EP1814932A2 - Dried emulsion, method for preparing same and uses thereof - Google Patents

Dried emulsion, method for preparing same and uses thereof

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Publication number
EP1814932A2
EP1814932A2 EP05821415A EP05821415A EP1814932A2 EP 1814932 A2 EP1814932 A2 EP 1814932A2 EP 05821415 A EP05821415 A EP 05821415A EP 05821415 A EP05821415 A EP 05821415A EP 1814932 A2 EP1814932 A2 EP 1814932A2
Authority
EP
European Patent Office
Prior art keywords
water
dried
dried emulsion
hydrophobic
surfactant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05821415A
Other languages
German (de)
French (fr)
Inventor
Jean-Pierre Hecaen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Chimie SAS
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Rhodia Chimie SAS
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Filing date
Publication date
Application filed by Rhodia Chimie SAS filed Critical Rhodia Chimie SAS
Publication of EP1814932A2 publication Critical patent/EP1814932A2/en
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/40—Mixing liquids with liquids; Emulsifying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/80—After-treatment of the mixture
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/017—Mixtures of compounds
    • C09K23/018—Mixtures of two or more different organic oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/34—Higher-molecular-weight carboxylic acid esters

Definitions

  • the present invention relates to a dried emulsion comprising a matrix comprising a water-soluble or water-dispersible polymer, in which a hydrophobic phase is dispersed.
  • the invention also relates to a process for preparing the dried emulsion, and uses of said emulsion.
  • the dried emulsions are compositions comprising a liquid hydrophobic phase dispersed in a solid matrix. They can be obtained by drying an emulsion comprising an aqueous phase in which the liquid hydrophobic phase is dispersed, generally with the aid of a surfactant, the aqueous phase comprising the water-soluble or water-dispersible compound which will constitute all or part of of the matrix after drying.
  • Compositions in the form of dried emulsions and methods for their preparation are known to those skilled in the art.
  • the dried emulsions are generally in the form of powder or granules.
  • Dried emulsions comprising a polyalkoxylated surfactant and a matrix comprising a polymer comprising hydrophilic units and units comprising hydrophobic groups or grafts are thus known.
  • Such dried emulsions are for example described in WO 00/26280 (R 98145), WO 02/32563 (R 00137), and WO 03/006148 (R 01103).
  • the dried emulsions are generally intended to be dispersed in an aqueous composition to obtain an emulsion or a dispersion comprising the hydrophobic phase dispersed in the aqueous composition.
  • the dried emulsions can thus facilitate or make economic the handling and / or the transport and / or the vectorization and / or the protection of the hydrophobic phase.
  • the dried emulsions can thus be formulated with other solid compounds and be brought into the presence of water by the end user. For example, it is possible to produce powder mixtures. This is the case for example for certain phytosanitary compositions, and for detergent formulations in powders or granules.
  • the dried emulsions may also be placed in the presence of water by an operator preparing an aqueous formulation comprising the hydrophobic phase. It is also noted that it may be interesting to trigger the re-dispersion by an external factor (for example a change in pH, temperature, chemical composition of the environment, by the release of aqueous substances such as urine or sweat altogether or to control the kinetics of the re-dispersion.
  • an external factor for example a change in pH, temperature, chemical composition of the environment, by the release of aqueous substances such as urine or sweat .
  • Qualities of a dried emulsion include: easy re-dispersion in water, no coalescence of water-immiscible hydrophobic phase during drying and / or redispersion, good powder flowability, shape easily manipulated, for example non-oily, a control of a coalescence or droplet size of the hydrophobic phase before drying or after drying, redispersion.
  • the invention provides a dried emulsion comprising a matrix comprising a water-soluble or water-dispersible polymer, in which a hydrophobic phase is dispersed, characterized in that:
  • the dried emulsion comprises a non-polyalkoxylated surfactant
  • the water-soluble or water-dispersible polymer included in the matrix is a polycarboxylate comprising hydrophobic units.
  • the invention also provides a process for preparing such emulsions, and uses.
  • the invention also proposes a surfactant mixture particularly suitable for the implementation of the dried emulsions according to the invention, or even for the implementation of emulsions in general.
  • water-soluble or water-dispersible polymer means a polymer which, at a concentration of 10% by weight in water at a temperature of 25 ° C., does not exhibit macroscopic phase separation.
  • water-soluble or water-dispersible quality refers to the preparation pH of the dried emulsion and / or the pH of use of the dried emulsion during the re-dispersion.
  • hydrophobic phase means a compound or a composition comprising several compounds, immiscible with water (forming a macroscopic phase separation), at a concentration of 10% by weight, at a temperature of 25 ° C. vs.
  • the hydrophobic or water-dispersible phase quality refers to the preparation pH of the dried emulsion and / or the pH of use of the dried emulsion during the re-dispersion.
  • the amounts of ingredients and ratios are given by weight of dry matter.
  • the dried emulsion comprises a matrix comprising a water-soluble or water-dispersible polymer in which a hydrophobic phase is dispersed.
  • the hydrophobic phase can be liquid or solid. It is preferably liquid. In the case where the hydrophobic phase is a solid phase, it may have been liquefied by heating and emulsified during the preparation of the emulsion of the dried emulsion.
  • the hydrophobic phase is present in the form of inclusions (droplets if it is a liquid phase) in the matrix, advantageously of a mean size of between 0.1 and 50 ⁇ m, preferably between 1 and 10 ⁇ m. for example between 1 and 5 microns (determined using a HOR1BA laser diffraction granulometer). The average size may vary depending on the final application.
  • the hydrophobic phase may comprise all kinds of compounds, alone or in mixtures, optionally in solution or in dispersion in a hydrophobic solvent.
  • the hydrophobic phase may consist only of a single hydrophobic liquid.
  • the hydrophobic phase may be an active hydrophobic compound, or a mixture comprising an active hydrophobic compound in solution or a dispersion in a hydrophobic solvent.
  • hydrophobic phases or compounds included in the hydrophobic phase are:
  • silicones for example silicone oils and gums, of the MD, MTD or MQ type, optionally solubilized in solvents, and optionally functionalized with groups such as amines, alcohols, polyols, etc.
  • groups such as amines, alcohols, polyols, etc.
  • oils organic, mineral or vegetable or mineral oils, and derivatives of these oils, said oils and derivatives being immiscible with water.
  • organic solvents immiscible with water immiscible with water.
  • the non-water-soluble or water-dispersible active substances optionally solubilized in a solvent.
  • the phytosanitary active ingredients may be chosen from the family of ⁇ -cyano-phenoxybenzyl carboxylates or ⁇ -cyanohalogenophenoxy carboxylates, the family of N-methylcarbonates comprising aromatic substituents, the active ingredients such as that Aldrin, Azinphos-methyl, Benfluralin, Bifenthrin, Chlorphoxim, Chlorpyrifos, Fluchloralin, Fluroxypyr, Dichloruos, Malathion, Molinate, Parathion, Permethrin, Profenofos, Propiconazole, Prothiophos, Pyrifenox, Butachlor, Metolachlor, Chlorimephos, Diazinon, Fluazifop-P-butyl , Heptopargil, Mecarbam, Propargite, Prosulfocarb, Bromophos-ethyl, Carbophenothion, Cyhalothrin, Novaluron
  • Phytosanitary active ingredients can be used in the presence of conventional additives, chosen for example from adjuvants for increasing the effectiveness of the active ingredient, anti-foaming agents, anti-caking agents, and water-soluble fillers. or not.
  • These active substances may in solutions in a hydrophobic solvent, for example chosen from aromatic hydrocarbon solvents such as xylene, dibenzyltoluene, phosphate or phosphonate solvents such as tri-n-butyl phosphate (TBP), aliphatic hydrocarbon solvents such as that mineral or vegetable oils, alcohols such as cyclohexanol, ketones such as cyclohexanone, amides such as N, N-dimethylcaprylamide-capramid, pyrrolidones such as N-methylpyrrolidone, N-octylpyrrolidone, N dodecylpyrrolidone, N-cyclohexylpyrrolidone, alkyllactates, solvents.
  • the hydrophobic phase may in particular be a hydrophobic phase comprising deltamethrin and tri-n-butyl phosphate (TBP). It may, however, be different from a hydrophobic phase comprising both detlamethrin and TBP.
  • the hydrophobic phase may in particular be a hydrophobic phase comprising deltamethrin and a xylene-based solvent such as Solvesso 200 or 200 ND. It may, however, be different from a hydrophobic phase comprising both detlamethrin and a xylene-based solvent such as Solvesso 200 or 200 ND.
  • the hydrophobic phase may in particular be a hydrophobic phase comprising deltamethrin, a xylene-based solvent such as Solvesso 200 or 200 ND and trisamethrin. n-butyl phosphate (TBP). It may, however, be different from a hydrophobic phase comprising both detlamethrin, a xylene-based solvent such as Solvesso 200 or 200 ND, and TBP.
  • silicone oils belonging in particular to the family of dimethicones
  • lipophilic vitamins such as vitamin A and its derivatives, vitamin B2, pantothenic acid, vitamin D and vitamin E
  • mono-, di- and triglycerides the perfumes ; bactericides; UV-absorbing agents, such as aminobenzoate derivatives of PABA and PARA type, salicylates, cinnamates, anthranilates, dibenzoylmethanes, camphor derivatives and mixtures thereof.
  • Anti-aging agents can likewise be used.
  • fatty acids and alcohols include, for example, those having linear or branched alkyl chains containing from 12 to 20 carbon atoms. It may in particular be linoleic acid.
  • anti-cellulite agents such as in particular isobutylmethylxanthine and theophylline
  • anti-acne agents such as resorcinol, resorcinol acetate, benzoyl peroxide and many natural compounds.
  • Aromas, perfumes, essential oils, essences can also be used as hydrophobic active material.
  • the antimicrobial agents may be selected from thymol, menthol, triclosan, 4-hexylresorcinol, phenol, eucalyptol, benzoic acid, benzoic peroxide, butyl paraben, and mixtures thereof.
  • suitable active materials for use in the field of paints include alkyd resins, epoxy resins, isocyanates blocked or not.
  • active ingredient amino silicones as a softening agent, silicone anti-foams, antimicrobial agents, perfumes, oils and essences, etc.
  • active ingredient amino silicones as a softening agent
  • silicone anti-foams silicone anti-foams
  • antimicrobial agents perfumes, oils and essences, etc.
  • hydrophobic active substances mention may also be made of:
  • saturated or unsaturated fatty acids comprising 10 to 40 carbon atoms; esters of such acids and of alcohol containing 1 to 6 carbon atoms;
  • saturated or unsaturated monoalcohols comprising 8 to 40 carbon atoms; these compounds being used alone or in a mixture.
  • organic oils / fats / waxes of animal origin there may be mentioned, in particular, sperm whale oil, whale oil, seal oil, shark oil, cod liver oil, pork, mutton fat, perhydrosqualene, beeswax, alone or in a mixture.
  • organic oils / fats / waxes of vegetable origin include rapeseed oil, sunflower oil, peanut oil, olive oil and others.
  • mineral oils / waxes mention may be made, inter alia, of naphthenic, paraffinic (petroleum), isoparaffinic and paraffinic waxes, alone or as a mixture.
  • Products derived from alcoholysis of the above-mentioned oils can also be used.
  • the fatty acids saturated or not, comprise 10 to 40 carbon atoms, more particularly 18 to 40 carbon atoms, and can include one or more ethylenic unsaturations, conjugated or not. It should be noted that said acids may comprise one or more hydroxyl groups.
  • saturated fatty acids examples include palmitic, stearic, isostearic and behenic acids.
  • unsaturated fatty acids examples include myristoleic, palmitoleic, oleic, erucic, linoleic, linolenic, arachidonic and ricinoleic acids, as well as their mixtures.
  • esters of the acids previously listed for which the portion derived from the alcohol comprises 1 to 6 carbon atoms, such as methyl, ethyl, propyl, and isopropyl esters. etc.
  • the hydrophobic phase may comprise an immiscible intermediate phase with water in which is dispersed an internal phase immiscible or insoluble in the intermediate phase. In this case we can speak of dried multiple emulsion.
  • the dried emulsion comprises several different hydrophobic phase dispersed matrix, consisting of two populations of inclusions.
  • the water-soluble or water-dispersible polymer of the matrix is a polycarboxylate comprising hydrophobic units.
  • R 2 which may be identical or different, represent a hydrogen atom, a linear or branched, optionally cyclic, saturated or ethylenically unsaturated, aliphatic or aromatic radical, at C 2 -C 6 O, with the proviso that the two radicals R 2 are not hydrogen atoms, and optionally (III) polyoxyalkylene ester of ethylenically unsaturated carboxylic acid.
  • the monomer (I) advantageously has the formula:
  • - R 3 is a hydrogen atom or a methyl group
  • - R 1 is a hydrogen atom, a hydrocarbon radical C-] - C-] o optionally comprising a group - COOX, or a -COOX group, forming optionally with the group - COOX an anhydride group -CO-O-OC-, and
  • X is a hydrogen atom or a cation, for example the cation of sodium, of potassium, or the ammonium cation.
  • the monomer (I) is advantageously chosen from acrylic, methacrylic, citraconic, maleic, fumaric, itaconic or crotonic acids or anhydrides, in acid form or in the form of salts, for example in the form of sodium or potassium salt.
  • the monomer (II) is chosen from 1-butene, isobutylene, n-1-pentene, 2-methyl-1-butene, n-1-hexene, 2-methyl-1-pentene, 4-methyl-pentene, 2-ethyl-1-butene, diisobutylene (or 2,4,4-trimethyl-1-pentene), 2-methyl-3,3-dimethyl-1-pentene.
  • the monomer (III) may correspond to the following formula:
  • R3 is a hydrogen atom or a methyl radical
  • R4 and R5 which may be identical or different, represent a hydrogen atom or an alkyl radical containing from 1 to 4 carbon atoms,
  • R ⁇ is an alkyl, aryl, alkylaryl or arylalkyl radical containing from 1 to 30, preferably from 8 to 30 carbon atoms, n is between 2 and 100, preferably between 6 and 10O m is between 0 and 50, under reserve that n is greater than or equal to m and their sum between 2 and
  • monomers of formula (M1) are used, for which R6 is an alkyl radical containing from 8 to 30 carbon atoms, or a phenyl radical substituted with one to three 1-phenylethyl groups, or an alkylphenyl radical whose alkyl radical. contains from 8 to 16 carbon atoms.
  • the copolymer may further comprise units derived from an optional monomer (IV) selected from the following monomers:
  • vinyl aromatic monomers such as styrene, vinyltoluene, C 1 -C 20 alkyl esters of ethylenically unsaturated acids such as methyl, ethyl and butyl acrylates or methacrylates,
  • vinyl or allyl esters of ethylenically unsaturated acids such as vinyl or allyl acetates or propionates
  • vinyl or vinylidene halides such as vinyl chloride or vinylidene
  • ethylenically unsaturated nitriles such as acrylonitrile
  • hydroxyalkyl esters of ethylenically unsaturated acids such as hydroxyethyl or hydroxypropyl acrylates or methacrylates
  • ethylenically unsaturated amides such as acrylamide and methacrylamide.
  • the polycarboxylate comprising hydrophobic units is a copolymer derived from maleic anhydride or from a maleic anhydride salt and from diisobutylene.
  • a copolymer derived from maleic anhydride or from a maleic anhydride salt and from diisobutylene.
  • Such a polymer is, for example, marketed by Rhodia under the name Geropon® EGPM (in solution, in sodium carboxylate form).
  • copolymers can be obtained in a manner known to those skilled in the art, for example by radical polymerization.
  • the non-polyalkoxylated surfactant may be a non-polyalkoxylated nonionic surfactant, a non-polyalkoxylated anionic surfactant, a non-polyalkoxylated amphoteric surfactant, or a mixture of these surfactants.
  • non-polyalkoxylated amphoteric surfactants mention may be made of amphoacetates, amphodiacetates, betaines (carboxybetaines such as alkylbetaines and alkylamidoalkyl betaines), amine oxides, sultaines (sulfobetaines), and mixtures thereof.
  • non-polyalkoxylated surfactants By way of examples of non-polyalkoxylated surfactants, mention may be made of alkyl sulphates, alkyl sulphonates, alkylarylsulphonates and alkylphosphates, and mixtures thereof.
  • non-polyalkoxylated nonionic surfactants mention may be made of the following surfactants: the alkylpolyglucosides,
  • the dried emulsion may be a dried emulsion comprising, as sole non-polyacyloxylated surfactant, a sorbitan ester such as the surfactant Alkamuls S80 marketed by Rhodia. It may, however, be a dried emulsion comprising in addition another surfactant. It may in particular be different from a dried emulsion comprising, as sole non-polyacyloxylated surfactant, a sorbitan ester such as the surfactant Alkamuls S80 marketed by Rhodia.
  • the dried emulsion may be a dried emulsion comprising, as sole non-polyacyloxylated surfactant, a sorbitan ester such as the surfactant Alkamuls S80 marketed by Rhodia and as a solvent for the active ingredient a xylene-based solvent such as Solvesso 200 or 200 ND or tri-n-butyl phosphate (TBP), or a mixture of these solvents.
  • a xylene-based solvent such as Solvesso 200 or 200 ND or tri-n-butyl phosphate (TBP), or a mixture of these solvents.
  • a dried emulsion comprising, as sole non-polyacrylated surfactant, a sorbitan ester such as the surfactant Alkamuls S80 marketed by Rhodia and as a solvent for active ingredient a xylene-based solvent such as Solvesso 200 or 200 ND or tri-n-butyl phosphate (TBP), or a mixture of these solvents.
  • a xylene-based solvent such as Solvesso 200 or 200 ND or tri-n-butyl phosphate (TBP), or a mixture of these solvents.
  • the non-polyalkoxylated surfactant is:
  • the mixture of the sorbitan ester and the fatty acid comprises, in dry matter, from 2 to 20% by weight of the fatty acid or salt.
  • the mixture of the sorbitan ester and the fatty acid is a surfactant (surfactant composition, or "blend” of surfactants) which makes it possible to control the emulsification of hydrophobic phases, especially the size of the droplets of an emulsion comprising a hydrophobic phase dispersed in an aqueous phase.
  • this surfactant this surfactant composition, or "blend” of surfactants
  • emulsions dried or not, comprising this surfactant (and the hydrophobic phase and the aqueous phase), or the use of the surfactant in the emulsions.
  • the weight ratio between the hydrophobic phase and the matrix is between 50% and 80%.
  • the weight ratio between the non-polyalkoxylated surfactant and the hydrophobic phase is between 0.003 and 0.3, preferably between 0.01 and 0.06.
  • the weight ratio between the non-polyalkoxylated surfactant and the matrix is between 0.006 and 0.6, preferably between 0.02 and 1.2.
  • the matrix comprises at least 90% by weight of the water-soluble or water-dispersible polymer.
  • the dried emulsion may comprise other ingredients, which may be useful in its preparation, or which may be useful in modulating its properties or applications.
  • active ingredients ie ingredients having a function during use, for example in a liquid formulation
  • active ingredients ie ingredients having a function during use, for example in a liquid formulation
  • antifoam agents daring as described in the document WO 03/055584 (R 01186), or complexing agents comprising at least one of the elements of columns HA, IVA, VA, VIII, IB, and IHB, to more easily control the release of the hydrophobic phase during a redispersion in water, as described in WO 03/006148 (R 01103).
  • the dried emulsion may optionally contain residual water.
  • the water content is advantageously less than 10% by weight, still more preferably less than 3%.
  • the dried emulsion according to the invention may be carried out according to a process comprising the following steps: a) preparing an emulsion comprising an aqueous phase in which the hydrophobic phase dispersed in liquid form is dispersed in water, the emulsion comprising the copolymer water-soluble or water-dispersible matrix of the non-polyalkoxylated surfactant, where appropriate by heating the hydrophobic phase above its melting point, b) removing the water, to obtain a dried emulsion, c) optionally putting the dried emulsion in the form of powder or granules, d) recovering the dried emulsion,
  • an emulsion comprising the hydrophobic phase dispersed in the aqueous phase is prepared.
  • the hydrophobic phase during this step, is in liquid form. If necessary, it is heated for this purpose.
  • the emulsion comprises the water-soluble or water-dispersible polymer, and the surfactant. All methods of preparing an emulsion can be used. They are known to those skilled in the art. Methods are described, for example, in "ENCYCLOPEDIA of EMULSIONS TECHNOLOGY", volumes 1 to 3 by Paul BECHER edited by MARCEL DEKKER INC, 1983, and may be implemented within the scope of the present invention. Thus, the so-called direct phase emulsification method can be used. It is briefly recalled that this method consists of preparing a mixture containing water and emulsifiers, including the water-soluble or water-dispersible polymer, and then introducing the hydrophobic phase in liquid form, with stirring.
  • phase inversion emulsification Another suitable method is phase inversion emulsification.
  • the hydrophobic phase is mixed with an emulsifier and water which can contain the other constituents, such as the water-soluble or water-dispersible polymer for example, is introduced dropwise and with stirring. From a certain amount of introduced water, an inversion of the emulsion occurs. A direct oil-in-water emulsion is then obtained. The resulting emulsion is then diluted in water to obtain a suitable dispersed phase volume fraction.
  • the emulsion can be prepared by using colloid mills such as MANTON GAULIN and MICROFLUIDIZER (MICROFLUIDICS).
  • the average size of the hydrophobic phase droplets dispersed in the aqueous phase is generally between 0.1 and 50 ⁇ m, often between 1 and 10 microns and preferably between 0.2 and 5 microns (expressed relative to the volume of particles; by means of a laser diffraction granulometer of the type
  • the emulsification can be carried out at a temperature close to room temperature, although lower or higher temperatures are possible.
  • the quantity of water present in the emulsion, before drying, may be between 5 and 99% by weight, preferably between 20% and 70% by weight. So Generally it is preferred to use small amounts of water since it must be removed later. Controlling the amount of water can be a way to manage the viscosity.
  • Steps b) c) d) drying, shaping The method used to remove water from the emulsion and obtain the dried emulsion may be carried out by any means known to those skilled in the art.
  • drying in an oven can be envisaged.
  • This drying preferably takes place in a thin layer. More particularly, the temperature at which the drying is carried out is less than or equal to 100 ° C., preferably between 30 and 90 ° C., preferably between 50 and 90 ° C.
  • the so-called rapid drying of the mixture (or emulsion) is carried out.
  • Suitable for this purpose is spray drying in a fluidized bed, using Duprat® drums, or freeze-drying (freezing-sublimation).
  • Spray drying for example using an NIRO apparatus, or in a fluidized bed, for example using an AEROMATIC apparatus, may be carried out in the usual manner in any known apparatus such as, for example, a tower atomization device associating a spray produced by a nozzle or a turbine with a stream of hot gas.
  • the inlet temperature of the hot gas (generally air) at the top of the column is preferably between 50 ° C. and 250 ° C. and the outlet temperature is preferably lower than the degradation temperature of the elements. constituents of the granule obtained.
  • additives such as anti-caking agents may be incorporated into the granules at the time of this drying step.
  • a filler chosen in particular from calcium carbonate, barium sulfate, kaolin, silica, bentonite, titanium oxide, talc, hydrated alumina and calcium sulfoaluminate.
  • the drying is carried out such that at least 90% by weight of the external aqueous phase is removed, preferably between 90 and 95% by weight.
  • the amount of residual water is preferably less than 3% by weight.
  • the dried emulsion can be used:
  • formulations for the care of laundry for example in powdered or tablet detergents, for the formulation of softeners, the vectorization of perfumes, the formulation of defoamers, or silicones for example for a deposit on fibers ,
  • silicone oils for example defoamers.
  • the dried emulsion can be used in phytosanitary formulations, the hydrophobic phase being a phytosanitary active compound, or a mixture comprising a hydrophobic active phytosanitary compound, in solution or dispersion in a hydrophobic solvent.
  • the dried emulsion may optionally be used with other phytosanitary products (association of phytosanitary products), for example in combination with a fertilizer.
  • the dried emulsion and the fertilizer may in particular be mixed in the same tank with water.
  • Dried emulsions whose hydrophobic phase is metolachlor are prepared by preparing an emulsion comprising metolachlor, a surfactant, water and the polymer (Geropon® EGPM marketed by Rhodia), followed by drying.
  • the compositions (ingredients and quantities) of the emulsions and dried emulsions are given in the tables below.
  • the polymer is weighed down with an antifoam if necessary.
  • the stirring is carried out at 500 rpm with a paddle frame.
  • the particle size is measured during re-dispersion (1 g of powder in 50 ml of tap water, with an electromagnetic stirrer, at 500 rpm for 5 minutes at room temperature.
  • the emulsion is coarse. It is not dried afterwards.
  • the emulsion is not dried subsequently.
  • the emulsion is coarse. It is not dried afterwards.
  • a mixture comprising an ester of oleic acid and sorbitan and 8% by weight of oleic acid.
  • Emulsion before drying - Dry extract 35,3% - Surfactant / (Metolachlor + surfactant): 3%

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  • Engineering & Computer Science (AREA)
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Abstract

The invention concerns a dried emulsion comprising a matrix including a water-soluble or water-dispersible polymer, wherein is dispersed a hydrophobic phase, characterized in that: the dried emulsion comprises a non-polyalkoxylated surfactant, the water-soluble or water-dispersible polymer comprised in the matrix is a polycarboxylate including hydrophobic units.

Description

Emulsion séchée, son procédé de préparation et ses utilisations Dried emulsion, process for its preparation and uses
La présente invention a pour objet une emulsion séchée comprenant une matrice comprenant un polymère hydrosoluble ou hydrodispersable, dans laquelle est dispersée une phase hydrophobe. L'invention a également pour objet un procédé de préparation de Pémulsion séchée, et des utilisations de ladite emulsion.The present invention relates to a dried emulsion comprising a matrix comprising a water-soluble or water-dispersible polymer, in which a hydrophobic phase is dispersed. The invention also relates to a process for preparing the dried emulsion, and uses of said emulsion.
Les émulsions séchées sont des compositions comprenant une phase hydrophobe liquide dispersée dans une matrice solide. Elles sont susceptibles d'être obtenues par séchage d'une emulsion comprenant une phase aqueuse dans laquelle est dispersée la phase hydrophobe liquide, généralement à l'aide d'un tensioactif, la phase aqueuse comprenant le composé hydrosoluble ou hydrodispersable qui constituera toute ou partie de la matrice après séchage. Des compositions sous forme d'émulsions séchées et leurs procédés de préparation sont connus de l'homme du métier. Les émulsions séchées se présentent généralement sous forme de poudre ou de granulés.The dried emulsions are compositions comprising a liquid hydrophobic phase dispersed in a solid matrix. They can be obtained by drying an emulsion comprising an aqueous phase in which the liquid hydrophobic phase is dispersed, generally with the aid of a surfactant, the aqueous phase comprising the water-soluble or water-dispersible compound which will constitute all or part of of the matrix after drying. Compositions in the form of dried emulsions and methods for their preparation are known to those skilled in the art. The dried emulsions are generally in the form of powder or granules.
On connaît ainsi des émulsions séchées comprenant un tensioactif polyalcoxylé et une matrice comprenant un polymère comprenant des unités hydrophiles et des unités comprenant des groupes ou greffons hydrophobes. De telles émulsions séchées sont par exemple décrites dans les documents WO 00/26280 (R 98145), WO 02/32563 (R 00137), et WO 03/006148 (R 01103).Dried emulsions comprising a polyalkoxylated surfactant and a matrix comprising a polymer comprising hydrophilic units and units comprising hydrophobic groups or grafts are thus known. Such dried emulsions are for example described in WO 00/26280 (R 98145), WO 02/32563 (R 00137), and WO 03/006148 (R 01103).
Les émulsions séchées sont généralement destinées à être dispersées dans une composition aqueuse pour obtenir une emulsion ou une dispersion comprenant la phase hydrophobe dispersée dans la composition aqueuse. Les émulsions séchées peuvent ainsi faciliter ou rendre économique la manipulation et/ou le transport et/ou la vectorisation et/ou la protection de la phase hydrophobe. Les émulsions séchées peuvent ainsi être formulées avec d'autres composés solides et être mises en présence d'eau par l'utilisateur final. On peut ainsi par exemple réaliser des mélanges de poudres. C'est le cas par exemple pour certaines compositions phytosanitaires, et pour des formulations détergentes en poudres ou granulés. Les émulsions séchées peuvent également être mises en présence d'eau par un opérateur préparant une formulation aqueuse comprenant la phase hydrophobe. On note aussi qu'il peut être intéressant de déclencher la re-dispersion par un facteur externe (par exemple un changement de pH, de température, de composition chimique de l'environnement, par la libération de substances aqueuses telles que l'urine ou la sueur...) ou de contrôler la cinétique de la re-dispersion. Des qualités d'une émulsion séchée incluent: une re-dispersion aisée dans l'eau, pas de coalescence de la phase hydrophobe non miscible à l'eau pendant le séchage et/ou à la redispersion, une bonne coulabilité de poudre, une forme aisément manipulable, par exemple non huileuse, un contrôle d'une coalescence ou d'une taille de gouttelettes de la phase hydrophobe avant séchage ou après séchage, à la redispersion.The dried emulsions are generally intended to be dispersed in an aqueous composition to obtain an emulsion or a dispersion comprising the hydrophobic phase dispersed in the aqueous composition. The dried emulsions can thus facilitate or make economic the handling and / or the transport and / or the vectorization and / or the protection of the hydrophobic phase. The dried emulsions can thus be formulated with other solid compounds and be brought into the presence of water by the end user. For example, it is possible to produce powder mixtures. This is the case for example for certain phytosanitary compositions, and for detergent formulations in powders or granules. The dried emulsions may also be placed in the presence of water by an operator preparing an aqueous formulation comprising the hydrophobic phase. It is also noted that it may be interesting to trigger the re-dispersion by an external factor (for example a change in pH, temperature, chemical composition of the environment, by the release of aqueous substances such as urine or sweat ...) or to control the kinetics of the re-dispersion. Qualities of a dried emulsion include: easy re-dispersion in water, no coalescence of water-immiscible hydrophobic phase during drying and / or redispersion, good powder flowability, shape easily manipulated, for example non-oily, a control of a coalescence or droplet size of the hydrophobic phase before drying or after drying, redispersion.
On a à présent trouvé de nouvelles émulsions séchées pouvant présenter des qualités améliorées parmi celles mentionnées ci-dessus.We have now found new dried emulsions which may have improved qualities among those mentioned above.
Ainsi l'invention propose une émulsion séchée comprenant une matrice comprenant un polymère hydrosoluble ou hydrodispersable, dans laquelle est dispersée une phase hydrophobe, caractérisée en ce que:Thus, the invention provides a dried emulsion comprising a matrix comprising a water-soluble or water-dispersible polymer, in which a hydrophobic phase is dispersed, characterized in that:
- l'émulsion séchée comprend un tensioactif non polyalcoxylé,the dried emulsion comprises a non-polyalkoxylated surfactant,
- le polymère hydrosoluble ou hydrodispersable compris dans la matrice est un polycarboxylate comprenant des unités hydrophobes.the water-soluble or water-dispersible polymer included in the matrix is a polycarboxylate comprising hydrophobic units.
L'invention propose également un procédé de préparation de telles émulsions, et des utilisations.The invention also provides a process for preparing such emulsions, and uses.
L'invention propose également un mélange de tensioactifs particulièrement adapté à la mise en œuvre des émulsions séchées selon l'invention, ou même à la mise en œuvre d'émulsions de manière générale.The invention also proposes a surfactant mixture particularly suitable for the implementation of the dried emulsions according to the invention, or even for the implementation of emulsions in general.
DéfinitionsDefinitions
Dans la présente demande, par polymère hvdrosoluble ou hydrodispersable, on entend un polymère qui à concentration de 10% en poids dans de l'eau, à une température de 25°C, ne présente pas de séparation macroscopique de phase. Dans la présente demande la qualité hydrosoluble ou hydrodispersable s'entend au pH de préparation de l'émulsion séchée et/ou au pH d'utilisation de l'émulsion séchée lors de la re-dispersion.In the present application, the term "water-soluble or water-dispersible polymer" means a polymer which, at a concentration of 10% by weight in water at a temperature of 25 ° C., does not exhibit macroscopic phase separation. In the present application the water-soluble or water-dispersible quality refers to the preparation pH of the dried emulsion and / or the pH of use of the dried emulsion during the re-dispersion.
Dans la présente demande, par phase hydrophobe, on entend un composé ou une composition comprenant plusieurs composés, non miscible à l'eau (formant une séparation macroscopique de phases), à une concentration de 10% en poids, à une température de 25°C. Dans la présente demande la qualité de phase hydrophobe ou hydrodispersable s'entend au pH de préparation de l'émulsion séchée et/ou au pH d'utilisation de l'émulsion séchée lors de la re-dispersion. Dans la présente demande, sauf indication contraire, les quantités d'ingrédients et les rapports sont donnés en poids de matière sèche.In the present application, hydrophobic phase means a compound or a composition comprising several compounds, immiscible with water (forming a macroscopic phase separation), at a concentration of 10% by weight, at a temperature of 25 ° C. vs. In the present application, the hydrophobic or water-dispersible phase quality refers to the preparation pH of the dried emulsion and / or the pH of use of the dried emulsion during the re-dispersion. In the present application, unless otherwise indicated, the amounts of ingredients and ratios are given by weight of dry matter.
Ingrédients de l'émulsion séchée L'émulsion séchée comprend une matrice comprenant un polymère hydrosoluble ou hydrodispersable, dans laquelle est dispersée une phase hydrophobe. La phase hydrophobe peut être liquide ou solide. Elle est de préférence liquide. Dans le cas où la phase hydrophobe est une phase solide, elle peut avoir été liquéfiée par chauffage et émulsifiée lors de la préparation de l'émulsion de l'émulsion séchée. La phase hydrophobe est présente sous forme d'inclusions (gouttelettes s'il s'agit d'une phase liquide) dans la matrice, avantageusement d'une taille moyenne comprise entre 0,1 et 50 μm, de préférence entre 1 et 10 μm, par exemple entre 1 et 5 μm (déterminée à l'aide d'un granulomètre à diffraction laser HORlBA). La taille moyenne peut varier selon l'application finale.Ingredients of the Dried Emulsion The dried emulsion comprises a matrix comprising a water-soluble or water-dispersible polymer in which a hydrophobic phase is dispersed. The hydrophobic phase can be liquid or solid. It is preferably liquid. In the case where the hydrophobic phase is a solid phase, it may have been liquefied by heating and emulsified during the preparation of the emulsion of the dried emulsion. The hydrophobic phase is present in the form of inclusions (droplets if it is a liquid phase) in the matrix, advantageously of a mean size of between 0.1 and 50 μm, preferably between 1 and 10 μm. for example between 1 and 5 microns (determined using a HOR1BA laser diffraction granulometer). The average size may vary depending on the final application.
On détaille ci-dessous différents ingrédients pouvant entrer dans la composition de l'émulsion sèche.Below is described below various ingredients that can be used in the composition of the dry emulsion.
Phase hvdrophobe La phase hydrophobe peut comprendre toutes sortes de composés, seuls ou en mélanges, éventuellement en solution ou en dispersion dans un solvant hydrophobe. Bien entendu, la phase hydrophobe peut n'être constituée que d'un simple liquide hydrophobe. La phase hydrophobe peut être un composé hydrophobe actif, ou un mélange comprenant composé hydrophobe actif en solution ou dispersion dans un solvant hydrophobe.Hydrophobic Phase The hydrophobic phase may comprise all kinds of compounds, alone or in mixtures, optionally in solution or in dispersion in a hydrophobic solvent. Of course, the hydrophobic phase may consist only of a single hydrophobic liquid. The hydrophobic phase may be an active hydrophobic compound, or a mixture comprising an active hydrophobic compound in solution or a dispersion in a hydrophobic solvent.
On cite à titre d'exemples de phase hydrophobe ou de composés compris dans la phase hydrophobe:Examples of hydrophobic phases or compounds included in the hydrophobic phase are:
- les silicones, par exemple des huiles et gommes silicones, de type MD, MTD, MQ, éventuellement solubilisées dans des solvants, et éventuellement fonctionnalisées par des groupes tels que des aminés, alcools, polyols etc. De tels silicones sont connues de l'homme du métier.silicones, for example silicone oils and gums, of the MD, MTD or MQ type, optionally solubilized in solvents, and optionally functionalized with groups such as amines, alcohols, polyols, etc. Such silicones are known to those skilled in the art.
- les parfums.- the perfumes.
- les huiles organiques, minérales ou végétales ou minérales, et les dérivés de ces huiles, lesdites huiles et dérivés étant non miscibles à l'eau.organic, mineral or vegetable or mineral oils, and derivatives of these oils, said oils and derivatives being immiscible with water.
- les solvants organiques non miscibles à l'eau. - les matières actives non hydrosolubles ou hydrodispersables, éventuellement solubilisées dans un solvant.organic solvents immiscible with water. the non-water-soluble or water-dispersible active substances, optionally solubilized in a solvent.
- leurs mélanges, en solutions, dispersions, ou émulsions.- their mixtures, in solutions, dispersions, or emulsions.
Dans le domaine de l'agrochimie, les matières actives phytosanitaires peuvent être choisies parmi la famille des α-cyano-phénoxybenzyl carboxylates ou des α-cyano- halogénophénoxy-carboxylates, la famille des N-méthylcarbonates comprenant des substituants aromatiques, les matières actives telles que Aldrin, Azinphos-methyl, Benfluralin, Bifenthrin, Chlorphoxim, Chlorpyrifos, Fluchloralin, Fluroxypyr, Dichloruos, Malathion, Molinate, Parathion, Permethrin, Profenofos, Propiconazole, Prothiofos, Pyrifenox, Butachlor, Metolachlor, Chlorimephos, Diazinon, Fluazifop-P-butyl, Heptopargil, Mecarbam, Propargite, Prosulfocarb, Bromophos-ethyl, Carbophenothion, Cyhalothrin, Novaluron, Deltaméthrine, Pendimethalin, Fluquinconazole, Tebuconazole, Alphamethrine, Chlothianidine, Betacyfluthrine, Cyfluthrine, Lambda-Cyhalothrine, Cyhalothrine, Fipronil, Thiaclopride, Imidaclopride, Phenmediphame, Desmediphame, Amidosulfuron, Ethofumesate. Les matières actives phytosanitaires peuvent être mises en œuvre en présence d'additifs classiques, choisis par exemple parmi les adjuvants permettant d'augmenter l'efficacité de la matière active, les agents anti-mousses, les agents anti-mottants, des charges, hydrosolubles ou non. Ces matières actives peuvent en solutions dans un solvant, hydrophobe, dpar exemple choisi parmi les solvant hydrocarbonés aromatiques tels que le xylène, le dibenzyltoluène, les solvants phosphates ou phosphonates tels que le tri-n- butylphosphate (TBP), les solvants hydrocarbonés aliphatiques tels que les huiles minérales ou végétales, les alcools tels que le cyclohexanol, les cétones telles que la cyclohexanone, les amides telles que la N,N-dimethylcaprylamide-caprarnide, les pyrrolidones tels que la N-methylpyrrolidone, la N-octylpyrrolidone, la N- dodecylpyrrolidone, la N-cyclohexylpyrrolidoen, les alkyllactates, les solvant.In the field of agrochemistry, the phytosanitary active ingredients may be chosen from the family of α-cyano-phenoxybenzyl carboxylates or α-cyanohalogenophenoxy carboxylates, the family of N-methylcarbonates comprising aromatic substituents, the active ingredients such as that Aldrin, Azinphos-methyl, Benfluralin, Bifenthrin, Chlorphoxim, Chlorpyrifos, Fluchloralin, Fluroxypyr, Dichloruos, Malathion, Molinate, Parathion, Permethrin, Profenofos, Propiconazole, Prothiophos, Pyrifenox, Butachlor, Metolachlor, Chlorimephos, Diazinon, Fluazifop-P-butyl , Heptopargil, Mecarbam, Propargite, Prosulfocarb, Bromophos-ethyl, Carbophenothion, Cyhalothrin, Novaluron, Deltamethrin, Pendimethalin, Fluquinconazole, Tebuconazole, Alphamethrin, Chlothianidin, Betacyfluthrin, Cyfluthrin, Lambda-Cyhalothrin, Cyhalothrin, Fipronil, Thiacloprid, Imidacloprid, Phenmedipham, Desmedipham , Amidosulfuron, Ethofumesate. Phytosanitary active ingredients can be used in the presence of conventional additives, chosen for example from adjuvants for increasing the effectiveness of the active ingredient, anti-foaming agents, anti-caking agents, and water-soluble fillers. or not. These active substances may in solutions in a hydrophobic solvent, for example chosen from aromatic hydrocarbon solvents such as xylene, dibenzyltoluene, phosphate or phosphonate solvents such as tri-n-butyl phosphate (TBP), aliphatic hydrocarbon solvents such as that mineral or vegetable oils, alcohols such as cyclohexanol, ketones such as cyclohexanone, amides such as N, N-dimethylcaprylamide-capramid, pyrrolidones such as N-methylpyrrolidone, N-octylpyrrolidone, N dodecylpyrrolidone, N-cyclohexylpyrrolidone, alkyllactates, solvents.
La phase hydrophobe peut être notamment une phase hydrophobe comprenant de la deltaméthrine et du tri-n-butylphosphate (TBP). Elle peut toutefois être différent d'une phase hydrophobe comprenant à la fois de la detlaméthrine et du TBP. La phase hydrophobe peut être notamment une phase hydrophobe comprenant de la deltaméthrine et un solvant à base de xylene tel que le Solvesso 200 ou 200 ND. Elle peut toutefois être différent d'une phase hydrophobe comprenant à la fois de la detlaméthrine et un solvant à base de xylene tel que le Solvesso 200 ou 200 ND. La phase hydrophobe peut être notamment une phase hydrophobe comprenant de la deltaméthrine, un solvant à base de xylene tel que le Solvesso 200 ou 200 ND et du tri- n-butylphosphate (TBP). Elle peut toutefois être différent d'une phase hydrophobe comprenant à la fois de la detlaméthrine, un solvant à base de xylene tel que le Solvesso 200 ou 200 ND, et du TBP.The hydrophobic phase may in particular be a hydrophobic phase comprising deltamethrin and tri-n-butyl phosphate (TBP). It may, however, be different from a hydrophobic phase comprising both detlamethrin and TBP. The hydrophobic phase may in particular be a hydrophobic phase comprising deltamethrin and a xylene-based solvent such as Solvesso 200 or 200 ND. It may, however, be different from a hydrophobic phase comprising both detlamethrin and a xylene-based solvent such as Solvesso 200 or 200 ND. The hydrophobic phase may in particular be a hydrophobic phase comprising deltamethrin, a xylene-based solvent such as Solvesso 200 or 200 ND and trisamethrin. n-butyl phosphate (TBP). It may, however, be different from a hydrophobic phase comprising both detlamethrin, a xylene-based solvent such as Solvesso 200 or 200 ND, and TBP.
On peut de même citer en tant que matières actives convenables dans le domaine des formulations phytosanitaires, les huiles végétales, minérales, les huiles silicones, les anti-mousses silicones, etc.It is also possible to mention as suitable active materials in the field of phytosanitary formulations, vegetable oils, mineral oils, silicone oils, silicone anti-foams, etc.
A titre d'exemples de matières actives utilisables dans le domaine de la cosmétique on peut citer les huiles silicones appartenant notamment à la famille des diméthicones ; les vitamines lipophiles, comme la vitamine A et ses dérivés, la vitamine B2, l'acide pantothénique, la vitamine D et la vitamine E ; les mono-, di- et triglycérides ; les parfums ; les bactéricides ; les agents absorbeurs d'UV, comme les dérivés aminobenzoate de type PABA et PARA, les salicylates, les cinnamates, les anthranilates, les dibenzoylméthanes, les dérivés du camphre et leurs mélanges. Les agents anti-vieillissement peuvent de même être utilisés. A titre d'exemples de tels agents on peut citer notamment citer les rétinoïdes, les acides α- et β- hydroxy, leurs sels et leurs esters, les vitamines liposolubles, le palmitate d'ascorbyle, les céramides, les pseudo-céramides, les phospholipides, les acides gras, les alcools gras, le cholestérol, les stérols et leurs mélanges. Comme acides gras et alcools préférés, on peut plus particulièrement citer ceux possédant des chaînes alkyles, linéaires ou ramifiées contenant de 12 à 20 atomes de carbone. Il peut notamment s'agir d'acide linoléique.As examples of active materials that can be used in the field of cosmetics, mention may be made of silicone oils belonging in particular to the family of dimethicones; lipophilic vitamins, such as vitamin A and its derivatives, vitamin B2, pantothenic acid, vitamin D and vitamin E; mono-, di- and triglycerides; the perfumes ; bactericides; UV-absorbing agents, such as aminobenzoate derivatives of PABA and PARA type, salicylates, cinnamates, anthranilates, dibenzoylmethanes, camphor derivatives and mixtures thereof. Anti-aging agents can likewise be used. Examples of such agents that may be mentioned include retinoids, α- and β-hydroxy acids, their salts and esters, fat-soluble vitamins, ascorbyl palmitate, ceramides, pseudo-ceramides, phospholipids, fatty acids, fatty alcohols, cholesterol, sterols and their mixtures. Preferred fatty acids and alcohols include, for example, those having linear or branched alkyl chains containing from 12 to 20 carbon atoms. It may in particular be linoleic acid.
On peut de même mettre en œuvre des agents anti-cellulite, tels que notamment l'isobutylméthylxanthine et la théophyline ; ainsi que des agents anti-acné, comme par exemple le résorcinol, l'acétate de résorcinol, le peroxyde de benzoyle et de nombreux composés naturels.It is likewise possible to use anti-cellulite agents, such as in particular isobutylmethylxanthine and theophylline; as well as anti-acne agents, such as resorcinol, resorcinol acetate, benzoyl peroxide and many natural compounds.
Les arômes, parfums, huiles essentielles, essences, peuvent aussi être utilisés en tant que matière active hydrophobe. A titre d'exemple, on peut citer les huiles et/ou essences de menthe, de menthe verte, de menthe poivrée, de menthol, de vanille, de cannelle, de laurier, d'anis, d'eucalyptus, de thym, de sauge, de feuille de cèdre, de noix de muscade, de citrus (citron, citron vert, pamplemousse, orange), de fruits (pomme, poire, pêche, cerise, prune, fraise, framboise, abricot, ananas, raisin, etc.), seules ou en mélanges.Aromas, perfumes, essential oils, essences can also be used as hydrophobic active material. By way of example, mention may be made of oils and / or essences of mint, spearmint, peppermint, menthol, vanilla, cinnamon, laurel, anise, eucalyptus, thyme, sage, cedar leaf, nutmeg, citrus (lemon, lime, grapefruit, orange), fruit (apple, pear, peach, cherry, plum, strawberry, raspberry, apricot, pineapple, grape, etc.). ), alone or in mixtures.
Les agents anti-microbiens peuvent être choisis parmi le thymol, le menthol, le triclosan, le 4-hexylrésorcinol, le phénol, l'eucalyptol, l'acide benzoïque, le peroxyde benzoïque, le parabène de butyle, et leurs mélanges. A titre d'exemples de matières actives convenables à l'invention et utilisables dans le domaine des peintures, on peut citer les résines alkydes, les résines époxy, les isocyanates bloqués ou non.The antimicrobial agents may be selected from thymol, menthol, triclosan, 4-hexylresorcinol, phenol, eucalyptol, benzoic acid, benzoic peroxide, butyl paraben, and mixtures thereof. As examples of suitable active materials for use in the field of paints include alkyd resins, epoxy resins, isocyanates blocked or not.
Dans le domaine du papier, on peut citer entre autres les résines telles que le dimère d'alkylcétène (AKD) ou l'anhydride alcényle succinique (ASA).In the field of paper, mention may be made, inter alia, of resins such as alkylketene dimer (AKD) or alkenyl succinic anhydride (ASA).
Dans le domaine de la détergence, on peut mentionner en tant que matière active possible, les silicones aminées en tant qu'agent adoucissant, les anti-mousses silicones, les agents anti-microbiens, les parfums, huiles et essences, etc. A ce titre, on pourra se référer à la liste des composés de ce type, indiqués dans le cadre de matières actives pour le domaine de la cosmétique.In the field of detergency, there may be mentioned as possible active ingredient, amino silicones as a softening agent, silicone anti-foams, antimicrobial agents, perfumes, oils and essences, etc. As such, we can refer to the list of compounds of this type, indicated in the context of active ingredients for the field of cosmetics.
Parmi les matières actives hydrophobes convenables, on peut aussi mentionner:Among the suitable hydrophobic active substances, mention may also be made of:
- les huiles/graisses/cires organiques d'origine animale ou d'origine végétale ;- oils / fats / organic waxes of animal origin or of vegetable origin;
- les huiles/cires minérales ; - les produits issus de Palcoolyse des huiles précitées ;- mineral oils / waxes; products derived from the alcoholysis of the aforementioned oils;
- les mono-, di- et tri- glycérides ;mono-, di- and triglycerides;
- les acides gras, saturé ou non, comprenant 10 à 40 atomes de carbone ; les esters de tels acides et d'alcool comprenant 1 à 6 atomes de carbone ;saturated or unsaturated fatty acids comprising 10 to 40 carbon atoms; esters of such acids and of alcohol containing 1 to 6 carbon atoms;
- les monoalcools, saturés ou non, comprenant 8 à 40 atomes de carbone ; ces composés étant utilisés seuls ou en mélange.saturated or unsaturated monoalcohols comprising 8 to 40 carbon atoms; these compounds being used alone or in a mixture.
Comme huiles / graisses / cires organiques d'origine animale, on peut citer en autres, l'huile de cachalot, l'huile de baleine, l'huile de phoque, l'huile de squale, l'huile de foie de morue, les graisses de porc, de mouton (suifs), le perhydrosqualène, la cire d'abeille, seules ou en mélange. A titres d'exemples d'huiles / graisses / cires organiques d'origine végétale, on peut mentionner, entre autres, l'huile de colza, l'huile de tournesol, l'huile d'arachide, l'huile d'olive, l'huile de noix, l'huile de maïs, l'huile de soja, l'huile d'avocat, l'huile de lin, l'huile de chanvre, l'huile de pépins de raisin, l'huile de coprah, l'huile de palme, l'huile de graines de coton, l'huile de palmiste, l'huile de babassu, l'huile de jojoba, l'huile de sésame, l'huile de ricin, l'huile de macadamia, l'huile d'amande douce, la cire de camauba, le beurre de karité, le beurre de cacao, le beurre de cacahuète, seuls ou en mélange.As organic oils / fats / waxes of animal origin, there may be mentioned, in particular, sperm whale oil, whale oil, seal oil, shark oil, cod liver oil, pork, mutton fat, perhydrosqualene, beeswax, alone or in a mixture. Examples of organic oils / fats / waxes of vegetable origin include rapeseed oil, sunflower oil, peanut oil, olive oil and others. , walnut oil, corn oil, soybean oil, avocado oil, linseed oil, hemp oil, grape seed oil, coconut oil, palm oil, cottonseed oil, palm kernel oil, babassu oil, jojoba oil, sesame oil, castor oil, macadamia, sweet almond oil, camauba wax, shea butter, cocoa butter, peanut butter, alone or mixed.
En ce qui concerne les huiles / cires minérales, on peut citer entre autres les huiles naphténiques, paraffiniques (vaseline), isoparaffiniques, les cires paraffiniques, seules ou en mélange.As regards mineral oils / waxes, mention may be made, inter alia, of naphthenic, paraffinic (petroleum), isoparaffinic and paraffinic waxes, alone or as a mixture.
Les produits issus de l'alcoolyse des huiles précitées peuvent aussi être utilisés.Products derived from alcoholysis of the above-mentioned oils can also be used.
Concernant les acides gras, ces derniers, saturés ou non, comprennent 10 à 40 atomes de carbone, plus particulièrement 18 à 40 atomes de carbone, et peuvent comprendre une ou plusieurs insaturations éthyléniques, conjuguées ou non. Il est à noter que lesdits acides peuvent comprendre un ou plusieurs groupements hydroxyles.Regarding the fatty acids, the latter, saturated or not, comprise 10 to 40 carbon atoms, more particularly 18 to 40 carbon atoms, and can include one or more ethylenic unsaturations, conjugated or not. It should be noted that said acids may comprise one or more hydroxyl groups.
Comme exemples d'acides gras saturés, on peut citer les acides palmitique, stéarique, isostéarique, béhénique.Examples of saturated fatty acids include palmitic, stearic, isostearic and behenic acids.
Comme exemples d'acides gras insaturés, on peut citer les acides myristoléique, palmitoléique, oléique, érucique, linoléique, linolénique, arachidonique, ricinoléique, ainsi que leurs mélanges.Examples of unsaturated fatty acids that may be mentioned include myristoleic, palmitoleic, oleic, erucic, linoleic, linolenic, arachidonic and ricinoleic acids, as well as their mixtures.
Pour ce qui a trait aux esters d'acides gras, on peut citer les esters des acides précédemment listés, pour lesquels la partie dérivant de l'alcool comprend 1 à 6 atomes de carbone, comme les esters méthyliques, éthyliques, de propyliques, isopropyliques, etc.With regard to the fatty acid esters, mention may be made of the esters of the acids previously listed, for which the portion derived from the alcohol comprises 1 to 6 carbon atoms, such as methyl, ethyl, propyl, and isopropyl esters. etc.
On mentionne que la phase hydrophobe peut comprendre une phase intermédiaire non miscible à l'eau dans laquelle est dispersée une phase interne non miscible ou non soluble dans à la phase intermédiaire. Dans ce cas on peut parler d'émulsion multiple séchée.It is mentioned that the hydrophobic phase may comprise an immiscible intermediate phase with water in which is dispersed an internal phase immiscible or insoluble in the intermediate phase. In this case we can speak of dried multiple emulsion.
Bien entendu, il n'est pas exclu que l'émulsion séchée comprenne plusieurs phase hydrophobes différentes dispersées la matrice, consistant deux populations d'inclusions.Of course, it is not excluded that the dried emulsion comprises several different hydrophobic phase dispersed matrix, consisting of two populations of inclusions.
Polymère hydrosoluble ou hydrodispersableWater-soluble or water-dispersible polymer
Le polymère hydrosoluble ou hydrodispersable de la matrice est un polycarboxylate comprenant des unités hydrophobes.The water-soluble or water-dispersible polymer of the matrix is a polycarboxylate comprising hydrophobic units.
Avantageusement c'est un copolymère comprenant des unités dérivant des monomères suivants:Advantageously, it is a copolymer comprising units deriving from the following monomers:
- (I) acide monocarboxylique ou polycarboxylique, ou anhydride, aliphatique, cyclique ou aromatique, linéaire ou ramifié, éthyléniquement insaturé,- (I) linear or branched, ethylenically unsaturated, linear or branched, monocarboxylic or polycarboxylic acid, or anhydride, aliphatic, cyclic or aromatic,
- (Il) monomère de formule (R2)(R2)C = CH(R3) dans laquelle - R3 est un atome d'hydrogène ou un groupe méthyle, et- (II) monomer of formula (R 2 ) (R 2 ) C = CH (R 3 ) in which - R 3 is a hydrogen atom or a methyl group, and
- R2, identiques ou différents, représentent un atome d'hydrogène, un radical saturé ou éthyléniquement insaturé, aliphatique ou aromatique, linéaire ou ramifié, éventuellement cyclique, en C2 - C-J O, à la condition que les deux radicaux R2 ne . soient pas des atomes d'hydrogène, et - optionnellement (III) ester polyoxyalkyléné d'acide carboxylique éthyléniquement insaturé. Le monomère (I) a avantageusement pour formule:- R 2 , which may be identical or different, represent a hydrogen atom, a linear or branched, optionally cyclic, saturated or ethylenically unsaturated, aliphatic or aromatic radical, at C 2 -C 6 O, with the proviso that the two radicals R 2 are not hydrogen atoms, and optionally (III) polyoxyalkylene ester of ethylenically unsaturated carboxylic acid. The monomer (I) advantageously has the formula:
(R3)HC = C(R1) - COOX (la), dans laquelle:(R 3 ) HC = C (R 1 ) -COOX (la), in which:
- R3 est un atome d'hydrogène ou un groupe méthyle, - R1 est un atome d'hydrogène, un radical hydrocarboné en C-] - C-] o comprenant éventuellement un groupe - COOX, ou un groupe -COOX, formant éventuellement avec le groupe - COOX un groupe anhydride -CO-O-OC-, et- R 3 is a hydrogen atom or a methyl group, - R 1 is a hydrogen atom, a hydrocarbon radical C-] - C-] o optionally comprising a group - COOX, or a -COOX group, forming optionally with the group - COOX an anhydride group -CO-O-OC-, and
- X est un atome d'hydrogène ou un cation, par exemple le cation du sodium, du potassium, ou le cation ammonium. Par exemple le monomère (I) est avantageusement choisi parmi les acides ou anhydrides acrylique, méthacrylique, citraconique, maléique, fumarique, itaconique, crotonique, sous forme acide ou sous forme de sels par exemple sous forme de sel de sodium ou de potassium.X is a hydrogen atom or a cation, for example the cation of sodium, of potassium, or the ammonium cation. For example, the monomer (I) is advantageously chosen from acrylic, methacrylic, citraconic, maleic, fumaric, itaconic or crotonic acids or anhydrides, in acid form or in the form of salts, for example in the form of sodium or potassium salt.
Avantageusement, le monomère (II) est choisi parmi le 1 -butène, l'isobutylène, le n-1-pentène, le 2-méthyl 1 -butène, le n-1-hexène, le 2-méthyl 1-pentène, le 4-méthyl 1- pentène, le 2-éthyl 1 -butène, le diisobutylène (ou 2,4,4-triméthyl 1-pentène), le 2-méthyl 3,3-diméthyl 1-pentène.Advantageously, the monomer (II) is chosen from 1-butene, isobutylene, n-1-pentene, 2-methyl-1-butene, n-1-hexene, 2-methyl-1-pentene, 4-methyl-pentene, 2-ethyl-1-butene, diisobutylene (or 2,4,4-trimethyl-1-pentene), 2-methyl-3,3-dimethyl-1-pentene.
Le monomère (III) peut correspondre à la formule suivante:The monomer (III) may correspond to the following formula:
CH2=C(R3)-C(O)-O-[CH2CH(R4)O]m-[CH(R5)-CH2θ]n-R6 formule dans laquelle :CH 2 = C (R 3) -C (O) -O- [CH 2 CH (R 4) O] m - [CH (R 5) -CH 2 O] n -R 6 in which formula:
R3 est un atome d'hydrogène ou un radical méthyle,R3 is a hydrogen atom or a methyl radical,
R4 et R5 identiques ou différents, représentent un atome d'hydrogène ou un radical alkyle contenant de 1 à 4 atomes de carbone,R4 and R5, which may be identical or different, represent a hydrogen atom or an alkyl radical containing from 1 to 4 carbon atoms,
Rδ est un radical alkyle, aryle, alkylaryle ou arylalkyle contenant de 1 à 30, de préférence de 8 à 30 atomes de carbone, n est compris entre 2 et 100, de préférence entre 6 et 10O m est compris entre O et 50, sous réserve que n soit supérieur ou égal à m et leur somme comprise entre 2 etRδ is an alkyl, aryl, alkylaryl or arylalkyl radical containing from 1 to 30, preferably from 8 to 30 carbon atoms, n is between 2 and 100, preferably between 6 and 10O m is between 0 and 50, under reserve that n is greater than or equal to m and their sum between 2 and
100, de préférence entre 6 et 100.100, preferably between 6 and 100.
De préférence, on utilise des monomères de formule (Ml) pour lesquels R6 est un radical alkyle contenant de 8 à 30 atomes de carbone, ou un radical phényle substitué par un à trois groupements 1-phényléthyle, ou un radical alkylphényle dont le radical alkyle contient de 8 à 16 atomes de carbone.Preferably, monomers of formula (M1) are used, for which R6 is an alkyl radical containing from 8 to 30 carbon atoms, or a phenyl radical substituted with one to three 1-phenylethyl groups, or an alkylphenyl radical whose alkyl radical. contains from 8 to 16 carbon atoms.
Parmi les monomères de ce type, susceptibles d'être mis en oeuvre, on peut citer ceux décrits dans les brevets EP 705 854, US 4 138 381 ou encore US 4 384 096. Le copolymère peut comprendre en plus des unités dérivant d'un monomère optionnel (IV) choisi parmi les monomères suivants:Among the monomers of this type that may be used include those described in patents EP 705 854, US 4 138 381 or US 4 384 096. The copolymer may further comprise units derived from an optional monomer (IV) selected from the following monomers:
- les monomères vinylaromatiques comme le styrène, le vinyltoluène, - les C-1-C20 alkylesters d'acides éthyléniquement insaturés comme les acrylates ou méthacrylates de méthyle, éthyle, butyle,vinyl aromatic monomers such as styrene, vinyltoluene, C 1 -C 20 alkyl esters of ethylenically unsaturated acids such as methyl, ethyl and butyl acrylates or methacrylates,
- les esters de vinyle ou d'allyle d'acides éthyléniquement insaturés comme les acétates ou propionates de vinyle ou d'allyle,vinyl or allyl esters of ethylenically unsaturated acids such as vinyl or allyl acetates or propionates,
- les halogénures de vinyle ou de vinylidène comme le chlorure de vinyle ou de vinylidène,vinyl or vinylidene halides such as vinyl chloride or vinylidene,
- les nitriles éthyléniquement insaturés comme l'acrylonitrile,ethylenically unsaturated nitriles such as acrylonitrile,
- les hydroxyalkylesters d'acides éthyléniquement insaturés comme les acrylates ou méthacrylates d'hydroxyéthyle ou d'hydroxypropyle,hydroxyalkyl esters of ethylenically unsaturated acids such as hydroxyethyl or hydroxypropyl acrylates or methacrylates,
- les amides éthyléniquement insaturés comme l'acrylamide, le méthacrylamide.ethylenically unsaturated amides, such as acrylamide and methacrylamide.
Selon un mode de réalisation avantageux le polycarboxylate comprenant des unités hydrophobes est un copolymère dérivant d'anhydride maléique ou d'un sel d'anhydride maléique, et de diisobutylène. Un tel polymère est par exemple commercialisé par le société Rhodia sous la dénomination Geropon® EGPM (en solution, sous forme carboxylate de sodium).According to an advantageous embodiment, the polycarboxylate comprising hydrophobic units is a copolymer derived from maleic anhydride or from a maleic anhydride salt and from diisobutylene. Such a polymer is, for example, marketed by Rhodia under the name Geropon® EGPM (in solution, in sodium carboxylate form).
On note que les copolymères peuvent être obtenus de manière connue de l'homme du métier, par exemple par polymérisation radicalaire.It is noted that the copolymers can be obtained in a manner known to those skilled in the art, for example by radical polymerization.
Tensioactif non polyalcoxyléNon-polyalkoxylated surfactant
Le tensioactif non polyalcoxylé peut être un tensioactif non ionique non polyalcoxylé, un tensioactif anionique non polyalcoxylé, un tensioactif amphotère non polyalcoxylé, ou un mélange de ces tensioactifs.The non-polyalkoxylated surfactant may be a non-polyalkoxylated nonionic surfactant, a non-polyalkoxylated anionic surfactant, a non-polyalkoxylated amphoteric surfactant, or a mixture of these surfactants.
A titre d'exemples de tensioactifs amphotères non polyalcoxylés on peut citer les amphoacétates, les amphodiacétates, les bétaines (carboxybétaïnes comme les alkylbetaïnes et les alkylamidoalkylbetaïnes), les aminé oxydes, les sultaïnes (sulfobétaïnes), leurs mélanges.As examples of non-polyalkoxylated amphoteric surfactants, mention may be made of amphoacetates, amphodiacetates, betaines (carboxybetaines such as alkylbetaines and alkylamidoalkyl betaines), amine oxides, sultaines (sulfobetaines), and mixtures thereof.
A titre d'exemples de tensioactifs non polyalcoxylés on peut citer les alkylsulfates, les alkylsulfonates, les alkylarylsulfonates, les alkyphosphates, leurs mélanges.By way of examples of non-polyalkoxylated surfactants, mention may be made of alkyl sulphates, alkyl sulphonates, alkylarylsulphonates and alkylphosphates, and mixtures thereof.
A titre d'exemples de tensioactifs non ioniques non polyalcoxylés on peut citer les tensioactifs suivants: - les alkylpolyglucosides,By way of examples of non-polyalkoxylated nonionic surfactants, mention may be made of the following surfactants: the alkylpolyglucosides,
- les esters de sorbitan non polyalcoxylés,the non-polyalkoxylated sorbitan esters,
- les acides gras,fatty acids,
- leurs mélanges.- their mixtures.
L'émulsion séchée peut être une émulsion séchée comprenant à titre d'unique tensioactif non polyacloxylé un ester de sorbitan tel que le tensioactif Alkamuls S80 commercialisé par Rhodia. Elle peut toutefois être une émulsion séchée comprenant en plus un autre tensioactif. Elle peut notamment être différente d'une émulsion séchée comprenant à titre d'unique tensioactif non polyacloxylé un ester de sorbitan tel que le tensioactif Alkamuls S80 commercialisé par Rhodia. L'émulsion séchée peut être une émulsion séchée comprenant à titre à titre d'unique tensioactif non polyacloxylé un ester de sorbitan tel que le tensioactif Alkamuls S80 commercialisé par Rhodia et à titre de solvant de matière active un solvant à base de xylene tel que le Solvesso 200 ou 200 ND ou du tri-n-butylphosphate (TBP), ou un mélange de ces solvants. Elle peut toutefois être différente d'une émulsion séchée comprenant à titre à titre d'unique tensioactif non polyacloxylé un ester de sorbitan tel que le tensioactif Alkamuls S80 commercialisé par Rhodia et à titre de solvant de matière active un solvant à base de xylene tel que le Solvesso 200 ou 200 ND ou du tri-n-butylphosphate (TBP), ou un mélange de ces solvants.The dried emulsion may be a dried emulsion comprising, as sole non-polyacyloxylated surfactant, a sorbitan ester such as the surfactant Alkamuls S80 marketed by Rhodia. It may, however, be a dried emulsion comprising in addition another surfactant. It may in particular be different from a dried emulsion comprising, as sole non-polyacyloxylated surfactant, a sorbitan ester such as the surfactant Alkamuls S80 marketed by Rhodia. The dried emulsion may be a dried emulsion comprising, as sole non-polyacyloxylated surfactant, a sorbitan ester such as the surfactant Alkamuls S80 marketed by Rhodia and as a solvent for the active ingredient a xylene-based solvent such as Solvesso 200 or 200 ND or tri-n-butyl phosphate (TBP), or a mixture of these solvents. It may, however, be different from a dried emulsion comprising, as sole non-polyacrylated surfactant, a sorbitan ester such as the surfactant Alkamuls S80 marketed by Rhodia and as a solvent for active ingredient a xylene-based solvent such as Solvesso 200 or 200 ND or tri-n-butyl phosphate (TBP), or a mixture of these solvents.
Selon un mode de réalisation avantageux le tensioactif non polyalcoxylé est:According to an advantageous embodiment, the non-polyalkoxylated surfactant is:
- un ester de sorbitan dérivant d'un acide gras en C8-C30, de préférence en C16-C22, oua sorbitan ester derived from a C 8 -C 30 , preferably C 16 -C 22 , fatty acid, or
- un mélange d'un ester de sorbitan dérivant d'un acide gras en C8-C30, de préférence en Ci6-C22, et d'un acide gras en C8-C30, de préférence en Ci6-C22, ou d'un sel de l'acide gras.- a mixture of a sorbitan ester derived from a fatty acid C 8 -C 30, preferably C 6 -C 22 fatty acid and of a C 8 -C 30, preferably C 6 - C 22 , or a salt of the fatty acid.
De préférence le mélange de l'ester de sorbitan et de l'acide gras comprend, en matière sèche, de 2 à 20% en poids de l'acide gras ou du sel.Preferably, the mixture of the sorbitan ester and the fatty acid comprises, in dry matter, from 2 to 20% by weight of the fatty acid or salt.
Le mélange de l'ester de sorbitan et de l'acide gras est un tensioactif (composition tensioactive, ou "blend" de tensioactifs) qui permet de contrôler l'émulsification de phases hydrophobes, notamment la taille des gouttelettes d'une émulsion comprenant une phase hydrophobe dispersée dans de une phase aqueuse. Ainsi l'invention concerne également ce tensioactif (cette composition tensioactive, ou "blend" de tensioactifs) en tant que tel, notamment un mélange comprenant l'ester de sorbitan et l'acide gras ou son sel, le cas échéant avec de l'eau, à une concentration en matière sèche supérieure à 20% ou 30% ou 50% ou 75%. L'invention concerne également les émulsions, séchées ou non, comprenant ce tensioactif (et la phase hydrophobe et la phase aqueuse), ou l'utilisation du tensioactif dans les émulsions.The mixture of the sorbitan ester and the fatty acid is a surfactant (surfactant composition, or "blend" of surfactants) which makes it possible to control the emulsification of hydrophobic phases, especially the size of the droplets of an emulsion comprising a hydrophobic phase dispersed in an aqueous phase. Thus, the invention also relates to this surfactant (this surfactant composition, or "blend" of surfactants) as such, in particular a mixture comprising the sorbitan ester and the fatty acid or its salt, where appropriate with water, at a solids concentration greater than 20% or 30% or 50% or 75%. The invention also relates to emulsions, dried or not, comprising this surfactant (and the hydrophobic phase and the aqueous phase), or the use of the surfactant in the emulsions.
Quantités d'ingrédients Avantageusement, le rapport pondéral entre la phase hydrophobe et la matrice est compris entre 50% et 80%.Quantities of ingredients Advantageously, the weight ratio between the hydrophobic phase and the matrix is between 50% and 80%.
Avantageusement, le rapport pondéral entre le tensioactif non polyalcoxylé et la phase hydrophobe est compris entre 0,003 et 0,3, de préférence entre 0,01 et 0,06.Advantageously, the weight ratio between the non-polyalkoxylated surfactant and the hydrophobic phase is between 0.003 and 0.3, preferably between 0.01 and 0.06.
Avantageusement, le rapport pondéral entre le tensioactif non polyalcoxylé et la matrice est compris entre 0,006 et 0,6, de préférence entre 0,02 et 1 ,2.Advantageously, the weight ratio between the non-polyalkoxylated surfactant and the matrix is between 0.006 and 0.6, preferably between 0.02 and 1.2.
Avantageusement, la matrice comprend au moins 90% en poids du polymère hydrosoluble ou hydrodispersable.Advantageously, the matrix comprises at least 90% by weight of the water-soluble or water-dispersible polymer.
Autres composés L'émulsion séchée peut comprendre d'autres ingrédients, qui peuvent être utiles lors de sa préparation, ou qui peuvent être utiles pour en moduler les propriétés ou les applications.Other Compounds The dried emulsion may comprise other ingredients, which may be useful in its preparation, or which may be useful in modulating its properties or applications.
Il peut notamment s'agir d'ingrédients actifs (c'est à dire d'ingrédients ayant une fonction lors de l'utilisation, par exemple dans une formulation liquide), compris dans la matrice, et formulables dans une phase aqueuse.It may especially be active ingredients (ie ingredients having a function during use, for example in a liquid formulation), included in the matrix, and formulated in an aqueous phase.
Il peut également s'agir d'agents anti-mousse, d'osés tels que décrits dans le document WO 03/055584 (R 01186), ou de complexants comprenant au moins un des éléments des colonnes HA, IVA, VA, VlII, IB, et IHB, permettant de contrôler plus aisément la libération de la phase hydrophobe lors d'une redispersion dans l'eau, comme décrit dans le document WO 03/006148 (R 01103).It may also be antifoam agents, daring as described in the document WO 03/055584 (R 01186), or complexing agents comprising at least one of the elements of columns HA, IVA, VA, VIII, IB, and IHB, to more easily control the release of the hydrophobic phase during a redispersion in water, as described in WO 03/006148 (R 01103).
L'émulsion séchée peut éventuellement contenir de l'eau résiduelle. La teneur en eau est avantageusement inférieure à 10% en poids, encore plus préférablement inférieure à 3%.The dried emulsion may optionally contain residual water. The water content is advantageously less than 10% by weight, still more preferably less than 3%.
ProcédéProcess
L'émulsion séchée selon l'invention peut être réalisée selon un procédé comprenant les étapes suivantes: a) préparer une émulsion comprenant une phase aqueuse dans laquelle est dispersée la phase hydrophobe dispersée sous forme liquide dans l'eau, l'émulsion comprenant le copolymère hydrosoluble ou hydrodispersable de la matrice le tensioactif non polyalcoxylé, le cas échéant en chauffant la phase hydrophobe au dessus de son point de fusion, b) éliminer l'eau, pour obtenir une émulsion séchée, c) éventuellement mettre l'émulsion séchée sous forme de poudre ou de granulés, d) récupérer l'émulsion séchée,The dried emulsion according to the invention may be carried out according to a process comprising the following steps: a) preparing an emulsion comprising an aqueous phase in which the hydrophobic phase dispersed in liquid form is dispersed in water, the emulsion comprising the copolymer water-soluble or water-dispersible matrix of the non-polyalkoxylated surfactant, where appropriate by heating the hydrophobic phase above its melting point, b) removing the water, to obtain a dried emulsion, c) optionally putting the dried emulsion in the form of powder or granules, d) recovering the dried emulsion,
Etape a) préparation de l'émulsionStep a) preparation of the emulsion
Lors d'une première étape du procédé, on prépare une émulsion comprenant la phase hydrophobe, dispersée dans la phase aqueuse. La phase hydrophobe, lors de cette étape, est sous forme liquide. Au besoin, elle est chauffée à cet effet. L'émulsion comprend le polymère hydrosoluble ou hydrodispersable, et le tensioactif. Toutes les méthodes de préparation d'une émulsion peuvent être utilisées. Elles sont connues de l'homme du métier. Des méthodes sont décrites, par exemple, dans "ENCYCLOPEDIA of EMULSIONS TECHNOLOGY", volumes 1 à 3 de Paul BECHER édités par MARCEL DEKKER INC, 1983, et peuvent être mises en œuvre dans le cadre de la présente invention. Ainsi, la méthode dite d'émulsification en phase directe peut être utilisée. Il est rappelé brièvement que cette méthode consiste à préparer un mélange contenant l'eau et des émulsifiants, y compris le polymère hydrosoluble ou hydrodispersable, puis à introduire la phase hydrophobe sous forme liquide, sous agitation.In a first step of the process, an emulsion comprising the hydrophobic phase dispersed in the aqueous phase is prepared. The hydrophobic phase, during this step, is in liquid form. If necessary, it is heated for this purpose. The emulsion comprises the water-soluble or water-dispersible polymer, and the surfactant. All methods of preparing an emulsion can be used. They are known to those skilled in the art. Methods are described, for example, in "ENCYCLOPEDIA of EMULSIONS TECHNOLOGY", volumes 1 to 3 by Paul BECHER edited by MARCEL DEKKER INC, 1983, and may be implemented within the scope of the present invention. Thus, the so-called direct phase emulsification method can be used. It is briefly recalled that this method consists of preparing a mixture containing water and emulsifiers, including the water-soluble or water-dispersible polymer, and then introducing the hydrophobic phase in liquid form, with stirring.
Une autre méthode convenable est l'émulsification par inversion de phases. Selon cette voie, on mélange la phase hydrophobe avec un émulsifiant et on introduit goutte à goutte et sous agitation, l'eau pouvant contenir les autres constituants tels que le polymère hydrosoluble ou hydrodispersable par exemple. A partir d'une certaine quantité d'eau introduite, il se produit une inversion de l'émulsion. On obtient alors une émulsion directe huile dans eau. On dilue ensuite l'émulsion obtenue dans l'eau de manière à obtenir une fraction volumique en phase dispersée appropriée.Another suitable method is phase inversion emulsification. According to this route, the hydrophobic phase is mixed with an emulsifier and water which can contain the other constituents, such as the water-soluble or water-dispersible polymer for example, is introduced dropwise and with stirring. From a certain amount of introduced water, an inversion of the emulsion occurs. A direct oil-in-water emulsion is then obtained. The resulting emulsion is then diluted in water to obtain a suitable dispersed phase volume fraction.
On peut enfin préparer l'émulsion en mettant en œuvre des broyeurs colloïdaux tels que MANTON GAULIN et MICROFLUIDIZER (MICROFLUIDICS).Finally, the emulsion can be prepared by using colloid mills such as MANTON GAULIN and MICROFLUIDIZER (MICROFLUIDICS).
La taille moyenne des gouttelettes de phase hydrophobe dispersées dans la phase aqueuse est en général comprise entre 0,1 et 50 μm, souvent entre 1 et 10 micromètres et préférentiellement entre 0,2 et 5 micromètres (exprimée par rapport au volume de particules ; mesurée au moyen d'un granulomètre à diffraction laser de typeThe average size of the hydrophobic phase droplets dispersed in the aqueous phase is generally between 0.1 and 50 μm, often between 1 and 10 microns and preferably between 0.2 and 5 microns (expressed relative to the volume of particles; by means of a laser diffraction granulometer of the type
HORIBA).HORIBA).
L'émulsification peut être réalisée à une température voisine de la température ambiante, bien que des températures plus faibles ou plus élevées soient envisageables.The emulsification can be carried out at a temperature close to room temperature, although lower or higher temperatures are possible.
La quantité d'eau présente dans l'émulsion, avant séchage, peut être comprise entre 5 et 99% en poids, de préférence entre 20% et 70% en poids. De manière générale on préfère utiliser de faibles quantités d'eau, car celle-ci doit être éliminée par la suite. Le contrôle de la quantité d'eau peut être un moyen de gérer la viscosité.The quantity of water present in the emulsion, before drying, may be between 5 and 99% by weight, preferably between 20% and 70% by weight. So Generally it is preferred to use small amounts of water since it must be removed later. Controlling the amount of water can be a way to manage the viscosity.
Etapes b) c) d) séchage, mise en forme La méthode mise en œuvre pour éliminer l'eau de l'émulsion et obtenir l'émulsion séchée, peut être effectuée par tout moyen connu de l'homme du métier.Steps b) c) d) drying, shaping The method used to remove water from the emulsion and obtain the dried emulsion may be carried out by any means known to those skilled in the art.
Cette opération a lieu de telle sorte que les divers éléments constitutifs du mélange sont soumis à des températures inférieures à celles de leur dégradation.This operation takes place so that the various constituent elements of the mixture are subjected to temperatures lower than those of their degradation.
Selon un premier mode de réalisation de l'invention, on peut envisager un séchage en étuve. De préférence, ce séchage a lieu en couche mince. Plus particulièrement, la température à laquelle est effectué le séchage est inférieure ou égale à 1000C, de préférence comprise entre 30 et 900C, de préférence entre 50 et 9O0C.According to a first embodiment of the invention, drying in an oven can be envisaged. This drying preferably takes place in a thin layer. More particularly, the temperature at which the drying is carried out is less than or equal to 100 ° C., preferably between 30 and 90 ° C., preferably between 50 and 90 ° C.
Selon un autre mode de réalisation particulier de l'invention, on effectue un séchage dit rapide, du mélange (ou de l'émulsion). Conviennent à ce titre le séchage par atomisation, en lit fluidisé, mettant en œuvre des tambours Duprat®, ou une lyophilisation (congélation-sublimation).According to another particular embodiment of the invention, the so-called rapid drying of the mixture (or emulsion) is carried out. Suitable for this purpose is spray drying in a fluidized bed, using Duprat® drums, or freeze-drying (freezing-sublimation).
Le séchage par atomisation, par exemple à l'aide d'un appareil NIRO, ou en lit fluidisé par exemple à l'aide d'un appareil AEROMATIC, 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. La température d'entrée du gaz chaud (en général de l'air), en tête de colonne, est de préférence comprise entre 500C et 25O0C et la température de sortie est de préférence inférieure à la température de dégradation des éléments constitutifs du granulé obtenu. Dans le cas d'opérations de séchage du mélange (ou de l'émulsion) réalisées au moyen de tambour Duprat®, ou de tout moyen permettant d'obtenir rapidement un film sec qui est séparé du support séchant par une opération de raclage par exemple, on obtient des particules que l'on peut éventuellement broyer. Si nécessaire, ces particules peuvent faire l'objet d'une mise en forme ultérieure, comme une étape d'agglomération, de manière à obtenir des granulés.Spray drying, for example using an NIRO apparatus, or in a fluidized bed, for example using an AEROMATIC apparatus, may be carried out in the usual manner in any known apparatus such as, for example, a tower atomization device associating a spray produced by a nozzle or a turbine with a stream of hot gas. The inlet temperature of the hot gas (generally air) at the top of the column is preferably between 50 ° C. and 250 ° C. and the outlet temperature is preferably lower than the degradation temperature of the elements. constituents of the granule obtained. In the case of drying operations of the mixture (or emulsion) carried out by means of Duprat® drum, or any means making it possible rapidly to obtain a dry film which is separated from the drying support by a scraping operation, for example particles are obtained which can optionally be ground. If necessary, these particles may be further shaped, such as an agglomeration step, so as to obtain granules.
Il est à noter que des additifs, tels que les agents antimottants peuvent être incorporés aux granulés au moment de cette étape de séchage.It should be noted that additives, such as anti-caking agents may be incorporated into the granules at the time of this drying step.
On recommande, à titre d'exemple, d'utiliser une charge choisie notamment parmi le carbonate de calcium, le sulfate de baryum, le kaolin, la silice, la bentonite, l'oxyde de titane, le talc, l'alumine hydratée et le sulfoaluminate de calcium. De préférence, le séchage est effectué de telle sorte que qu'au moins 90% en poids de la phase aqueuse externe sont éliminés, de préférence entre 90 et 95 % en poids. La quantité d'eau résiduelle est de préférence inférieure à 3% en poids.By way of example, it is recommended to use a filler chosen in particular from calcium carbonate, barium sulfate, kaolin, silica, bentonite, titanium oxide, talc, hydrated alumina and calcium sulfoaluminate. Preferably, the drying is carried out such that at least 90% by weight of the external aqueous phase is removed, preferably between 90 and 95% by weight. The amount of residual water is preferably less than 3% by weight.
Utilisations:uses:
L'émulsion séchée peut être utilisée:The dried emulsion can be used:
- dans des formulations phytosanitaires,- in phytosanitary formulations,
- dans des formulations pour le soin du linge, par exemple dans des lessives en poudre ou en tablettes, pour la formulation d'adoucissants, la vectorisation de parfums, la formulation d'antimousses, ou de silicones par exemple pour un dépôt sur des fibres,in formulations for the care of laundry, for example in powdered or tablet detergents, for the formulation of softeners, the vectorization of perfumes, the formulation of defoamers, or silicones for example for a deposit on fibers ,
- dans des formulations pour lave-vaisselle automatique, sous forme de poudres ou tablettes,in formulations for automatic dishwashers, in the form of powders or tablets,
- dans des formulations cosmétiques,in cosmetic formulations,
- dans des lingettes pour les soins domestiques, - dans des lingettes ou pour les soins de la peau- in wipes for household care, - in wipes or for skincare
- dans des lingettes pour le soin des bébés,- in wipes for the care of babies,
- dans des couches-culotte- in diapers
- dans des lingettes de démaquillage,- in cleansing wipes,
- dans des formulations de sels de bains, - dans des formulations de matériaux de bâtiments et/ou de travaux publics, par exemple pour la formulation de retardateurs ou d'accélérateurs de prise de ciments,in formulations of bath salts, in formulations of building materials and / or public works, for example for the formulation of retarders or accelerators for setting cement,
- dans des formulations de revêtements de surfaces, par exemple dans des peintures.in surface coating formulations, for example in paints.
- pour formuler sous forme solide des huiles silicones, par exemple des antimousses.to formulate in solid form silicone oils, for example defoamers.
De manière plus détaillée, l'émulsion séchée peut être utilisée dans des formulations phytosanitaires, la phase hydrophobe étant un composé actif phytosanitaire, ou un mélange comprenant composé un composé hydrophobe actif phytosanitaire, en solution ou dispersion dans un solvant hydrophobe. L'émulsion séchée peut éventuellement utilisée avec d'autres produits phytosanitaires (association de produits phytosanitaires), par exemple en association avec un fertilisant. L'émulsion séchée et le fertilisant peuvent notamment êtres mélangés dans un même réservoir avec de l'eau.In more detail, the dried emulsion can be used in phytosanitary formulations, the hydrophobic phase being a phytosanitary active compound, or a mixture comprising a hydrophobic active phytosanitary compound, in solution or dispersion in a hydrophobic solvent. The dried emulsion may optionally be used with other phytosanitary products (association of phytosanitary products), for example in combination with a fertilizer. The dried emulsion and the fertilizer may in particular be mixed in the same tank with water.
D'autres détails ou avantages de l'invention pourront apparaître au vu des exemples ci- dessous, sans caractère limitatif. On réalise des émulsions séchées dont la phase hydrophobe est du métolachlor, par préparation d'une émulsion comprenant du métolachlor, un tensioactif, de l'eau et le polymère (Geropon® EGPM commercialisé par Rhodia), puis séchage. Les compositions (ingrédients et quantités) des émulsions et des émulsions séchées sont données dans les tableaux ci-dessous.Other details or advantages of the invention may appear in light of the examples below, without limitation. Dried emulsions whose hydrophobic phase is metolachlor are prepared by preparing an emulsion comprising metolachlor, a surfactant, water and the polymer (Geropon® EGPM marketed by Rhodia), followed by drying. The compositions (ingredients and quantities) of the emulsions and dried emulsions are given in the tables below.
Mode opératoire: a) Réalisation de l'émulsionProcedure: a) Realization of the emulsion
- On pèse le polymère avec éventuellement un antimousse - On met sous agitation à 500 tours/minutes avec une pale cadreThe polymer is weighed down with an antifoam if necessary. The stirring is carried out at 500 rpm with a paddle frame.
- On ajoute la totalité de l'eau ou une partie- Add all or part of the water
- On ajoute un mélange de métolachlor et du tensioactif.- A mixture of metolachlor and surfactant is added.
- On homogénéise et on acidifie par HCI 2N (goutte à goutte)- Homogenize and acidify with HCl 2N (drop by drop)
- On laisse sous agitation à 500 tours/minutes 15 minutes - On ajoute le cas échéant le reste de l'eau- It is stirred at 500 revolutions / minutes 15 minutes - If necessary the rest of the water is added
- On laisse sous agitation 30 minutes- Let stir 30 minutes
- On mesure la granulométrie (Horiba) en fonction du temps b) Séchage- The particle size (Horiba) is measured as a function of time b) Drying
- On sèche sur plateau en étuve à 750C pendant une nuit - On broie grossièrement.- Dry on a tray in an oven at 75 0 C overnight - Coarsely ground.
- On mesure la granulométrie lors d'une re-dispersion (1 g de poudre dans 50 ml d'eau de ville, avec un agitateur électro-magnétique, à 500 tours/minutes pendant 5 minutes à température ambiante. The particle size is measured during re-dispersion (1 g of powder in 50 ml of tap water, with an electromagnetic stirrer, at 500 rpm for 5 minutes at room temperature.
Exemple 1 (Comparatif)Example 1 (Comparative)
Tristyrylphenol polyethoxyléPolyethoxylated tristyrylphenol
Emulsion avant séchageEmulsion before drying
- Métolachlor / sec: 63,7%- Metolachlor / sec: 63.7%
- Extrait Sec: 34,9%- Sec clip: 34.9%
- Tensioactif / (Métolachlor + tensioactif) : 6,8%- Surfactant / (Metolachlor + surfactant): 6.8%
- Tensioactif / polymère : 13,2 %- Surfactant / Polymer: 13.2%
L'émulsion est grossière. Elle n'est pas séchée par la suite. The emulsion is coarse. It is not dried afterwards.
Exemple 2 (Comparatif)Example 2 (Comparative)
(1) Tristyrylphenol polyethoxylé(1) Polyethoxylated tristyrylphenol
Emulsion avant séchageEmulsion before drying
- Extrait Sec: 34,9%- Sec clip: 34.9%
- Tensioactif / (Métolachlor + tensioactif) : 3%- Surfactant / (Metolachlor + surfactant): 3%
- Tensioactif / (tensioactif + polymère sec) : 6,0 %- Surfactant / (surfactant + dry polymer): 6.0%
Granulométrie avant séchage:Granulometry before drying:
D10 = 0,54 μmD10 = 0.54 μm
D50 = 1 ,30 μmD50 = 1, 30 μm
D90 = 3,35 μmD90 = 3.35 μm
(D90-D10) / D50 = 2,16(D90-D10) / D50 = 2.16
L'émulsion n'est pas séchée par la suite. The emulsion is not dried subsequently.
Exemple 3Example 3
(2) Ester de sorbitan(2) Sorbitan Ester
Emulsion avant séchageEmulsion before drying
- Extrait Sec: 35,3%- Dry extract: 35.3%
- Tensioactif / (Métolachlor + tensioactif) : 3%- Surfactant / (Metolachlor + surfactant): 3%
- Tensioactif / (tensioactif + polymère sec) : 6,0 %- Surfactant / (surfactant + dry polymer): 6.0%
Granulométrie avant séchage:Granulometry before drying:
D10 = 0,228 μm bipopulée 21 , 156 μmD10 = 0.228 μm bipopulated 21, 156 μm
D50 = 0,329 μm bipopulée 28,625 μmD50 = 0.329 μm bipopulated 28.625 μm
D90 = 0,453 μm bipopulée 38,645 μmD90 = 0.453 μm bipopulated 38.645 μm
(D90-D10) / D50 = 0,684 bipopulée 0,611(D90-D10) / D50 = 0.684 bipopulated 0.611
L'émulsion n'est pas séchée par la suite. Exemple 4The emulsion is not dried subsequently. Example 4
(3) mélange comprenant un ester d'acide oléique et de sorbitan et 15% en poids d'acide oléique.(3) A mixture comprising an ester of oleic acid and sorbitan and 15% by weight of oleic acid.
Emulsion avant séchageEmulsion before drying
- Extrait Sec: 35,3%- Dry extract: 35.3%
- Tensioactif / (Métolachlor + tensioactif) : 3%- Surfactant / (Metolachlor + surfactant): 3%
- Tensioactif / (tensioactif + polymère sec) : 6,0 %- Surfactant / (surfactant + dry polymer): 6.0%
Granulométrie avant séchage:Granulometry before drying:
D10 = 0,233 μmD10 = 0.233 μm
D50 = 0,303 μmD50 = 0.303 μm
D90 = 0,42 μmD90 = 0.42 μm
(D90-D10) / D50 = 0,617 L'émulsion n'est pas séchée par la suite. Exemple 5 (Comparatif)(D90-D10) / D50 = 0.617 The emulsion is not dried subsequently. Example 5 (Comparative)
(4) acide oléique.(4) oleic acid.
Emulsion avant séchageEmulsion before drying
- Extrait Sec: 36,4- Extract Sec: 36.4
L'émulsion est grossière. Elle n'est pas séchée par la suite.The emulsion is coarse. It is not dried afterwards.
Exemple 6Example 6
(5) mélange comprenant un ester d'acide oléique et de sorbitan et 8% en poids d'acide oléique.(5) A mixture comprising an ester of oleic acid and sorbitan and 8% by weight of oleic acid.
Emulsion avant séchage - Extrait Sec: 35,3% - Tensioactif / (Métolachlor + tensioactif) : 3%Emulsion before drying - Dry extract: 35,3% - Surfactant / (Metolachlor + surfactant): 3%
- Tensioactif / (tensioactif + polymère sec) : 6,0 %- Surfactant / (surfactant + dry polymer): 6.0%
Granulométrie avant séchage: D10 = 0,124 μm D50 = 0,168 μm D90 = 0,226 μm (D90-D10) / D50 = 0,607Particle size before drying: D10 = 0.124 μm D50 = 0.168 μm D90 = 0.226 μm (D90-D10) / D50 = 0.607
Granulométrie après re-dispersion:Granulometry after re-dispersion:
D10 = 0,258 μmD10 = 0.258 μm
D50 = 0,396 μmD50 = 0.396 μm
D90 = 0,591 μmD90 = 0.591 μm
(D90-D10) / D50 = 0,841(D90-D10) / D50 = 0.841
Les granulométries avant séchage et après re-dispersion sont remarquables. The granulometries before drying and after re-dispersion are remarkable.

Claims

REVENDICATIONS
1. Emulsion séchée comprenant une matrice comprenant un polymère hydrosoluble ou hydrodispersable, dans laquelle est dispersée une phase hydrophobe, caractérisée en ce que:A dried emulsion comprising a matrix comprising a water-soluble or water-dispersible polymer, in which a hydrophobic phase is dispersed, characterized in that:
- l'émulsion séchée comprend un tensioactif non polyalcoxylé,the dried emulsion comprises a non-polyalkoxylated surfactant,
- le polymère hydrosoluble ou hydrodispersable compris dans la matrice est un polycarboxylate comprenant des unités hydrophobes.the water-soluble or water-dispersible polymer included in the matrix is a polycarboxylate comprising hydrophobic units.
2. Emulsion séchée selon la revendication 1 , caractérisée en ce que la phase hydrophobe est une phase hydrophobe liquide, ou une phase hydrophobe solide.2. Dried emulsion according to claim 1, characterized in that the hydrophobic phase is a liquid hydrophobic phase, or a solid hydrophobic phase.
3. Emulsion séchée selon l'une des revendications précédentes, caractérisé en ce que la phase hydrophobe est un composé hydrophobe actif, ou un mélange comprenant un composé hydrophobe actif en solution ou dispersion dans un solvant hydrophobe.3. Dried emulsion according to one of the preceding claims, characterized in that the hydrophobic phase is an active hydrophobic compound, or a mixture comprising a hydrophobic active compound in solution or dispersion in a hydrophobic solvent.
4. Emulsion séchée selon l'une des revendications précédentes, caractérisée en ce que le polycarboxylate comprenant des unités hydrophobes est un copolymère comprenant des unités dérivant des monomères suivants: - (I) acide monocarboxylique ou polycarboxylique, ou anhydride, aliphatique, cyclique ou aromatique, linéaire ou ramifié, éthyléniquement insaturé,4. Dried emulsion according to one of the preceding claims, characterized in that the polycarboxylate comprising hydrophobic units is a copolymer comprising units deriving from the following monomers: - (I) monocarboxylic or polycarboxylic acid, or anhydride, aliphatic, cyclic or aromatic , linear or branched, ethylenically unsaturated,
- (Il) monomère de formule (R2)(R2) C = CH (R3) dans laquelle- (II) monomer of formula (R 2 ) (R 2 ) C = CH (R 3 ) in which
- R3 est un atome d'hydrogène ou un groupe méthyle, et - R2, identiques ou différents, représentent un atome d'hydrogène, un radical saturé ou éthyléniquement insaturé, aliphatique ou aromatique, linéaire ou ramifié, éventuellement cyclique, en C2 - C10, à la condition que les deux radicaux R2 ne soient pas des atomes d'hydrogène, et- R 3 is a hydrogen atom or a methyl group, and - R 2 , identical or different, represent a hydrogen atom, a linear or branched, optionally cyclic, saturated or ethylenically unsaturated, aliphatic or aromatic radical, in C2 - C10, with the proviso that the two radicals R2 are not hydrogen atoms, and
- optionnellement (III) ester polyoxyalkyléné d'acide carboxylique éthyléniquement insaturé.optionally (III) polyoxyalkylene ester of ethylenically unsaturated carboxylic acid.
5. Emulsion séchée selon la revendication 4, caractérisée en ce que le monomère (I) a pour formule5. Dried emulsion according to claim 4, characterized in that the monomer (I) has the formula
(R3)HC = C(R1) - COOX (la) dans laquelle:(R 3 ) HC = C (R 1 ) - COOX (la) in which:
- R3 est un atome d'hydrogène ou un groupe méthyle, - R1 est un atome d'hydrogène, un radical hydrocarboné en C-] - C-io comprenant éventuellement un groupe - COOX, ou un groupe -COOX, formant éventuellement avec le groupe - COOX un groupe anhydride -CO-O-OC-, etR 3 is a hydrogen atom or a methyl group, R 1 is a hydrogen atom, a C 1 -C 10 hydrocarbon radical optionally comprising a COOX group, or a -COOX group, optionally forming, with the group COOX, an anhydride group -CO-O-OC; -, and
- X est un atome d'hydrogène ou un cation.X is a hydrogen atom or a cation.
6. Emulsion séchée selon la revendication 5, caractérisé en ce que le monomère (I) est choisi parmi les acides ou anhydrides acrylique, méthacrylique, citraconique, maléique, fumarique, itaconique, crotonique.6. Dried emulsion according to claim 5, characterized in that the monomer (I) is chosen from acrylic, methacrylic, citraconic, maleic, fumaric, itaconic and crotonic acids or anhydrides.
7. Emulsion séchée selon l'une des revendications 4 à 6, caractérisée en ce que le monomère (11) est choisi parmi le 1 -butène, l'isobutylène, le n-1-pentène, le 2-méthyl 1- butène, le n-1-hexène, le 2-méthyl 1-pentène, le 4-méthyl 1-pentène, le 2-éthyl 1- butène, le diisobutylène, le 2-méthyl 3,3-diméthyl 1-pentène.7. Dried emulsion according to one of claims 4 to 6, characterized in that the monomer (11) is selected from 1-butene, isobutylene, n-1-pentene, 2-methyl-1-butene, n-1-hexene, 2-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-butene, diisobutylene, 2-methyl-3, 3-dimethyl-1-pentene.
8. Emulsions séchées selon l'une des revendications précédentes, caractérisée en ce que le polycarboxylate comprenant des unités hydrophobes est un copolymère dérivant d'anhydride maléique ou d'un sel d'anhydride maléique, et de diisobutylène.8. Dried emulsions according to one of the preceding claims, characterized in that the polycarboxylate comprising hydrophobic units is a copolymer derived from maleic anhydride or a maleic anhydride salt, and diisobutylene.
9. Emulsions séchées selon l'une des revendications précédentes, caractérisée en ce que le tensioactif non polyalcoxylé est un tensioactif non ionique non polyalcoxylé, un tensioactif anionique non polyalcoxylé, un tensioactif amphotère non polyalcoxylé, ou un mélange de ces tensioactifs.9. Dried emulsions according to one of the preceding claims, characterized in that the non-polyalkoxylated surfactant is a non-polyalkoxylated nonionic surfactant, a non-polyalkoxylated anionic surfactant, a non-polyalkoxylated amphoteric surfactant, or a mixture of these surfactants.
10. Emulsion séchée selon la revendication 9, caractérisée en ce que le tensioactif non ionique non polyalcoxylé est choisi parmi les tensioactifs suivants:10. Dried emulsion according to claim 9, characterized in that the non-polyalkoxylated nonionic surfactant is chosen from the following surfactants:
- les alkylpolyglucosides,the alkylpolyglucosides,
- les esters de sorbitan non polyalcoxylés,the non-polyalkoxylated sorbitan esters,
- les acides gras,fatty acids,
- leurs mélanges.- their mixtures.
11. Emulsion séché selon la revendication 9, caractérisée en ce que le tensioactif non non polyalcoxylé est:Dried emulsion according to claim 9, characterized in that the non-polyalkoxylated surfactant is:
- un ester de sorbitan dérivant d'un acide gras en C8-C30, de préférence en Ci6-C22, oua sorbitan ester derived from a C 8 -C 30 fatty acid, preferably a C 6 -C 2 2 fatty acid, or
- un mélange d'un ester de sorbitan dérivant d'un acide gras en C8-C30, de préférence en Ci6-C22, et d'un acide gras en C8-C30, de préférence en C16-C22, ou d'un sel de l'acide gras. a mixture of a sorbitan ester derived from a C 8 -C 30 fatty acid, preferably a C 6 -C 22 fatty acid, and a C 8 -C 30 fatty acid, preferably a C 16 -C 20 fatty acid; C 22 , or a salt of the fatty acid.
12. Emulsion séchée selon la revendication 11 , caractérisée en ce que le mélange de l'ester de sorbitan et de l'acide gras comprend, en matière sèche, de 2 à 20% en poids de l'acide gras ou du sel.12. Dried emulsion according to claim 11, characterized in that the mixture of the sorbitan ester and the fatty acid comprises, in dry matter, 2 to 20% by weight of the fatty acid or salt.
13. Emulsion séchée selon l'une des revendications précédentes caractérisé en ce que le rapport pondéral entre la phase hydrophobe et la matrice est compris entre 50% et 80%.13. Dried emulsion according to one of the preceding claims characterized in that the weight ratio between the hydrophobic phase and the matrix is between 50% and 80%.
14. Emulsion séchée selon l'une des revendications précédentes caractérisée en ce que le rapport pondéral entre le tensioactif non polyalcoxylé et la phase hydrophobe est compris entre 0,003 et 0,3, de préférence entre 0,01 et 0,06.14. Dried emulsion according to one of the preceding claims characterized in that the weight ratio between the non-polyalkoxylated surfactant and the hydrophobic phase is between 0.003 and 0.3, preferably between 0.01 and 0.06.
15. Emulsion séchée selon l'une des revendications précédentes, caractérisée en ce que le rapport pondéral entre le tensioactif non polyalcoxylé et la matrice est compris entre 0,006 et 0,6, de préférence entre 0,02 et 1 ,2.15. Dried emulsion according to one of the preceding claims, characterized in that the weight ratio between the non-polyalkoxylated surfactant and the matrix is between 0.006 and 0.6, preferably between 0.02 and 1, 2.
16. Emulsion séchée selon l'une des revendications précédentes caractérisée en ce que la matrice comprend au moins 90% en poids du polymère hydrosoluble ou hydrodispersable.16. Dried emulsion according to one of the preceding claims characterized in that the matrix comprises at least 90% by weight of the water-soluble or water-dispersible polymer.
17. Procédé de préparation d'une emulsion séchée selon l'une des revendications précédentes, comprenant les étapes suivantes: a) préparer une emulsion comprenant une phase aqueuse dans laquelle est dispersée la phase hydrophobe dispersée sous forme liquide dans l'eau, l'émulsion comprenant le copolymère hydrosoluble ou hydrodispersable de la matrice le tensioactif non polyalcoxylé, le cas échéant en chauffant la phase hydrophobe au dessus de son point de fusion, b) éliminer l'eau, pour obtenir une emulsion séchée, c) éventuellement mettre l'émulsion séchée sous forme de poudre ou de granulés, d) récupérer l'émulsion séchée.17. Process for the preparation of a dried emulsion according to one of the preceding claims, comprising the following steps: a) preparing an emulsion comprising an aqueous phase in which is dispersed the hydrophobic phase dispersed in liquid form in water, the an emulsion comprising the water-soluble or water-dispersible copolymer of the matrix, the non-polyalkoxylated surfactant, where appropriate by heating the hydrophobic phase above its melting point, b) removing the water, to obtain a dried emulsion, c) optionally adding the dried emulsion in the form of powder or granules, d) recovering the dried emulsion.
18. Procédé selon la revendication 17, caractérisé en ce que lors de l'étape b) l'eau est éliminée par évaporation en couche mince, lyophilisation, ou par atomisation de l'émulsion. 18. The method of claim 17, characterized in that during step b) the water is removed by evaporation in a thin layer, lyophilization, or by atomization of the emulsion.
19. Procédé selon l'une des revendications 17 ou 18, caractérisé en ce que la proportion pondérale entre la phase aqueuse et la phase hydrophobe est comprise entre 5 et 99%.19. Method according to one of claims 17 or 18, characterized in that the weight ratio between the aqueous phase and the hydrophobic phase is between 5 and 99%.
20. Utilisation de l'émulsion séchée selon l'une des revendications 1 à 16 ou préparée par le procédé selon l'une des revendications 17 à 19, dans des formulations phytosanitaires, dans des formulations pour le soin du linge, dans des formulations pour lave-vaisselle, dans des formulations cosmétiques, dans des lingettes pour les soins domestiques ou pour les soins de la peau ou pour le soin des bébés, dans des couches- culottes, dans des formulations de matériaux de bâtiments et/ou de travaux publics, dans des formulations de revêtements de surfaces, par exemple dans des peintures.20. Use of the dried emulsion according to one of claims 1 to 16 or prepared by the method according to one of claims 17 to 19, in phytosanitary formulations, in formulations for the care of laundry, in formulations for dishwashers, in cosmetic formulations, in household or skin care or baby care wipes, in diapers, in building material formulations and / or public works, in surface coating formulations, for example in paints.
21. Utilisation de l'émulsion séchée selon la revendication 20, dans des formulations phytosanitaires, la phase hydrophobe étant un composé actif phytosanitaire, ou un mélange comprenant composé un composé hydrophobe actif phytosanitaire, en solution ou dispersion dans un solvant hydrophobe, l'émulsion séchée étant éventuellement utilisée en association avec un fertilisant.21. Use of the dried emulsion according to claim 20, in phytosanitary formulations, the hydrophobic phase being a phytosanitary active compound, or a mixture comprising a hydrophobic compound active phytosanitary, in solution or dispersion in a hydrophobic solvent, the emulsion. dried being optionally used in combination with a fertilizer.
22. Utilisation selon la revendication 21 , en association avec un fertilisant, l'émulsion séchée et le fertilisant étant mélangés dans un même réservoir avec de l'eau. 22. Use according to claim 21, in combination with a fertilizer, the dried emulsion and the fertilizer being mixed in the same tank with water.
EP05821415A 2004-11-22 2005-11-22 Dried emulsion, method for preparing same and uses thereof Withdrawn EP1814932A2 (en)

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FR2878170A1 (en) 2006-05-26

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