Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D19/00—Degasification of liquids
  • B01D19/02—Foam dispersion or prevention
  • B01D19/04—Foam dispersion or prevention by addition of chemical substances
  • B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
  • B01D19/0409—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing Si-atoms
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
  • A01N25/12—Powders or granules
  • A01N25/14—Powders or granules wettable
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D19/00—Degasification of liquids
  • B01D19/02—Foam dispersion or prevention
  • B01D19/04—Foam dispersion or prevention by addition of chemical substances
  • B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance

Definitions

• the subject of the present invention is a composition comprising a silicone substance having defoaming properties in an aqueous medium, as well as phytosanitary formulations, solid or liquid, comprising it.
• Phytosanitary formulations in addition to active ingredients and fillers, contain surfactants, which, among other things, have the role of improving the wetting and dispersion of the formulations during their use.
• surfactants are the cause of difficulties associated with the production of foam; difficulties not only in the preparation of these formulations, but i auss, and especially when using them.
• French patent FR 2 306 635 proposes adding to the phytosanitary formulation in powder form, an anti-foaming agent comprising a support on which a silicone is deposited.
• the support which is inert vis-à-vis the active substance, can be either for example chosen mineral powder from talc, kaolin, diatomaceous earth, sil i this, or else an organic compound, such as starch.
• the phytosanitary formulation is obtained in several stages. The first consists in mixing, in general by grinding, the constituent elements such as the active material, the fillers, the various wetting, dispersing surfactants. Then, in a second step, the agent ant i - supra foam is mixed with the formulation obtained above.
• this solution is more suitable than the first, it don 'remains that it is only partial, and this all the more that the phytosanitary formulation desired requires an intermediate step of grinding, wet or dry. Indeed, the introduction of this anti-foaming agent after the preparation of the formulation requires the installation of an additional mixing apparatus. Or it is not possible to introduce the antifoam at the stage of preparation of the agent is formulat i phytosanitary proper. In fact, during the aforementioned grinding step, the antifoaming agent is destroyed, which causes a release of the silicone. The effectiveness of controlling the formation of foam will therefore be reduced in all cases, or even nonexistent if the preparation of the formulation requires the addition of water, as is the case in particular of preparations using a wet grinding, or granulation.
• an anti-foaming composition based on a silicone and a matrix, firstly comprising at least one porous support, and secondly, a combination of an amphiphilic polymer and an anionic surfactant.
• composition according to the invention can be introduced into the phytosanitary formulation as soon as it is prepared without losing its effectiveness, even when the preparation requires grinding of the constituent elements, and / or their placing in form by granulation.
• a first subject of the invention consists of a composition comprising: - at least one silicone substance having defoaming properties in aqueous systems,
• At least one matrix comprising: • at least one porous support, a combination of at least one copolymer having carboxyl groups and at least one alkylaryl sulphonate or an alkylaryl sulphate of alkali metal, alkaline earth metal or ammonium.
• Another object of the present invention is constituted by a process for the preparation of such a composition, consisting in bringing the silicone substance into contact with the matrix, then optionally drying the whole.
• Another object of the present invention consists of a phytosanitary formulation comprising, in addition to one or more phytosanitary active ingredients, and conventional additives, the composition according to the invention, as an additive having defoaming properties in aqueous systems.
• a final object of the present invention consists of a process for the preparation of such phytosanitary formulations, in which the following steps are implemented:
• composition according to the invention comprises:
• At least one matrix comprising: • at least one porous support, a combination of at least one copolymer having carboxyl groups and at least one alkylaryl sulfonate or an alkylaryl sulfate of alkali, alkaline-earth metal or ammonium.
• the silicone substance (or silicone) is more particularly chosen from polyorganosiloxanes in which at least 50% of the organic substituents are methyl radicals.
• the other radicals of the silicone substance may be hydrogen atoms, hydroxyls, linear or branched C1-C10 alkyl radicals, linear or branched, C-2-C10 alkenyl radicals, aryl or alkylaryl radicals in C5-C10.
• silicone substances used correspond to the following formula:
• radicals R1 identical or different, substituted or not, represent a linear alkyl or branched, C1-C10; a C2-C10 linear or branched alkenyl radical; an aryl, alkyl-aryl, aryl-alkyl, aryl-alkenyl, alkenyl-aryl radical, C5-C10 for the aryl part and C1-C4 for the alkyl or alkenyl part, or a hydroxyl;
• radicals R2, R3, R4_ substituted or not, identical or different, represent linear or branched C1-C10 alkyl; a C2-C10 linear or branched alkenyl radical; an aryl, alkyl-aryl, aryl-alkyl, aryl-alkenyl, alkenyl-aryl radical, C5-C10 for the aryl part and C1-C4 for the alkyl or alkenyl part;
• R1 identical or different, represent methyl, ethyl, vinyl, phenyl, hydroxyl radicals.
• the preferred radicals R 1 are methyl radicals.
• R 2, R 3, R4_ ⁇ are methyl, ethyl, vinyl, phenyl are preferred, bearing in mind that according to a particular embodiment, at least 80% of said radicals are methyl.
• the silicone substance used can be in the form of an oil, an emulsion, or even a compound.
• the continuous medium can be chosen from water or any other compound which does not or substantially does not dissolve the silicone.
• compound is a conventional term in the field of silicones, and which designates a silicone substance associated with at least one mineral filler.
• the compounds more particularly have a viscosity of between 30 and 60,000 mPa.s, using one or more silicone oils.
• the mineral fillers used to obtain the compounds have a specific surface, measured according to BET methods, of at least 50 m 2 / g, in particular between 50 and 400 m 2 / g, preferably greater at 70 n 7g.
• They also have an average particle size of less than 0.1 ⁇ m and an apparent density of less than 200 g / l.
• the mineral filler is chosen from silica, ground quartz, calcined clays, or even diatomaceous earth, alone or in mixtures.
• the mineral filler associated with the silicone substance is silica.
• hydrophobing treatment it may possibly have undergone a surface treatment aimed at hydrophobing it. It should be noted that this treatment can be carried out beforehand or in situ. Preferably, when it is precipitated silica, the hydrophobation treatment is carried out.
• the hydrophobation treatment consists in contacting the silica with one or more organosilicon compounds.
• organosilicon compounds such as hexamethyldisiloxane, octamethylcyclotetrasiloxane; methylpolysilazanes such as hexamethyldisilazane, hexamethylcyclotrisilazane; chlorosilanes such as dimethyldichlorosilane, trimethylchlorosilane, methylvinyldichlorosilane, dimethylvinylchlorosilane; alkoxysilanes such as dimethylmethoxysilane.
• the silicas can increase their starting weight up to a rate of 20%.
• the proportion of silicone oil with respect to the mineral filler, and more particularly with respect to silica varies between 2 and 15 and preferably between 2 and 10.
• the compounds are prepared in the usual manner by mixing the two components, then heating the mixture obtained between 60 and 200 ° C, in particular around 150 ° C, preferably under reduced pressure.
• the silica undergoes a heat treatment at a temperature above 100 - 150 ° C., in the absence of the aforementioned silicic compounds.
• silicone compounds in the form of an oil, an emulsion or a compound, commercially available and capable of entering into the composition according to the invention, there may be mentioned for example, Rhodorsil® oil 47V1000, Rhodorsil ® 432 (30% silicone emulsion), Rhodorsil® 471, Rhodorsil® 471 LV compounds,
• composition according to the invention may comprise one or more silicone substances, as such or combined with one or more mineral fillers.
• the matrix will now be described.
• the first constituent of the latter is a porous support. All porous compounds, substantially inert towards the substance, may be suitable for the invention. By substantially inert is meant that the support, to a large extent, does not react with the silicone substance to reduce its anti-foaming and / or defoaming properties.
• said support depending on its final form, can be soluble or insoluble in water.
• porous support there may be mentioned without intending to be limited, silica, silico-aluminates, bentonite, zeolites, gypsum, calcium citrate, calcium carbonate.
• the porous support is chosen from silico-aluminates or silica.
• compounds are used in precipitated form.
• the composition comprises, as the support, silica, and advantageously, precipitated silica.
• the matrix forming part of the composition according to the invention further comprises a combination of at least one copolymer comprising carboxyl groups and at least one alkylaryl sulfonate or an alkylaryl sulfate.
• the copolymer carrying carboxyl groups is obtained by polymerization, preferably radical, of at least one monomer, monocarboxylic or polycarboxylic acid, or anhydride, linear, branched, cyclic or aromatic, and ethylenically unsaturated; and at least one aliphatic hydrocarbon monomer, linear or branched, and carrying at least one ethylenic unsaturation.
• hydrocarbon monomer corresponds to the following formula:
• R2 radicals identical or different, represent a hydrocarbon radical, linear or branched, preferably saturated, with C * ⁇ - C30.
• monomers capable of being used there may be mentioned, inter alia, ethylene, propylene, 1 -butene, isobutylene, 1 -n pentene, 2-methyl-butene, 1 - n hexene, 2-methyl 1 -pentene, 4-methyl 1 -pentene, 2-ethyl 1-butene, diisobutylene (or 2,4,4-trimethyl 1 -pentene), 2-methyl 3,3 -dimethyl 1- pentene.
• Said polymer can also be in acid form, in the form of an ester or in the form of an alkali metal, alkaline earth metal or ammonium salt, these forms possibly being present alone or in combination.
• ammonium is meant a radical of the type -NR3Z in which R, identical or different, represent hydrogen or a C1-C4 alkyl radical.
• the matrix comprises, in the abovementioned combination, at least one maleic anhydride / diisobutylene copolymer, in acid form, or in the form of an alkali metal, alkaline earth metal or ammonium salt, these forms possibly being present alone or combined.
• the copolymer is in the form of an alkali, alkaline earth metal or ammonium salt.
• it is in the form of a sodium salt.
• the matrix of the composition according to the invention more particularly has a weight ratio of the support, and preferably of silica or of silico-aluminate, to the copolymer, of between 2/1 and 4/1.
• the combination present in the matrix comprises, at least one alkylaryl sulphate or an alkylaryl sulphonate.
• the aforementioned combination comprises at least one alkylaryl sulfonate or an alkylaryl sulfate having a counterion chosen from alkali metals, alkaline earth metals or the groups -NR3 + in which R, identical or different, represent a linear or branched or cyclic alkyl or hydroxyalkyl radical comprising 1 to 10 carbon atoms.
• R identical or different, represent a linear or branched or cyclic alkyl or hydroxyalkyl radical comprising 1 to 10 carbon atoms.
• alkylbenzene sulfonates the alkyl part of which, linear or branched, comprises 8 to 15 carbon atoms. It should be noted that one could consider using alkylnaphthalene sulfonates comprising 1 to 3 linear or branched alkyl radicals, having 1 to 4 carbon atoms.
• dodecylbenzene sulfonate and preferably, sodium dodecylbenzene sulfonate.
• alkylaryl sulphates can comprise 1 to 80 oxyalkylenated units (oxyethylenated and or oxypropylenated).
• the sulfates of di- or tri-styrylphenol optionally oxyethylenated (3 to 40 units).
• the particularly advantageous combination used in the composition of the matrix is based on a maleic anhydride / diisobutylene copolymer, in the form of a sodium salt and sodium dodecylbenzene sulfonate (90/10 ratio).
• This compound is sold in particular under the name Geropon® TA / 72 (product of Rhodia Chimie).
• the matrix of the composition according to the invention has a weight ratio of the copolymer to the alkylaryl sulfonate and or to the alkylaryl sulfate, of between 1.5 / 1 and 10/1.
• the combination of the copolymer and the alkylaryl sulphate and / or alkylaryl sulphonate is obtained by jointly drying these two types of compounds, preferably by atomization.
• the composition according to the present invention has a weight ratio of the silicone substance to the matrix as just described, between 5/95 and 80/20. Preferably, said weight ratio is between 30/70 and 80/20.
• the composition according to the invention can also comprise at least one partially or completely water-soluble compound.
• solid anti-foaming composition according to the invention when added to a phytosanitary formulation not requiring wet grinding in the presence of water, said compound can, at least in part, constitute the porous support of the matrix .
• saccharides such as glucose, fructose, galactose, arabinose, mannose, dextrose, saccharose, lactose or their mixtures. According to a preferred variant, at least one saccharide having a melting point above 100 ° C. is used.
• a particularly interesting saccharide is lactose, in particular D-lactose monohydrate (form).
• alkali metal, alkaline earth metal or ammonium phosphates such as tripolyphosphates, dihydrogenophosphates, alkali metal, alkaline earth metal or ammonium sulfates.
• ammonium is meant the radical -NR3 + in which R, identical or not, represent a hydrogen atom or a C1-C4 alkyl radical, such as methyl, ethyl, propyl and its isomers , butyl and its isomers.
• the partially or completely water-soluble compound is present at a content such that the weight ratio of the support, and preferably of silica or of silico-aluminate, said compound is between 1, 5/1 and 6/1 .
• composition according to the invention is obtained by bringing the silicone substance into contact with the matrix, then optionally drying the whole.
• the silicone substance or substances are added to the matrix.
• This contacting can be done by any means, such as in particular spraying by means of a nozzle.
• the operation takes place with stirring so as to homogenize the mixture. Conventionally, it is carried out in a L ⁇ dige type mixer.
• the assembly can be dried if necessary.
• drying takes place in air.
• the temperature is advantageously between 20 and 50 ° C. More particularly, and as an indication, the drying time is between a few minutes and 3 hours.
• composition of the invention is more particularly in the form of a powder.
• the composition is in the form of a granule.
• a step of granulating the matrix and silicone substance (s) assembly is carried out, once the contacting has been carried out.
• the granulation operation can be done during contacting, if the silicone substance is used in a form comprising water (emulsion for example). If this is not the case, then once the contacting has been carried out, and preferably after homogenization of the matrix / silicone assembly, the required quantity of water is added to effect the granulation of the mixture.
• water emulsion for example
• the amount of water represents 10 to 40% by weight relative to the weight of the silicone / matrix assembly.
• the resulting granule can be dried. What has been said on this subject remains valid and will therefore not be repeated now.
• composition according to the invention is advantageously used as an agent having defoaming properties in aqueous systems.
• composition according to the invention can be suitably used as an additive in phytosanitary formulations.
• composition according to the invention can be used in many types of phytosanitary formulations, whether these are in the form of powder or granules, but also in the form of suspensions.
• the present invention therefore relates to phytosanitary formulations comprising, in addition to one or more phytosanitary active ingredients, and conventional additives, the composition which has just been described in detail, as an additive having defoaming properties in aqueous systems.
• composition according to the invention represents between 0.1 and 10% by weight, relative to the total weight of the formulation.
• composition represents 0.1 and 5% by weight relative to the same reference.
• phytosanitary formulation any formulation intended for applications in the field of agriculture, comprising at least one biologically active material, such as pesticides in particular.
• pesticides such as herbicides, fungicides, acaricides, insecticides, nematicides.
• Suitable active ingredients include, among others, Amethryne, Diuron, Linuron, Chlortoluron, Isoproturon, Nicosulfuron, Metamitron, Primsulfuron-methyl, Metsulfuron-ethyl, Glyphosate , the Aclonifen, Atrazine, Chlorothalonil, cymoxanil, Glufosinate, Mancozeb, Zineb, Phenmedipham, phenoxy family, CMPP, MCPA, 2,4-D, Simazine, Bromoxynil, active products of the series of imidazolinones such as Imazapyr, Imazaquine, Imazethapyr, Imazamethabenz.
• the content of active ingredient in the formulation depends on the form in which the formulation is found, in the form of a solid or a suspension.
• the amount of active material is generally of the order of 10 to 90% by weight relative to the total weight of the formulation.
• the amount of active material is generally between 10 and 70% by weight relative to the total weight of the formulation.
• the phytosanitary formulations in addition to the active ingredient (s) and the composition according to the invention, comprise at least one wetting agent.
• N-methyl-N-oleoyl taurates alkyl diphenyl ether sulfonate salts, alkylnaphthalene sulfonates, mono-alkyl sulfosuccinates, di-alkyl sulfosuccinates.
• alkyl diphenyl ether sulfonate salts alkylnaphthalene sulfonates
• mono-alkyl sulfosuccinates di-alkyl sulfosuccinates.
• wetting surfactants examples include Geropon® SDS, Geropon® T / 77, Supragil® NC / 85, Rhodacal® DS / 10, Supragil® WP, sold by the company Rhône- Poulenc Chemistry.
• the amount of wetting agent may be between 0.5 and 10% by weight, relative to the total weight of the formulation, preferably between 1 and 5% by weight, relative to the same reference.
• the phytosanitary formulations according to the present invention can also comprise at least one dispersing agent.
• the alkali metal or ammonium salts of polycarboxylates such as polyacrylates
• alkali metal or ammonium salts of alkylnaphthalene sulfonates condensed with formalin the alkali metal or ammonium salts of 4,4'-dihydroxybiphenylsulfonate condensed with formalin
• alkali or ammonium salts of alkylarylphosphates or of alkylarylsulphates such as phosphated or sulphated mono-, di- or tri-styrylphenols, neutralized or not
• alkali metal or ammonium salts of lignosulfonates and mixtures thereof.
• the dispersing agents can be chosen from the following products: Geropon® T / 36, Geropon® TA / 72, Geropon® SC / 213, Supragil® MNS / 90, Supragil® GN, Soprophor® FL, Soprophor® FLK, Soprophor® 4D384. O 99/21635
• the amount of dispersing agent of the formulation is generally between 2 and 20% by weight, relative to the total weight of the formulation, preferably between 2 and 15% by weight, relative to the same reference. It is advantageously between 2 and 10% by weight, relative to the total weight of the formulation.
• the formulations according to the present invention can also comprise at least one charge which is inert with respect to the other constituents of the formulation and more particularly to the active material.
• the inert filler can be, indifferently soluble or insoluble in water, depending on whether the phytosanitary formulation in which it is incorporated requires or does not require the use of wet grinding.
• inert filler capable of entering into the composition of the phytosanitary formulations according to the invention, mention may be made, without being limited thereto, of soluble or partially soluble starch, bentonite, kaolin, diatomaceous earths, attapulgite, zeolites, calcium carbonate, talc, mica, silica, silico-aluminates, sulfates of alkali metal, alkaline earth metal or ammonium.
• the formulations according to the invention can comprise between 1 and 15% by weight of inert filler relative to the total weight of the formulation.
• Step (c) optionally shaping the resulting mixture.
• Step (a) is implemented conventionally in the field.
• the various constituent elements are mixed in an appropriate apparatus.
• Step (b) can be carried out in the presence or absence of a solvent.
• the procedure is carried out in the absence of solvent (dry grinding), it is conventionally carried out in an apparatus of the air jet mill type or even hammer mill.
• dry grinding is understood a grinding of individual particles, which can however contain a certain level of humidity. Conventionally, this moisture content is between 0 and 5% by weight relative to the total weight of the formulation.
• the operation is generally carried out in air.
• the duration is such that a homogeneous product is obtained which has the particle size between 1 and 100 ⁇ m.
• the solvent is advantageously water.
• other products could be used such as, for example, vegetable oils, mineral oils, fatty acid esters.
• the solvent content is such that a slurry is subjected to grinding.
• the amount of solvent is between 20 and 70% by weight relative to the total weight of the formulation.
• the operation is generally carried out in air.
• the duration is such that a homogeneous product is obtained which has the particle size between 1 and 15 ⁇ m.
• the resulting product can optionally be shaped.
• the final product corresponds to the product obtained after the grinding step (b).
• the product is then in the form of a powder and can be used as it is, conventionally in the field.
• the granulation operation is classic in the field. It is used by adding a solvent in an amount usually between 5 and 50% by weight relative to the weight of the product obtained at the end of the grinding step, preferably 5 to 20% by weight relative to the same reference.
• the granulation operation can be carried out in any suitable granulation device well known to those skilled in the art. However, it is preferred to use a Lôdige type granulator during this step. We can then proceed to an additional shaping step, such as extrusion for example.
• drying of the resulting product is preferably carried out.
• the drying is advantageously carried out in air.
• the operation can be carried out in a fixed, fluidized or transported bed.
• the temperature is chosen according to several criteria such as the stability of the active material, that of the anti-foaming composition according to the invention, or even the nature of the solvent used during the granulation. Conventionally, this temperature varies from 20 to 80 ° C.
• the drying time is such that a moisture content of between 0 and 3% is obtained.
• a formulation is obtained in the form of granules, optionally extruded.
• the first variant consists in using the product in the form of the suspension obtained at the end of the grinding step.
• the second variant in the case where the grinding was carried out in the presence of solvent, consists in drying the resulting suspension.
• Drying takes place using conventional means. However, preferably, said drying takes place by atomization, that is to say by spraying the suspension in a hot atmosphere (spray-drying).
• the atomization can be carried out by means of any sprayer known per se, for example by a spray nozzle of the sprinkler apple type or the like.
• spraying techniques likely to be used in the present process, reference may be made in particular to the basic work by MASTERS entitled "SPRAY-DRYING" (second edition, 1976, Editions George Godwin - London).
• the drying temperature is lower than the degradation temperature of the active material, however, for example, the drying temperature is between 90 and 300 ° C.
• a phytosanitary formulation is then obtained in the form of a powder.
• the formulation according to the invention whatever its formatting, has the advantage of being easily dispersible when it is mixed with water before its application, and of not causing excessive foaming during mixing with the water.
• This example relates to the preparation of the composition according to the invention.
• a mixture of powders is prepared comprising:
• the mixture obtained is then brought into contact with a Rhodorsil® 454 silicone defoamer, in weight proportions of 50/50.
• the mixing operation is carried out in a L ⁇ dige device.
• This example relates to the preparation of a phytosanitary composition based on Atrazine, comprising the composition obtained according to Example 1.
• composition prepared is as follows:
• Igepal ethoxylated nonylphenol (10 EO)
• the resulting granules are finally dried in a fluidized bed (60 ° C).
• the foam height of the composition is then measured, from its preparation and after a 15-day treatment at 54 ° C., according to the following test:
• phytosanitary formulation comprising the composition according to the invention has retained low foaming properties.
• EXAMPLE 3 The subject of this example is the preparation of a phytosanitary composition based on Amethryne, comprising the composition obtained according to Example 1.
• composition example 1 1%
• the formulation is obtained using the same method as that used to obtain the formulation according to Example 2.
• the foam height of the composition is then measured, from its preparation and after a treatment of 1 month at 54 ° C., according to the test described in Example 2. The results are collated in the table below:

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Toxicology (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Health & Medical Sciences (AREA)
• Dispersion Chemistry (AREA)
• Pest Control & Pesticides (AREA)
• Dentistry (AREA)
• Wood Science & Technology (AREA)
• Zoology (AREA)
• Environmental Sciences (AREA)
• Engineering & Computer Science (AREA)
• Plant Pathology (AREA)
• Agronomy & Crop Science (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)

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• 1997
  • 1997-10-28 FR FR9713520A patent/FR2770148B1/fr not_active Expired - Fee Related
• 1998
  • 1998-10-28 EP EP98952809A patent/EP1027126A1/de not_active Withdrawn
  • 1998-10-28 WO PCT/FR1998/002312 patent/WO1999021635A1/fr not_active Application Discontinuation
  • 1998-10-28 AU AU10372/99A patent/AU1037299A/en not_active Abandoned
• 2001
  • 2001-11-08 US US10/007,996 patent/US20020049279A1/en not_active Abandoned

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