following conditions: Pressure: 500 bars - 3 passages in the microfiuidizer - Cold water bath at the outlet of the microfiuidizer.
L'émulsion obtenue présente une granulométrie poiydisperse avec un diamètre médian (d50) de 0,7 mm.The emulsion obtained has a poiydisperse particle size with a median diameter (d50) of 0.7 mm.
- Incorporation de la matrice d'acide polvacrylique :- Incorporation of the polyacrylic acid matrix:
La matrice incorporée à l'émulsion est un acide polyacrylique de masse molaire 2000 g/mol de Bevaloid.The matrix incorporated into the emulsion is a polyacrylic acid with a molar mass of 2000 g / mol of Bevaloid.
La composition de l'émulsion formulée est la suivante : 18,6 % ParfumThe composition of the emulsion formulated is as follows: 18.6% Perfume
1 ,1 % Synpemonic A11 (émulsifiant)1.1% Synpemonic A11 (emulsifier)
4,9 % Acide polyacrylique Mw=2000 g/mol (matrice)4.9% Polyacrylic acid Mw = 2000 g / mol (matrix)
75,4 % Eau permutée75.4% deionized water
Son extrait sec est de 24,6 %. La composition de l'émulsion ainsi formulée correspond à un rapport pondéral en secIts dry extract is 24.6%. The composition of the emulsion thus formulated corresponds to a weight ratio in sec
A /B de 80/20 avec :A / B of 80/20 with:
A= Parfum + Synperonic A11 / % total matière sèche X 100A = Perfume + Synperonic A11 /% total dry matter X 100
B= Acide polyacrylique / % total matière sèche X 100B = Polyacrylic acid /% total dry matter X 100
- Séchage de l'émulsion formulée : Cette formulation est ensuite séchée par lyophilisation. Les granulés issus de ce traitement ont la composition suivante : 75,6 % Parfum 4,5 % Synperonic A11 (émulsifiant ou dispersant)- Drying of the formulated emulsion: This formulation is then dried by lyophilization. The granules resulting from this treatment have the following composition: 75.6% Perfume 4.5% Synperonic A11 (emulsifier or dispersant)
19.9 % Acide polyacrylique (matrice) La redispersion des granulés dans l'eau donne à nouveau une emulsion de parfum de distribution granulométrique poiydisperse avec un diamètre médian (d50) de 1 ,5 mm.19.9% Polyacrylic acid (matrix) The redispersion of the granules in water again gives an emulsion of fragrance of poiydisperse particle size distribution with a median diameter (d50) of 1.5 mm.
Suivant les conditions de stockage, il peut être nécessaire d'ajouter une silice dans les proportions suivantes :Depending on the storage conditions, it may be necessary to add silica in the following proportions:
66,70 % Parfum 4,00 % Synperonic A11 (émulsifiant ou dispersant)66.70% Perfume 4.00% Synperonic A11 (emulsifier or dispersant)
17,55 % Acide polyacrylique (matrice)17.55% Polyacrylic acid (matrix)
11 ,75 % Silice Tixosil T38A (Rhône - Poulenc) 11.75% Silica Tixosil T38A (Rhône - Poulenc)

Claims

14 14
REVENDICATIONS
1) Granulés dispersables dans l'eau, comprenant1) Water dispersible granules, comprising
- au moins un parfum hydrophobe (P), sous forme de gouttelettes, finement divisé dans et encapsulé par une matrice organique solide hydrosoluble ou hydrodispersable (MO), choisie parmi- at least one hydrophobic perfume (P), in the form of droplets, finely divided into and encapsulated by a water-soluble or water-dispersible (MO) solid organic matrix, chosen from
* les polypeptides (PP) d'origine végétale ou synthétique hydrosolubles ou hydrodispersables * water-soluble or water-dispersible polypeptides (PP) of plant or synthetic origin
* les polyelectrolytes (PE) appartenant à la famille des polyacides faibles * ou leurs mélanges. * polyelectrolytes (PE) belonging to the family of weak polyacids * or their mixtures.
- et au moins un agent émulsifiant (AE) à l'interface gouttelette/matrice.- And at least one emulsifying agent (AE) at the droplet / matrix interface.
2) Granulés selon la revendication 1 ), caractérisés en ce qu'ils comprennent2) Granules according to claim 1), characterized in that they comprise
- de 5 à 90 %, de préférence de 25 à 70 % de leur poids, de parfum (P), - de 5 à 90 %, de préférence de 25 à 70 % de leur poids, de matrice organique hydrosoluble ou hydrodispersable (MO),- from 5 to 90%, preferably from 25 to 70% by weight, of perfume (P), - from 5 to 90%, preferably from 25 to 70% by weight, of water-soluble or water-dispersible organic matrix (MO ),
- de 0,02 à 20 %, de préférence de 0,1 à 10 % de leur poids, d'agent émulsifiant (AE), lesdits pourcentages étant exprimés en poids de matière sèche.- from 0.02 to 20%, preferably from 0.1 to 10% by weight, of emulsifying agent (AE), said percentages being expressed by weight of dry matter.
3) Granulés selon la revendication 1 ) ou 2), caractérisés en ce que les gouttelettes présentent une granulométrie moyenne de l'ordre de 0,1 à 10μm, de préférence de l'ordre de 0,2 à 5 μm.3) Granules according to claim 1) or 2), characterized in that the droplets have an average particle size of the order of 0.1 to 10 μm, preferably of the order of 0.2 to 5 μm.
4) Granulés selon l'une quelconque des revendications 1 ) à 3), caractérisés en ce que le parfum (P) comprend des produits odorants naturels ou synthétiques à base de cétones aliphatiques ou aromatiques, aldéhydes aliphatiques ou aromatiques, produits de condensation des aldéhydes et des aminés, lactones aromatiques ou aliphatiques, éthers ou esters aromatiques ou aliphatiques, alcools aliphatiques, hydrocarbures saturés ou insaturés linéaires, cycliques ou aromatiques, terpéniques, polynucléaires ou non.4) Granules according to any one of claims 1) to 3), characterized in that the perfume (P) comprises natural or synthetic odorous products based on aliphatic or aromatic ketones, aliphatic or aromatic aldehydes, condensation products of aldehydes and amines, aromatic or aliphatic lactones, aromatic or aliphatic ethers or esters, aliphatic alcohols, saturated or unsaturated hydrocarbons, linear, cyclic or aromatic, terpenic, polynuclear or not.
5) Granulés selon l'une quelconque des revendications 1) à 4), caractérisés en ce que les polypeptides (PP) sont choisis parmi5) Granules according to any one of Claims 1) to 4), characterized in that the polypeptides (PP) are chosen from
- les homopolymères ou copolymères de synthèse dérivés de la polycondensation d'acides aminés ou de précurseurs d'acides aminés, preferentiellement de l'acide aspartique et/ou glutamique ou de leurs précurseurs, et hydrolyse- synthetic homopolymers or copolymers derived from the polycondensation of amino acids or amino acid precursors, preferably aspartic and / or glutamic acid or their precursors, and hydrolysis
- les protéines d'origine végétale, notamment du soja ou du blé, de préférence hydrolysées avec un degré d'hydrolyse inférieur ou égal à 40%. 15- proteins of plant origin, in particular soy or wheat, preferably hydrolyzed with a degree of hydrolysis less than or equal to 40%. 15
6) Granulés selon l'une quelconque des revendications 1 ) à 4), caractérisés en ce que les polyelectrolytes (PE) sont choisis parmi les polyacides faibles de masse moléculaire en poids inférieure à 20000 g/mole, de préférence comprise entre 1000 et 5000 g/moie.6) Granules according to any one of claims 1) to 4), characterized in that the polyelectrolytes (PE) are chosen from weak polyacids of molecular weight by weight less than 20,000 g / mole, preferably between 1000 and 5000 g / half.
7) Granulés selon l'une quelconque des revendications 1 ) à 6), caractérisés en ce que l'agent émulsifiant (AE) est non-ionique, anionique, cationique ou amphotère.7) Granules according to any one of claims 1) to 6), characterized in that the emulsifying agent (AE) is non-ionic, anionic, cationic or amphoteric.
8) Granulés selon la revendication 7), caractérisés en ce que l'agent émulsifiant8) Granules according to claim 7), characterized in that the emulsifying agent
(AE) est non-ionique et choisi parmi les agents tensioactifs polyoxyalkylénés.(AE) is non-ionic and chosen from polyoxyalkylenated surfactants.
9) Granulés selon la revendication 7), caractérisées en ce que l'agent émulsifiant (AE) est amphotère et choisi parmi les protéines et hydrolysats de protéines.9) Granules according to claim 7), characterized in that the emulsifying agent (AE) is amphoteric and chosen from proteins and protein hydrolysates.
10) Procédé de préparation en deux étapes, de granulés dispersables dans l'eau, comprenant10) Process for the preparation in two stages of water dispersible granules, comprising
- au moins un parfum hydrophobe (P), sous forme de gouttelettes, finement divisé dans et encapsulé par une matrice organique solide hydrosoluble ou hydrodispersable (MO), choisie parmi- at least one hydrophobic perfume (P), in the form of droplets, finely divided into and encapsulated by a water-soluble or water-dispersible (MO) solid organic matrix, chosen from
* les polypeptides (PP) d'origine végétale ou synthétique hydrosolubles ou hydrodispersables* water-soluble or water-dispersible polypeptides (PP) of plant or synthetic origin
* les polyelectrolytes (PE) appartenant à la famille des polyacides faibles* polyelectrolytes (PE) belonging to the family of weak polyacids
* ou leurs mélanges. - et au moins un agent émulsifiant (AE) à l'interface gouttelette/matrice, la première étape consistant à préparer une emulsion dans l'eau comprenant au moins un parfum hydrophobe (P), au moins un agent émulsifiant (AE) et ladite matrice organique hydrosoluble ou hydrodispersable (MO), la deuxième étape consistant à sécher ladite emulsion jusqu'à formation d'un granulé.* or their mixtures. - And at least one emulsifying agent (AE) at the droplet / matrix interface, the first step consisting in preparing an emulsion in water comprising at least one hydrophobic perfume (P), at least one emulsifying agent (AE) and said water-soluble or water-dispersible (MO) organic matrix, the second step consisting in drying said emulsion until a granule is formed.
11 ) Procédé selon la revendication 10), caractérisé en ce que les quantités relatives de parfum (P), d'agent émulsifiant (AE) et de matrice organique hydrosoluble ou hydrodispersable (MO) mises en oeuvre sont telles que ladite emulsion, exprimée en sec, comprenne - de 5 à 90 %, de préférence de 25 à 70 % de leur poids, de parfum hydrophobe (P),11) Method according to claim 10), characterized in that the relative amounts of perfume (P), of emulsifying agent (AE) and of water-soluble or water-dispersible organic matrix (MO) used are such that said emulsion, expressed in dry, comprises - from 5 to 90%, preferably from 25 to 70% of their weight, of hydrophobic perfume (P),
- de 5 à 90 %, de préférence de 25 à 70 % de leur poids, de matrice organique hydrosoluble ou hydrodispersable (MO),- from 5 to 90%, preferably from 25 to 70% by weight, of water-soluble or water-dispersible (MO) organic matrix,
- de 0,02 à 20 %, de préférence de 0,1 à 10 % de leur poids, d'agent émulsifiant (AE), 16- from 0.02 to 20%, preferably from 0.1 to 10% of their weight, of emulsifying agent (AE), 16
lesdits pourcentages étant exprimés en poids de matière sèche.said percentages being expressed by weight of dry matter.
12) Procédé selon la revendication 10) ou 11 ), caractérisé en ce que la quantité de matière sèche de l'émulsion est comprise entre 10 et 70 % en poids et preferentiellement entre 20 et 60% en poids.12) Method according to claim 10) or 11), characterized in that the amount of dry matter of the emulsion is between 10 and 70% by weight and preferably between 20 and 60% by weight.
13) Procédé selon l'une quelconque des revendications 10) à 12), caractérisé en ce que la granulométrie moyenne de l'émulsion est comprise entre 0,1 et 10 micromètres et preferentiellement entre 0,2 et 5 micromètres.13) Method according to any one of claims 10) to 12), characterized in that the average particle size of the emulsion is between 0.1 and 10 micrometers and preferably between 0.2 and 5 micrometers.
14) Procédé selon l'une quelconque des revendications 10) à 13), caractérisé en ce que le parfum (P), l'agent émulsifiant (AE) et la matrice organique hydrosoluble ou hydrodispersable (MO) sont choisis parmi ceux mentionnés aux revendications 4), 5), 6), 7), 8) ou 9).14) Method according to any one of claims 10) to 13), characterized in that the perfume (P), the emulsifying agent (AE) and the water-soluble or water-dispersible organic matrix (MO) are chosen from those mentioned in the claims 4), 5), 6), 7), 8) or 9).
15) Procédé selon l'une quelconque des revendications 10) à 14), caractérisé en ce que le séchage de la dispersion est réalisé par lyophilisation ou par atomisation.15) Method according to any one of claims 10) to 14), characterized in that the drying of the dispersion is carried out by lyophilization or by atomization.
16) Procédé selon l'une quelconque des revendications 10) à 15), caractérisé en ce que des agents antimottants sont introduits pendant l'étape de séchage.16) Method according to any one of claims 10) to 15), characterized in that anti-caking agents are introduced during the drying step.
17) Utilisation dans les compositions cosmétiques ou les compositions détergentes pour le lavage du linge, des granulés faisant l'objet des revendications 1 ) à 9) ou obtenues selon le procédé faisant l'objet des revendications 10) à 16) comme agent parfumant.17) Use in cosmetic compositions or detergent compositions for washing clothes, of the granules which are the subject of claims 1) to 9) or obtained according to the process which is the subject of claims 10) to 16) as a perfuming agent.
18) Compositions cosmétiques comprenant lesdits granulés faisant l'objet des revendications 1) à 9) ou obtenues selon le procédé faisant l'objet des revendications 10) à 16).18) Cosmetic compositions comprising said granules which are the subject of claims 1) to 9) or obtained according to the process which is the subject of claims 10) to 16).
19) Compositions détergentes pour le lavage du linge comprenant lesdits granulés faisant l'objet des revendications 1 ) à 9) ou obtenues selon le procédé faisant l'objet des revendications 10) à 16).19) Detergent compositions for washing clothes comprising said granules which are the subject of claims 1) to 9) or obtained according to the process which is the subject of claims 10) to 16).
20) Utilisation selon la revendication 17) ou compositions détergentes selon la revendication 19), caractérisées en ce que les granulés sont mis en oeuvre à raison d'environ 0,01 à 0,5% de préférence de 0,05 à 0,2% par rapport auxdites compositions détergentes. 20) Use according to claim 17) or detergent compositions according to claim 19), characterized in that the granules are used in an amount of about 0.01 to 0.5%, preferably from 0.05 to 0.2 % relative to said detergent compositions.
PCT/FR1999/000132 1998-02-02 1999-01-22 Water dispersible granulates comprising a perfume in a water soluble or water dispersible matrix and preparation method WO1999038945A1 (en)

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WO2005100454A1 (en) 2004-03-15 2005-10-27 Rhodia Chimie Dried emulsion, method for the production thereof, and its uses
WO2012084061A1 (en) 2010-12-23 2012-06-28 Symrise Ag Fragrance granules for detergents
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CN112601805B (en) * 2018-07-09 2022-04-01 宝洁公司 Packaged composition

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