EP1404437A1 - Granulate hergestellt durch trocknung einer mischung mit einem polymer und einem regulierungsmittel - Google Patents

Granulate hergestellt durch trocknung einer mischung mit einem polymer und einem regulierungsmittel

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Publication number
EP1404437A1
EP1404437A1 EP02764981A EP02764981A EP1404437A1 EP 1404437 A1 EP1404437 A1 EP 1404437A1 EP 02764981 A EP02764981 A EP 02764981A EP 02764981 A EP02764981 A EP 02764981A EP 1404437 A1 EP1404437 A1 EP 1404437A1
Authority
EP
European Patent Office
Prior art keywords
chosen
polyalkoxylated
granules according
mixture
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP02764981A
Other languages
English (en)
French (fr)
Inventor
Laurent Taisne
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
Original Assignee
Rhodia Chimie SAS
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Filing date
Publication date
Application filed by Rhodia Chimie SAS filed Critical Rhodia Chimie SAS
Publication of EP1404437A1 publication Critical patent/EP1404437A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0216—Solid or semisolid forms
    • A61K8/022—Powders; Compacted Powders
    • A61K8/0225—Granulated powders
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • B01J2/02—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops
    • B01J2/04—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops in a gaseous medium
    • 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
    • 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
    • C09K23/14—Derivatives of phosphoric acid
    • 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
    • C09K23/16—Amines or polyamines
    • 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
    • C09K23/54—Silicon compounds

Definitions

  • the subject of the present invention is granules capable of being obtained by drying a mixture, in particular an emulsion, comprising inter alia a control agent.
  • solid formulations comprising high contents of active materials and capable of releasing them in a controlled manner, whether in the form of a gradual release over time and / or in the form of form of a release triggered by the appearance of a specific phenomenon.
  • active materials which it is desired to incorporate are in the form of a hydrophobic liquid or in a pasty form at room temperature.
  • drying emulsions comprising, in addition to the active material, a surfactant and a compound making it possible to obtain a solid matrix after elimination of the aqueous phase from the emulsion.
  • the object of the present invention is to provide granules which make it possible to obtain, with the same composition, on the one hand large concentrations of active material (s) in solid formulations, and on the other hand, a spreading release in the time and / or triggered of said active material, once the formulation has been applied.
  • the present invention therefore relates to granules which can be obtained by drying a mixture comprising:
  • At least one surfactant chosen from nonionic polyalkoxylated surfactants, anionic surfactants, or mixtures thereof,
  • At least one water-soluble or water-dispersible compound chosen from (i) the polymers obtained by polymerization:
  • At least one acid monomer chosen from monocarboxylic or polycarboxylic acids, or carboxylic anhydrides; aliphatic, cyclic or aromatic; linear or branched; bearing at least one ethylenic unsaturation; said monomers being used in acid form or in salt form, or in the form of macromonomers; and
  • polypeptides of natural or synthetic origin optionally comprising at least one hydrophobic graft, comprising 4 to 30 carbon atoms, saturated or not, aromatic or not, optionally interrupted by one or more heteroatoms, and comprising at least one function carboxylic acid and / or a hydroxyl function;
  • the emulsion comprises at least one control agent chosen from:
  • the present invention likewise relates to the use of such granules as additives in formulations which can be used in the fields of food, cosmetics, pharmaceuticals, detergents, paints, paper, agrochemicals, working or deformation of metals.
  • the granules according to the invention have the advantage, when they are used, of reducing, even eliminating, the risks of temporary overdosage of the active substances released into the medium.
  • the problems of toxicity, of ecotoxicity are considerably reduced.
  • the granules according to the invention also make it possible to increase the effectiveness of a formulation, due to the controlled, progressive or triggered release of the active material. Consequently, the concentration of active ingredient in the medium to be treated is no longer zero or can be adapted as required.
  • the granules according to the invention are obtained from a mixture which can be in the form of an aqueous solution or of a direct oil-in-water emulsion, depending on whether the constituent elements are miscible or not in the aqueous phase.
  • the granules comprise at least one active ingredient.
  • the active materials used are present at room temperature, in the form of a liquid immiscible or very slightly miscible in water, or in a form dissolved in an organic solvent , the whole being immiscible or very slightly miscible in water.
  • slightly miscible is meant active materials whose solubility in water does not exceed 10% by weight between 20 and 30 ° C.
  • the present invention can equally well be applied to the shaping of active materials whose melting point is less than or equal to 100 ° C., more particularly less than or equal to 80 ° C., and in particular understood. between 20 and 80 ° C. Consequently, the term hydrophobic liquid will also relate to such active materials.
  • active material means either the pure active material or the active material dissolved in a solvent.
  • the active materials which can be used in the granules according to the invention can belong to very diverse fields, such as those of food, detergency, cosmetics, pharmaceutical industry, paints, paper, l agrochemistry, working or deformation of metals, etc.
  • active ingredients in the food sector there may be mentioned mono-, di- and triglycerides, essential oils, flavorings, colorings, lipophilic vitamins.
  • active materials which 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 the PABA and PARA type, salicylates, cinnamates, anthranilates, dibenzoylmethanes, camphor derivatives and their mixtures.
  • Anti-aging agents can also be used.
  • examples of such agents that may be mentioned include retinoids, ⁇ - and ⁇ -hydroxy acids, their salts and their esters, fat-soluble vitamins, ascorbyl palmitate, ceramides, pseudoceramides, phospholipids, fatty acids, fatty alcohols, cholesterol, sterols and their mixtures.
  • fatty acids and alcohols mention may more particularly be made of those having linear or branched alkyl chains containing from 12 to 20 carbon atoms. It can in particular be linoleic acid.
  • anti-cellulite agents such as in particular isobutylmethylxanthine and theophyline
  • anti-acne agents such as resorcinol, resorcinol acetate, benzoyl peroxide and many natural compounds.
  • Aromas, perfumes, essential oils, essences, can also be used as a hydrophobic active material.
  • the antimicrobial agents can be chosen from thymol, menthol, triclosan, 4-hexylresorcinol, phenol, eucalyptol, benzoic acid, benzoic peroxide, butyl paraben, and their mixtures.
  • active materials suitable for the invention and usable in the field of paints mention may be made of alkyd resins, epoxy resins, blocked or non-blocked isocyanates.
  • phytosanitary active ingredients can be used.
  • active ingredients which are soluble or dissolved in the organic phase and which can be used in the field of phytosanitary formulations, mention may be made, for example, of the active ingredients chosen from the family of ⁇ -cyano-phenoxybenzyl carboxylates or ⁇ -cyano- halophenoxy-carboxylates, the family of N-methylcarbonates comprising aromatic substituents, active ingredients such as Azinphos-methyl, Benfluralin, Bifenthrin, Chlorphoxim, Chlorpyrifos, Fluchloralin, Fluroxypyr, Dichlorvos, Malathion, Molinate, Parathion, Permethrin
  • Imazapyr Imazaquin
  • Imazethapyr or mixtures thereof. Mention may likewise be made, as suitable active materials in the field of phytosanitary formulations, vegetable and mineral oils, silicone oils, silicone anti-foaming agents, etc.
  • hydrophobic active substances include - organic oils / fats / waxes of animal or vegetable origin;
  • organic oils / fats / waxes of animal origin mention may be made, among others, of sperm whale oil, whale oil, seal oil, shark oil, cod liver oil, pork and mutton fats (tallow), perhydrosqualene, beeswax, alone or in a mixture.
  • organic oils / fats / waxes of vegetable origin there may be mentioned, inter alia, rapeseed oil, sunflower oil, peanut oil, olive oil , walnut oil, corn oil, soybean oil, avocado oil, linseed oil, hemp oil, grape seed oil, copra, palm oil, cotton seed oil, palm kernel oil, babassu oil, jojoba oil, sesame oil, castor oil, macadamia, sweet almond oil, carnauba wax, shea butter, cocoa butter, peanut butter, alone or in a mixture.
  • rapeseed oil sunflower oil, peanut oil, olive oil , walnut oil, corn oil, soybean oil, avocado oil, linseed oil, hemp oil, grape seed oil, copra, palm oil, cotton seed oil, palm kernel oil, babassu oil, jojoba oil, sesame oil, castor oil, macadamia, sweet almond oil, carnauba wax, shea butter, cocoa butter, peanut butter, alone or in a mixture.
  • mineral oils / waxes there may be mentioned, inter alia, naphthenic, paraffinic (petrolatum), isoparaffinic oils, paraffinic waxes, alone or as a mixture.
  • fatty acids saturated or unsaturated, contain 10 to 40 carbon atoms, more particularly 18 to 40 carbon atoms, and can comprise one or more ethylenic unsaturations, conjugated or not. It should be noted that said acids can comprise one or more hydroxyl groups.
  • saturated fatty acids mention may be made of palmitic, stearic, isostearic and behenic acids.
  • unsaturated fatty acids there may be mentioned myristoleic, palmitoleic, oleic, erucic, linoleic, linolenic, arachidonic, ricinoleic acids, as well as their mixtures.
  • esters As regards fatty acid esters, mention may be made of the esters of the acids listed above, for which the part deriving from alcohol comprises 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, etc.
  • the active material is chosen from nonionic, anionic surfactants or their mixtures. More particularly, the nonionic surfactants are chosen from nonionic polyalkoxylated surfactants, such as for example:
  • (poly) alkoxylated is meant ethoxylated, propoxylated units, or combinations thereof.
  • the surfactants comprise ethoxylated, or ethoxylated / propoxylated units.
  • the number of ethoxylated (EO) and / or propoxylated (OP) units of these surfactants usually varies from 1 to 100, more particularly from 1 to 50.
  • the fatty alcohols OE or OE / OP generally comprise from 6 to 22 carbon atoms, the units OE and OP being excluded from these numbers. Preferably, these units are ethoxylated units (EO).
  • the fatty acids OE or OE / OP include in particular from 6 to 22 carbon atoms, the units OE and OP being excluded from these numbers. Preferably, these units are ethoxylated units (EO).
  • the triglycerides OE or OE / OP, preferably OE, are more particularly triglycerides of plant or animal origin, such as for example such as linseed oil, soybean oil, castor oil, oil rapeseed, etc.
  • esters of fatty acids OE or OE / OP generally comprise, for the acid part, from 6 to 22 carbon atoms, the units OE and OP being excluded from these numbers, and are preferably ethoxylated (OE).
  • esters of sorbitan OE or OE / OP are more particularly esters of cyclized sorbitol of fatty acid comprising from 10 to 20 carbon atoms such as lauric acid, stearic acid or oleic acid.
  • triglyceride OE or OE / OP is intended in the present invention, both the products obtained by alkoxyiation of a triglyceride with ethylene oxide and / or by propylene oxide as those obtained by transesterification of a triglyceride with a polyethylene glycol and / or polypropylene glycol.
  • fatty acid ester OE or OE / OP includes both the products obtained by alkoxyiation of a fatty acid with ethylene oxide and / or propylene oxide as well as those obtained by transesterification of a fatty acid with a polyethylene glycol and / or polypropylene glycol.
  • the amines and fatty amides OE or OE / OP generally have from 6 to 22 carbon atoms, the OE and OP units being excluded from these numbers, and are preferably ethoxylated (OE).
  • the amidoamines OE or OE / OP usually have from 2 to 22 carbon atoms for the hydrocarbon units, the units OE and OP being excluded from these numbers, and are preferably ethoxylated (OE).
  • the alkylphenols OE or OE / OP are conventionally 1 or 2 alkyl groups, linear or branched, having 4 to 12 carbon atoms. By way of example, mention may in particular be made of octyl, nonyl or dodecyl groups.
  • the polysiloxanes are more particularly linear or branched polyalkylsiloxanes, comprising 2 to 10 silicon atoms, and in which the alkyl groups are preferably methyl radicals.
  • Suitable terpene hydrocarbons are in particular those derived from - or from ⁇ -pinenes. They have been described in international application WO 96/01245.
  • the alkylpolyglycosides can be obtained by condensing glucose with primary fatty alcohols having a C4-C20 alkyl group as well as an average number of glucose units of the order of 0.5 to 3 per mole of alkylpolyglycoside.
  • anionic surfactants the following may be mentioned in particular:
  • alkyl esters sulfonates for example of formula R-CH (SO 3 M) -CH 2 COOR ', where R represents a C 8 -C 2 o, preferably C 10 -C 16 hydrocarbon radical, optionally carrying one or more unsaturations, R 1 an alkyl radical in C Ce, preferably in CC 3 and M is a hydrogen atom, an alkaline cation (sodium, potassium, lithium) alkaline earth (calcium for example) or unsubstituted ammonium or substituted (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethyl piperidinium ...) or derived from an alkanolamine
  • the alkyl sulphates for example of formula ROSO 3 M, where R represents a C 10 -C 2 , preferably C 12 -C 2 o, alkyl or hydroxyalkyl radical; M has the above meaning;
  • the alkylamide sulfates for example of formula RCONHR'OSO 3 M where R represents an alkyl radical in C 2 -C 22 , preferably in C 6 -C 2 o, R 'an alkyl radical in C 2 -C 3 , M has the above meaning, as
  • salts of saturated or unsaturated fatty acids for example like those in C 8 - C 24 , preferably in C 14 -C 2 o and of a cation having the same definition as M, N-acyl N-alkyltaurates , alkylisethionates, alkylsuccinamates, monoesters or diesters of sulfosuccinates, N-acyl sarcosinates, polyethoxycarboxylates; and
  • alkyl- or dialkyl-sulfosuccinates for example such as those in C 6 -C 24 ; the cation being of the same definition as M; especially sodium dioctylsulfosuccinate;
  • (RO) x -P ( O) (OM) x or R represents an alkyl, alkylaryl, arylalkyl, aryl radical, optionally polyalkoxylated, x and x 'being equal to 1 or 2, provided that the sum of x and x 'is equal to 3, M has the above meaning; in particular derived from polyalkoxylated fatty alcohols, di- and tri- (1-phenylethyl) polyalkoxylated phenols; polyalkoxylated alkylphenols; alone or in mixtures.
  • the active ingredients can be used in the presence of a solvent for said active ingredients.
  • this solvent is chosen from products which are not soluble or hardly miscible in water in the sense indicated above. It is specified here that all of the hydrophobic liquid active materials which have just been described can be used, alone or in mixtures, as a solvent for one or more other active materials, or one or more other surfactants.
  • solvent aromatic petroleum cuts, terpenic compounds such as D-limonene, or the L-limonene, and solvents such as Solvesso ®.
  • solvents such as Solvesso ®.
  • aliphatic esters such as methyl esters of a mixture of acetic, succinic and glutaric acids (mixture of acids by-products of nylon synthesis), and chlorinated solvents. It should be noted that it would not go beyond the scope of the present invention to combine various active materials, various surfactants, or even their combinations, as soon as they are compatible with each other.
  • the total amount of active ingredient in the granule represents 30 to 90% by dry weight.
  • the emulsion from which the granules are obtained can also comprise at least one surfactant.
  • surfactants which have just been mentioned among the possible active materials can be used as surfactant.
  • the surfactant in the case where the active material used in the composition of the emulsion is chosen from hydrophobic active materials, in other words from species different from the surfactants, the surfactant, if present, is preferably chosen from the surfactants polyalkoxylated nonionics. In a particularly advantageous manner, the surfactant and chosen from polyalkoxylated sorbitan esters, polyalkoxylated triglycerides, alone or as a mixture. In the case where the active ingredient is chosen from hydrophobic active ingredients, the total content of surfactant, if present, in the granule is between 0 excluded and 10% by dry weight.
  • one of the essential constituent elements of the emulsion from which the granules can be obtained is the water-soluble or water-dispersible compound (hereinafter called compound).
  • water-soluble or water-dispersible denotes the compounds which do not precipitate or sediment when they are in solution / dispersion in an aqueous phase, optionally with the surfactant, under the conditions for preparing the mixture, and in particular the emulsion ( concentration); the temperature being from 20 to 30 ° C.
  • concentration concentration
  • temperature being from 20 to 30 ° C.
  • the compound is chosen from polymers obtained by polymerization (i) of at least one acid monomer chosen from monocarboxylic or polycarboxylic acids, or carboxylic anhydrides; aliphatic, cyclic or aromatic; linear or branched; bearing at least one ethylenic unsaturation; said monomers being used in acid form or in salt form, or in the form of macromonomer; and at least one hydrocarbon monomer carrying at least one ethylenic unsaturation, in the form of a monomer or a macromonomer.
  • macromonomer designates a macromolecule carrying one or more polymerizable functions.
  • R1 represents a hydrogen atom, a -COOM group or a - (CH2) n - COOM group in which n is between 1 and 4, a C1-C4 alkyl radical
  • R 2 represents a hydrogen atom, a - (CH2) m - COOM group in which m is between 1 and 4, a C1-C4 alkyl radical
  • M represents a hydrogen atom, an alkali metal (such as sodium, potassium, lithium, magnesium), or an ammonium group of NR4 + type with R, identical or different, representing a hydrogen atom, a alkyl radical comprising 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms, substituted or not by an oxygen atom; said monomer being used alone or as a mixture, or in the form of macromonomers of one or more of them.
  • said acid monomer is such that the radical R1 represents a hydrogen atom, a group -COOM or - (CH 2 ) -COOM, a methyl radical, and the radical R 2 represents a hydrogen atom, a group -CH 2 -COOM or a methyl radical.
  • the acid monomer is chosen from acrylic, methacrylic, citraconic, maleic, fumaric, itaconic, crotonic acids or anhydrides, alone or as a mixture, their salts, or in the form of macromonomers one or more of them.
  • the hydrocarbon monomer the latter more particularly corresponds to the following formula:
  • R2 (R2) (R2) - C CH2 (M) formula in which the radicals R 2 , identical or different, represent a hydrogen atom, a linear or branched, cyclic or cycloaliphatic aliphatic radical, in C1-C10 optionally carrying an ethylenic unsaturation; or an aromatic radical, preferably containing 6 carbon atoms, optionally substituted by at least one alkyl radical in C1-C10 "optionally bearing ethylenic unsaturation.
  • Said monomers can, here again, be used alone or as a mixture, or in the form of macromonomers of one or more of them.
  • the aforementioned hydrocarbon monomer can be advantageously chosen from ethylene, propylene, 1 -butene, pisobutylene, 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, styrene, Pcc-methylstyrene, vinyltoluene, butadiene, chloroprene, isoprene, or mixtures thereof, as well as macromonomers derived from such monomers.
  • the radicals R2 identical or different, represent a hydrogen atom, a saturated radical, linear or branched aliphatic, cyclic, or C-
  • the monomers and their respective proportions are chosen such that the resulting copolymer is water-soluble or water-dispersible.
  • the distribution of the monomers in the copolymer is random.
  • block copolymers it would not be departing from the scope of the present invention to use block copolymers.
  • the compounds used in the emulsion are copolymers well known to those skilled in the art and are prepared before their introduction into the mixture, in particular of the emulsion. They are conventionally obtained by implementing a radical polymerization, conventional or controlled, or of the anionic type.
  • the compound is chosen from polypeptides of natural or synthetic origin, comprising at least one carboxylic acid function and / or at least one hydroxyl function.
  • polypeptides are chosen from: - polypeptides of plant origin such as proteins originating from protein seeds (in particular those of peas, field beans, lupins, beans and lentils); proteins from cereal grains (such as those from wheat, barley, rye, corn, rice, oats, millet); proteins from oil seeds
  • polypeptides of animal origin such as muscle proteins; proteins from milk (such as casein, lactoglobulin); fish protein; as well as their hydrolysates.
  • Said polypeptides are more particularly water-soluble or water-dispersible polymers in the sense indicated above.
  • the degree of hydrolysis of said proteins is more especially less than or equal to 40%.
  • These polymers are homopolymers or copolymers derived from the polycondensation of amino acids, in particular aspartic acid, and / or glutamic or other copolymerizable amino acids, such as for example glycine, alanine, leucine, isoleucine , phenyl alanine, methionine, histidine, proline, lysine, serine, threonine, cysteine, etc.
  • the compound is chosen from highly depolymerized polysaccharides, comprising at least one carboxylic acid function and / or at least one hydroxyl function.
  • said highly depolymerized polysaccharides are obtained from: - polysaccharides of bacterial origin such as xanthan gum, succinoglycans,
  • polysaccharides of animal or vegetable origin such as carrageenans, galactomannans (such as guar, carob), glucomannans, cellulose, maltodextrins; alone or in mixtures.
  • Polymers are said to be “highly depolymerized”, within the meaning of the present invention, when their molar mass by weight is less than or equal to
  • highly depolymerized polysaccharides mention may be made of those obtained from starch, maltodextrins, xanthan gum and galactomannans such as guar or carob.
  • the compounds of the second and third variants may optionally include hydrophobic grafts. These grafts can be linked to the polypeptide or to the polysaccharide via amide, ester, urea, urethane, isocyanate, amino bonds. These grafted polymers are for example obtained by reaction of a part of the amino acid functions, or free alcohols, with compounds making it possible to create the abovementioned bonds.
  • hydrophobic graft if it is present, it is more particularly chosen from aliphatic, cyclic, aromatic, alkylaromatic, arylaliphatic radicals comprising 4 to 30 carbon atoms, and which can be interrupted by one or more heteroatoms, such as oxygen or nitrogen.
  • the molecular weights of the polymers as well as the respective proportions of the monomers present and optionally of the hydrophobic grafts, are such that the polymer concerned is water-soluble or water-dispersible.
  • the molar mass by weight of the polymers of the three above-mentioned variants is more particularly less than or equal to 50,000 g / mol, advantageously less than or equal to 20,000 g / mole (absolute value determined by MALLS (Multiangle laser light scattering) coupled with gel permeation chromatography, or by NMR).
  • the content of compound in the granule represents 10 to 70% by dry weight.
  • a granule comprises at least one hydrophobic liquid active material chosen from species other than surfactants and a surfactant
  • the compound content is such that the weight ratio of the concentrations
  • [surfactant (s) / compound] is between 1/99 and 70/30, more particularly between 1/99 and 50/50, preferably 1/99 and 30/70.
  • the mixture (and in particular the emulsion) from which the granules are obtained also comprises at least one control agent chosen from:
  • the complexing agents are in an ionic, anionic or cationic form, or also in the form of oxide or hydroxide particles.
  • the size of the oxide particles is nanometric (more particularly less than 200 nm, preferably less than or equal to 100 nm).
  • the control agent chosen from complexing agents comprises at least one of the elements chosen from calcium, magnesium, titanium, zirconium, copper, vanadium, iron , cobalt, aluminum, boron, as well as their mixtures.
  • the counter ions of the complexing agents which have just been mentioned are preferably chosen from mineral or organic ions which give species which are soluble in aqueous media, when they are combined with the complexing agent.
  • anionic mineral counter-ion examples include halides, such as, for example, chlorides, carbonates, nitrates, sulfates, hydrosulfates, alkyl sulfates (for example comprising 1 to 6 carbon atoms), phosphates, citrates, formates, acetates.
  • halides such as, for example, chlorides, carbonates, nitrates, sulfates, hydrosulfates, alkyl sulfates (for example comprising 1 to 6 carbon atoms), phosphates, citrates, formates, acetates.
  • anionic organic counter-ion mention may in particular be made of acetates, formates and lactates.
  • cationic counter-ion mention may be made of alkali metals, ammonium ions of the NR4 + type with R, identical or different, representing a hydrogen atom, an alkyl radical, comprising 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms, substituted or not by an oxygen atom.
  • the complexing agents can create ionic interactions with the compound. This is the case, for example, of ions of the borate, aluminate, vanadate, vanadyl sulfate, titanate, titanyl sulfate type, etc.
  • Complexing agents can likewise create interactions of the hydrogen bond type with the compound in the form of oxide or hydroxide, for example.
  • the molar ratio [number of metal atoms / number of hydroxyl and / or carboxylic functions of the compound] is between 1/1 and 1/100.
  • control agent is chosen from cationic polymers.
  • the latter are chosen from polyvinylpyrrolidone, cationic guars, cationic celluloses, cationic starches, synthetic polymers whose net charge is cationic.
  • the net charge represents the difference between the positive charges and the negative charges of the polymer, under the pH conditions of the emulsion.
  • the cationic group is more particularly a quaternary ammonium group carrying three radicals, identical or not, chosen from hydrogen, an alkyl radical comprising 1 to
  • the latter can be chosen from halides, such as, for example, chlorides, carbonates, nitrates, sulfates, hydrosulfates, alkyl sulfates (for example comprising 1 to 6 carbon atoms), phosphates, citrates, formates, acetates.
  • halides such as, for example, chlorides, carbonates, nitrates, sulfates, hydrosulfates, alkyl sulfates (for example comprising 1 to 6 carbon atoms), phosphates, citrates, formates, acetates.
  • cationic polymers comprising hydrophobic groups such as C1-C14, preferably C2-C8 alkyl chains, optionally having a hydroxyl group. These hydrophobic groups are attached to the main polymer chain, in particular via ether bonds.
  • the monomers comprising at least one secondary, tertiary or quaternary amine function, or a heterocyclic group containing a nitrogen atom, vinylamine, ethylene imine;
  • the polymers under the pH conditions of the mixture (and in particular of the emulsion) have cationic charges.
  • trimethylammonium ethyl (meth) acrylate chloride trimethylammonium ethyl acrylate methyl sulfate, benzyl dimethylammonium ethyl (meth) acrylate chloride, 4-benzoylbenzyl dimethyl ammonium ethyl acrylate chloride, trimethyl ammonium ethyl (meth) chloride acrylamido, trimethyl ammonium chloride, vinylbenzyl;
  • the counterion of these monomers can be chosen from halides, such as for example chlorides, carbonates, nitrates, sulfates, hydrosulfates, alkyl sulfates (for example comprising 1 to 6 carbon atoms), phosphates, citrates, formates, acetates.
  • halides such as for example chlorides, carbonates, nitrates, sulfates, hydrosulfates, alkyl sulfates (for example comprising 1 to 6 carbon atoms), phosphates, citrates, formates, acetates.
  • these synthetic cationic polymers comprise one or more anionic units under the conditions of preparation of the mixture (in particular of the emulsion), as soon as the net charge of the polymer is positive.
  • the anionic monomers can be chosen from those carrying at least one carboxylic, sulfonic, sulfuric, phosphonic, phosphoric, sulfosuccinic function, the corresponding salts. More particularly, said monomers can be chosen from:
  • vinyl sulfonic acid vinylbenzene sulfonic acid, vinyl phosphonic acid, vinylidene phosphoric acid, vinyl benzoic acid, as well as alkali metal salts, such as sodium, potassium, or ammonium ;
  • the salts are more particularly alkali metal or ammonium salts of NR4 + type with R, identical or different, representing a hydrogen atom, an alkyl radical comprising 1 to 4 carbon atoms, preferably 1 to 2 atoms carbon, whether or not substituted by an oxygen atom.
  • the polymers can likewise comprise one or more monomers which do not carry an ionic charge under the conditions of the mixture (in particular of the emulsion).
  • certain monomers listed in the context of cationic or anionic monomers may not have an ionic charge.
  • monomers which, whatever the pH conditions of the emulsion, do not carry an ionic charge.
  • monomers of this type the following are suitable: - ethylene oxide;
  • esters of (meth) acrylic acid with an alcohol comprising 1 to 12 carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) n-butyl acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl acrylate, hydroxyethyl (meth) acrylate;
  • N-alkyl (meth) acrylamide such as isopropyl acrylamide, N-methyloI (meth) acrylamide;
  • the cationic polymers used are copolymers comprising at least one cationic monomer and at least one anionic monomer, under the pH conditions of the mixture (in particular of the emulsion), it being understood that the net charge of said polymer is a cationic charge.
  • the polymers used may or may not have a statistical distribution of the monomers.
  • Such polymers can in particular be obtained by radical polymerization, controlled or not, conventionally for those skilled in the art.
  • the amount of cationic polymer is such that the molar ratio [number of cationic charges / number of hydroxyl and / or carboxylic functions of the compound] is between 1/1 and 1/100.
  • the redispersible granules of the present invention may also contain at least one additional ionic surfactant.
  • the additional ionic surfactants can more particularly be amphoteric surfactants, alkyl betaines, alkyldimethylbetaines, alkylamidopropylbetaines, alkylamido-propyldimethylbetaines, alkyltrimethylsulfobetaines, imidazoline derivatives such as alkylamphoacetates, alkylamphoacetates, alkylamphoacetates, alkylamphoethanes alkyl amphodipropionates, alkylsultaines or alkylamidopropyl-hydroxysultaines, condensation products of fatty acids and protein hydrolysates, amphoteric derivatives of alkylpolyamines such as Amphionic XL® sold by Rhodia, Ampholac 7T / X® and Ampholac 7C / X® marketed by Berol
  • the cation is generally an alkali or alkaline earth metal, such as sodium, potassium, lithium, magnesium, or an ammonium group NR4 "1" with R, identical or different, representing a hydrogen atom, a alkyl radical, comprising 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, substituted or not by an oxygen or nitrogen atom. It is possible to add to the redispersible granules according to the invention, any conventional additive according to the field of application of the latter such as anti-caking agents, wetting agents, disintegrant, etc.
  • the granules according to the invention are capable of being obtained by implementing the following steps: - a mixture is prepared from an aqueous solution comprising the compound, optionally the surfactant, and the material active;
  • this is a direct oil-in-water emulsion.
  • a solution of the (the) active material (s), optionally in a form dissolved in an appropriate solvent is prepared. Then the aqueous solution is added to the solution of hydrophobic active material (s), with stirring. In this case, a direct emulsion is then obtained.
  • the mixture and depending on the case the emulsion, is more particularly prepared at a temperature below 100 ° C. and preferably between 20 and 90 ° C. It should be noted that the temperature at which the mixture (or emulsion) is prepared is such that the various ingredients are in a liquid form. So, in the event that a hydrophobic active material is present, the temperature conditions lead to the production of an emulsion.
  • the average droplet size (dso) is generally between 0.1 and 10 micrometers and preferably between 0.2 and 5 micrometers (observation by light scattering).
  • the amount of dry matter in the mixture (and in particular in the emulsion) is generally between 10 and 80% by weight.
  • the respective contents of the various constituents in the mixture (or the emulsion) are chosen such that the dried granules have the composition defined above.
  • control agent is added, which is preferably in the form of an aqueous solution.
  • the third step of the preparation process according to the invention consists in drying the mixture (or the emulsion) thus formulated to obtain granules.
  • the method used to remove water from the mixture (or emulsion) and obtain granules can be carried out by any means known to those skilled in the art.
  • This operation takes place in such a way that the various constituent elements of the mixture are subjected to temperatures lower than those of their degradation.
  • the temperature at which the drying is carried out is less than or equal to 100 ° C., preferably between 50 and 90 ° C.
  • so-called rapid drying is carried out of the mixture (or of the emulsion).
  • spray drying in a fluidized bed using Duprat® drums or freeze-drying (freeze-sublimation) are suitable.
  • Drying by atomization or in a fluidized bed can be carried out in the usual manner in any known device such as for example an atomization tower associating a spraying carried out by a nozzle or a turbine with a stream of hot gas.
  • the inlet temperature of the hot gas (generally air) at the top of the column is preferably between 100 and 250 ° C. and the outlet temperature is preferably lower than the degradation temperature of the components of the granule obtained.
  • particles are obtained which can possibly be ground. If necessary, these particles can be subjected to a subsequent shaping, such as an agglomeration step, so as to obtain granules. It should be noted that additives, such as anti-caking agents can be incorporated into the granules at the time of this drying step.
  • a filler chosen in particular from calcium carbonate, barium sulphate, kaolin, silica, bentonite, titanium oxide, talc, hydrated alumina and calcium sulfoaluminate.
  • the granules according to the invention can be used in a large number of fields. In fact, they can be used as additives in formulations which can be used in the food, detergency, cosmetic, pharmaceutical industry, paints, paper, agrochemicals, metal working or deformation.
  • composition for 165 g of dry granulate, is as follows
  • the aqueous phase is first prepared by dissolving the polymer in water, and adding sodium hydroxide.
  • the rapeseed oil in which the surfactant is dissolved is then incorporated into the aqueous phase.
  • the whole is stirred at 1000 rpm for 10 minutes.
  • the crosslinking agent (Aquarhone) is added slowly with stirring.
  • the pH of the emulsion is around 7.
  • the emulsion obtained is dried in a thin film oven (12 hours, 75 ° C).
  • the film is then ground to obtain a powder which is sieved (size less than 400 ⁇ m).
  • Three samples are prepared which are brought into contact with an aqueous solution at variable pH and the dissolution of the powders is observed.

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EP02764981A 2001-07-12 2002-07-12 Granulate hergestellt durch trocknung einer mischung mit einem polymer und einem regulierungsmittel Withdrawn EP1404437A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0109391 2001-07-12
FR0109391A FR2827193B1 (fr) 2001-07-12 2001-07-12 Granules obtenus par sechage d'emulsion comprenant un polymere et un agent de controle
PCT/FR2002/002480 WO2003006148A1 (fr) 2001-07-12 2002-07-12 Granules obtenus par sechage d'un melange comprenant un polymere et un agent de controle

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DE602004013316T2 (de) 2003-06-25 2009-05-14 Rhodia Chimie Verfahren zur stimulierung einer ölbohrung durch verwendung verschiedener ablagerungsinhibitoren
FR2867395B1 (fr) * 2004-03-15 2006-06-16 Rhodia Chimie Sa Emulsion sechee, son procede de preparation, et ses utilisations
FR2878170B1 (fr) * 2004-11-22 2007-07-20 Rhodia Chimie Sa Emulsion sechee, son procede de preparation et ses utilisations

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US3886084A (en) * 1966-09-29 1975-05-27 Champion Int Corp Microencapsulation system
FR2740357B1 (fr) * 1995-10-25 1997-11-28 Rhone Poulenc Chimie Granules redispersables dans l'eau comprenant une matiere active sous forme liquide et un tensio-actif non ionique du type alcoxyles
EP1059339B1 (de) * 1998-02-24 2004-10-13 Matsumoto Yushi-Seiyaku Co., Ltd. Wärmeausdehnbare mikrokapseln, verfahren zur herstellung und verwendung derselben
FR2785198B1 (fr) * 1998-10-30 2002-02-22 Rhodia Chimie Sa Granules redispersables dans l'eau comprenant une matiere active sous forme liquide
EP1002569A3 (de) * 1998-11-19 2000-09-06 Beiersdorf Aktiengesellschaft Zubereitungen vom Emulsionstyp W/O mit erhöhtem Wassergehalt enthaltend kationische Polymere

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FR2827193A1 (fr) 2003-01-17
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US20040213854A1 (en) 2004-10-28

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