CN100469245C - Agrochemical suspension formulations - Google Patents
Agrochemical suspension formulations Download PDFInfo
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- CN100469245C CN100469245C CNB018101747A CN01810174A CN100469245C CN 100469245 C CN100469245 C CN 100469245C CN B018101747 A CNB018101747 A CN B018101747A CN 01810174 A CN01810174 A CN 01810174A CN 100469245 C CN100469245 C CN 100469245C
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- methyl
- styrene
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- suspension concentrate
- dispersant
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/30—Derivatives containing the group >N—CO—N aryl or >N—CS—N—aryl
-
- 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
- A01N25/02—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 containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- 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
- A01N25/30—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 characterised by the surfactants
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
- A01N43/68—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms with two or three nitrogen atoms directly attached to ring carbon atoms
- A01N43/70—Diamino—1,3,5—triazines with only one oxygen, sulfur or halogen atom or only one cyano, thiocyano (—SCN), cyanato (—OCN) or azido (—N3) group directly attached to a ring carbon atom
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/20—N-Aryl derivatives thereof
-
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
-
- 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
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
- A01N59/20—Copper
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Agrochemical suspension concentrates, particularly in aqueous or liquid oil based medium, comprise solid particles including one or more agrochemical active components; and a dispersing agent including a water soluble or dispersible styrene (meth)acrylic acid copolymer. In particular the styrene (meth)acrylic acid copolymer has a molar ratio of residues of (meth)acrylic acid monomer(s) to styrene monomer(s) from 20:1 to 1:5, particularly from 3:1 to 1:1. The formulation will usually also contain wetting agents; and/or adjuvants. The agrochemical active can be plant growth regulators, herbicides, and/or pesticides, for example insecticides, fungicides, acaricides, nematocides, miticides, rodenticides, bactericides, molluscicides and bird repellants. The suspension formulations will typically be used diluted in water and sprayed onto plants or the soil surrounding the plants.
Description
The present invention system is about the farming composite, and particularly about the solid suspension type of this composite, this solid suspension comprises the farming active matter that is contained in liquid medium, and the present invention is meant can be dispersed in the water to obtain the suspension-concentrates of agrochemical suspension especially; And about with this agrochemical suspension (especially the suspension of dilution outstanding contract thing composite) methods for the treatment of plants.
The farmingization composite is normally used with spray pattern, and it is normally based on the spraying composite of water.Wherein a kind of composite form is the suspension of solid particle, comprises the farming active matter (the normally insoluble active matter of water) that is contained in liquid medium, and at the beginning through being allocated as concentrate (suspension-concentrates), it is spray through dilution before using usually.Following dispersant, as naphthalene sulfonic acid-formaldehyde condensation product, ligninsulfonate, copolymer-maleic anhydride and through the salt of the phenol sulfonic acid of condensation, and nonionic dispersant such as EO/PO section connect copolymer and include usually in agrochemical suspension and suspension-concentrates, part being dispersed in the medium auxiliary activity is formed, it particularly can improve the dispersiveness of solid farmingization thing in the spraying composite of this suspension and dilution in concentrate.
The general system of the present invention is about the farming thing of water-dilutable suspension-type, especially suspension-concentrates, it comprises with styrene (methyl) acrylic copolymer as dispersant mixing in the farming thing that is used in suspension-concentrates and with water, even and particularly after with this suspension-concentrates long term storage (wearing out) good dispersiveness and suspension characteristics still can be provided.
In view of the above, the present invention can provide the farmingization composite, and it can dilute through water, is to comprise the active suspension-type of forming the solid particle of parts of one or more tool farmingizations, and it is particularly with waterborne liquid or based on the medium of liquid oil; And the dispersant that comprises water soluble or dispersible styrene (methyl) acrylic copolymer.
The included farming composite of the present invention more comprises:
1. one or more wetting agents; And/or
2. one or more adjuvants;
The present invention includes the method for preparing the spray mixture, agrochemical suspension concentrate composite wherein of the present invention is to be dispersed in the water.The present invention more comprises methods for the treatment of plants, wherein is this plant or the soil that surrounds this plant to be sprayed agrochemical suspension concentrate of the present invention mix prepared spray mixture with water.Before the present invention's farming composite and farmingization composite used in the present invention particularly adopt and use through water dilution can dilute the concentrate type, it generally dilutes suspension (dispersion liquid) to generate the farmingization thing through water, and the present invention particularly including:
A agrochemical suspension concentrate wherein is dispersed at least a farmingization thing in the water carrier fluid, and it more comprises the dispersant that contains the dispersible benzene second of water rare (methyl) acrylic copolymer, reaches the preferable at least a adjuvant surfactant that more comprises;
B agrochemical suspension concentrate wherein is dispersed at least a farmingization thing in the non-aqueous carrier fluid, and it more comprises the dispersant that contains the dispersible styrene of water (methyl) acrylic copolymer, reaches the preferable at least a adjuvant surfactant that more comprises;
C agrochemical suspension concentrate comprises the microcapsule-type farmingization thing that is suspended in carrier fluid, and it comprises the dispersant that contains the dispersible styrene of water (methyl) acrylic copolymer, reaches the preferable at least a adjuvant surfactant that more comprises;
D farmingization suspension emulsion concentrate (in this skill, being called " suspension emulsion " usually for short), comprise the farmingization thing that is contained in the water for use, solid particle system comprising at least a farmingization thing is dispersed in the carrier fluid, it comprises the dispersant of the dispersible styrene of at least a water (methyl) acrylic copolymer, it more comprises the solution or the dispersion liquid of at least a emulsifier and at least a dispersant surfactants, and preferablely comprises at least a adjuvant surfactant;
Use can disperse styrene (methyl) acrylic copolymer for simplicity at water of the present invention, sometimes in the following polymeric dispersant that is called as.This polymeric dispersant is styrene (methyl) acrylic copolymer.Heavily cover the residue that unit is considered to the set of monomers composition usually in the copolymer.
(methyl) acrylic monomers can be acrylic acid, methacrylic acid, butenoic acid and aforementioned two or more mixture.This (methyl) acrylic monomers can be or include (methyl) acrylic monomers that it is for including it (methyl) acrylic acid derivative of strong acid (particularly sulfuric acid or sulfonic acid group or its salt).The example of this monomer comprises acrylamide group methyl propyl sulfonic acid salt (AMPS) and (methyl) acrylic acid isethionate.When being current with the monomer of modifying through strong acid, the acrylic monomers in copolymer is generally 1 to 30 mole of %, and more normal is 2 to 20 moles of %, and is preferably 5 to 15 moles of %.
The styrene that this styrene monomer can be and be preferably styrene itself or be substituted, the styrene that replaces through alkyl (being preferably alkyl) particularly, wherein this substituting group is on the cinnamic vinyl or on the aromatic ring, for example, and AMS and vinyltoluene.When having (methyl) acrylic monomers, this styrene monomer can be or comprise the styrene monomer that contains strong acid (especially sulfonic acid substituting group).When be current with the monomer through the strong acid modification, the styrene monomer in copolymer has 1 to 30 mole of % usually, and more normal have 2 to 20 moles of %, and preferable 5 to 15 moles of % is arranged.
In the dispersible styrene of water used in the present invention (methyl) acrylic copolymer, (methyl) acrylic monomers residue is to the mol ratio of styrene monomer residue 20:1 to 1:5 normally, and more normal is 10:1 to 1:2 and particularly 3:1 to 1:1.Therefore, the weight ratio ratio of monomer residue normally, (methyl) acrylic monomers is 93 to 10%, more normal is 87 to 25%, particularly 67 to 40%, and styrene monomer is 7 to 90%, more normal is 13 to 75%, particularly 33 to 60%.
Monomer in other can be included in comprises as acid monomer routine methylene-succinic acid or maleic acid or acid anhydrides; Strong acid monomer is as methallylsulfonic acid (or its salt); Or nonacid acrylic monomers, as acrylate, it can be Arrcostab (C particularly
1To C
6Arrcostab such as methyl methacrylate, butyl methacrylate or butyl acrylate) or hydroxyalkyl acrylate (C particularly
1To C
6Hydroxyalkyl acrylate, as methacrylic acid hydroxyl ethyl ester, or methacrylic acid hydroxyl propyl ester); Or vinyl monomer, as vinyl acetate.In general, the ratio of these other monomers will not be higher than the about 25 moles of % of the total monomer that uses, be not higher than about 15 moles of % usually, more normal is not to be higher than about 5 moles of %.In general, the weight ratio of these other monomers is not to be higher than approximately 30%, is not higher than approximately 20% usually, and more normal is not to be higher than about 10%.
Polymeric dispersant can be single styrene acrylic copolymer or comprises the admixture of two or more these copolymers.Especially when containing the strong acid residue in polymeric dispersant, this dispersant can be the admixture that includes strong acid residue copolymer and do not include this residue copolymer.In this admixture, general preferable be that the weight ratio of this copolymer is by 1:10 to 10:1, more normal is by 5:1 to 1:5.Especially the ratio that includes the copolymer of strong acid residue is preferably and accounts for 25% of polymeric dispersant weight ratio at least, and more normal is to account at least 40%.
When including the strong acid residue in the polymeric dispersant, the overall ratio that includes the monomer residue of strong acid group is preferably by 0.25 to 25 moles of % more often are by 0.5 to 20 mole of % and are preferably by 1 to 10 mole of %.
When diluting with hard water, comprising the monomer with strong acid substituted radical in polymeric dispersant can provide the solid that gives the farmingization composite to form a part preferable dispersiveness, especially be higher than 500ppm when hardness of water, for example up to 1000ppm, up to 2000ppm or even during up to 5000ppm.
Preferable is that the molecular weight of this polymeric dispersant is by 750 to 50000, and more normal is not to be higher than approximately 20000, and better is by 1000 to 10000 and particularly by 1500 to 5000.This polymeric dispersant can free acid or the mode of salt use.In fact, the form that presents in the composite will be determined by the acidity of composite.Be preferably this composite near neutral, thereby most acid groups will exist in the mode of salt.Cation in any this salt can be alkali metal (particularly sodium and/or potassium), ammonium or amine (comprising alkanolamine such as monoethanolamine, particularly three-monoethanolamine).Use is preferably not contain can interferon activity to form at polymeric dispersant of the present invention and divides or cause that particle is stained with sticking solvent.Better be this polymeric dispersant be heat endurance and do not generate colloid.
This polymeric dispersant can utilize through the initial polymerisation of free radical and prepare, for example utilize peroxide or oxidoreduction initiator, particularly with the polymerisation in solution compositing monomer, it also can utilize chain-transferring agent according to circumstances, as alkanethiol, this chain-transferring agent can be used to control the molecular weight of polymer.Suitable method is for example being described among the EP0697422A.
Be the auxiliary active dispersion of forming part in this spray composite after the water dilution, the surface that is preferably the soluble material of any water (comprising activity farmingization thing) that exists in this polymeric dispersant and the composite is compatible, and more normal be strong interaction.The insoluble farmingization active matter of water can utilize the powder mode, absorbs/be adsorbed on the solid support, or when particularly being used in the liquid active matter, then available microcapsule-type.When preferably using the microcapsules active matter, polymeric dispersant is preferable also can be compatible with the material that is commonly used in this microcapsule shell wall, routine polyureas, polyurethane, polyester, Merlon, polysulfonamide and comprise the polyamide of protein (as gelatin).
The dispersant of use in composite of the present invention can be that styrene (methyl) acrylic copolymer or its can comprise other dispersant material fully, traditional as the aforementioned dispersant, routine naphthalenesulfonate formaldehyde condensation compound, ligninsulfonate, copolymer-maleic anhydride and through the phenol sulfonic acid and the salt thereof of condensation.When using in said composition, the weight ratio of styrene (methyl) acrylic copolymer and this tradition dispersant is 1:5 usually at least, and more normal be by 1:4 to 10:1, particularly by 1:2 to 5:1.
Other traditional dispersant and disperse additive, as polyvinyl pyrrolidone (PVP), polyvinyl alcohol (PVOH, phosphate (as phosphate) based on three hard ester group phenol (tristeryl phenol), routine Soprofor FL, carboxyl methoxyl group cellulose (CMC), starch, alginates, gum Arabic, sorbierite, and sucrose (as described above) can be included.When using this tradition material, it normally forms part as the trace of dispersant, and example accounts for 1 to 20 weight % of total points powder.
This farming active matter can be one or more dispersible farmingization active matters of water widely.This active matter is described as water is dispersible to be meant it and can be dispersed in the water and (can use dispersant if necessary), and it comprises the water dispersible active farmingization thing of solid forms, himself can be not dispersed in the water, example is absorbed in the holder or is adsorbed on the farming thing on the holder or is (little) capsule-type liquid or solution.Particularly this active matter can be one or more plant growth regulators, weed killer herbicide, and/or insecticide, for example insecticide, fungicide, arachnicide, nematocide, miticide, rodenticide, bactericide, invertebrate poison and bird expellent.Usually this active matter is insoluble or not mixed with the water material of water.The special example of active matter comprises:
Weed killer herbicide: comprise triazine (triazine), as Aunar cloud (Atrazine) { 6-chloro-N-ethyl-N '-(1-Methylethyl)-1,3,5-triazine-2, the 4-diamines, and special cloud (the Prometryn) { N of Baume, N '-two (1-Methylethyl)-6-(methyl sulfenyl)-1,3, the 5-triazine }-2,4-diamines }, be substituted urea, as Dai Youlong (Diuron) { N '-(3, the 4-dichlorophenyl)-N, N-dimethyl urea }, sulfonylureas, as U.S.A's grand (metsulfuron) { 2-[[[[(4-methoxyl group-6-methyl isophthalic acid of clothes that contracts, 3,5-triazine-2-yl) amido] carbonyl] amido] sulfonyl] methyl benzoate }, the spy contracts and obeys grand (triasulfuron) { 2-(2-chloroethoxy)-N-[[(4-methoxyl group-6-methyl isophthalic acid, 3,5-triazine-2-yl) amido] carbonyl] benzsulfamide }, special this excellent grand (tribenuron) { 2-[[[[(4-methoxyl group-6-methyl isophthalic acid, 3,5-triazine-2-yl)-the methyl amido] carbonyl] amido] sulfonyl] methyl benzoate } and gram dimension grand (chlorsulfuron) { the 2-chloro-N-[[(4-methoxyl group-6-methyl isophthalic acid of clothes that contracts, 3,5-triazine-2-yl) amido] carbonyl] benzsulfamide }, two-the amido formates, as divide beauteously emperor (Phenmedipham) { 3-[(methoxycarbonyl) amido] phenyl (3-aminomethyl phenyl) amido formates };
Fungicide: comprise sulfenyl amido formates, especially alkylidene two (disulfide group amido formates), as Ma Neibai (Maneb) { [1,2-ethane two base is two-[amido formyl disulfide group] (2-)] manganese and right (Mancozeb) { [[1 of violent gram, 2-ethane two bases-two-[amido formyl disulfide group] is (2-)] manganese and [[1,2-ethane two bases-two-[amido formyl disulfide group] is (2-)] zinc] mixture, Shi Te is than empty woods (strobilurins), as Ya Ruoxishizhuo refined (azoxystrobin) (E)-2-[[6-(2-cyano-benzene oxygen)-4-pyrimidine radicals] the oxygen base]-a-(methoxyl group is stretched methyl) methyl phenylacetate and Ke Liexin (kresoxim) (E)-a-(methoxyl group imide)-2-[(2-methylphenoxy) methyl] methyl phenylacetate, the inferior acid amides of dicarboxyl, { 3-(3 with (iprodione) as clothing ripple two, the 5-dichlorophenyl)-and N-isopropyl-2,4-dioxy base imidazoline-1-Carboxylamide }; Azoles (azole), { 1-[2-(2 to criticize health azoles (propiconazole) as general dimension, 4-two chloro-phenyl)-and 4-propyl group-1,3-dioxolane-2-base-methyl isophthalic acid H-1,2,4-triazole], and too butoconazole (tebuconazole) (RS)-1-is right-chlorphenyl-4,4-dimethyl-3-(1H-1,2,4 ,-triazol-1-yl methyl)-penta-3-alcohol }; The halogen phthalonitrile is as Crow Sa Long Neil (chlorothalonil) { 2,4,5,6-tetrachloro-1,3-dicyanobenzenes }; And inorganic fungicide, as Kocide SD { Cu (OH)
2;
Biocide: comprise benzoyl urea, as this resistance of generation clothes swell (Diflubenzuron) the N-[[(4-chlorphenyl) amido] carbonyl]-2,6-difluoro benzamide } }; And the amido formates, as sevin (carbary1) { 1-naphthyl amido methyl formate };
Arachnicide comprises: tetrazine, and as Crow dtex qin (Clofentezine) { 3, two (the 2-chlorphenyls)-1,2,4 of 6-, 5-tetrazine }.
This suspension formulations can comprise solid support, filler or thinner material, and it is preferably does not have a functionality to the farming active matter, and it can be dispersed in easily in the water and (can mix mutually with dispersant if necessary).It can be used to adjust the viscosity of this concentrate or dilution spray blender and/or as the holder of active matter.The example comprises clay, and as kaolin (Chinese clay) and bentonite clay, it can be natural bentonite or modified bentonite, for example activated bentonite; The synthetic diatom silica that reaches; Calcium silicates and magnesium; Titanium dioxide; Aluminium carbonate, calcium or magnesium; Ammonium sulfate, sodium, potassium, calcium or barium; Graphite; Starch comprises modified starch, as alkyl and carboxyalkyl starch; Cellulose, as avicel cellulose, and cellulose derivatives such as carboxyalkyl cellulose; And the mixture of two or more aforementioned solid supports, filler, thinner material.
The another kind of method system that the farming active matter is added composite among the present invention and uses with liquid or solution active matter to be dissolved in suitable (normally water can not mix) solvent, therein with it microencapsulation.The liquid that this water can not mix mutually is formula (I) compound or comprises at least a formula (I) compound, and it can be or part has liquid that microcapsules disperse and/or can be as the solvent (when using) of active matter in the microcapsules in the middle of being.These microcapsules can utilize traditional method to be prepared by emulsifying liquid liquid, or active matter is dissolved in the liquid of water-based normally, for example to condense mode, particularly with protein polymer (as gelatin), in-situ polymerization such as urea and/or melamino-formaldehyde polymer are with the generation capsule-wall or with the polymerization of interfacial polymerization mode.In case behind microencapsulation, this active matter will be disperseing in large composite that thing presents, and it can be adjusted through following manner.
Particle in the agrochemical suspension or comprise that the particle size of active farmingization thing should be enough little makes it not have the danger of obstruction spray nozzle.Generally speaking, when the modulation composite, the mean particle size of sneaking into this solid farmingization thing of composite is 50 to 100 microns, but this composite usually can be through wet lapping to reduce mean particle size to 1 to 10, particularly 1 to 5 micron after mixing.In fact the farming thing that is adsorbed on the solid support or is absorbed in it has the particle size of this holder, is preferably by 1 to 5 micron., more normal through the microcapsules mean particle size of encapsulated farming thing by 5 to 10 microns normally by 1 to 10 micron.Using a dispersant part is for fear of when storing and use, this farming composition granule or comprise the condensing of particle of farmingization thing.
This farming composite can comprise adjuvant, particularly surface active agent ad uvants, nonionic surfactant especially, and as pure alkoxide, routine b-oxide, particularly C
8To C
18Alcohol, it can be straight chain, side chain or straight chain/side chain mixture; The alkanamine alkoxide, routine b-oxide, particularly C
8To C
18The alkanamine class; Sorbierite and fatty acid esters of sorbitan, particularly C
8To C
18Fatty acid, ester and ethoxyquin derivative thereof; And alkyl, particularly C
6To C
14Alkyl, polysaccharide.For example, general adjuvant is by 1:3 to 10:1 with the weight ratio of farmingization active matter.Adjuvant itself can be included in the composite or its can be adsorbed on the solid support or within, this solid support is for example silica or diatomite, it can be solid support, filler or thinner as before, or it is included as clatraten urea clatraten especially.
Other surfactants that can be included particularly comprise wetting agent, and it can quicken the wettability of the dispersion of this concentrate in water to form spray or can strengthen plant leaf blade with spray.The example of wetting agent comprises nonionic surfactant, as pure b-oxide, for example C
9To C
15, especially elementary alcohol, it can be straight or branched, particularly has the single side chain b-oxide by 5 to 30 moles oxirane; The alkoxide that this is pure, b-oxide/the propoxide of Hun Heing particularly, the alkoxide that its section of can be connects or mixes arbitrarily generally comprises 3 to 10 ethylene oxide residue and 1 to 5 propylene oxide residue, particularly with the polyalkoxide chain of expoxy propane unit's end-blocking; The polyoxyethylene/polyoxypropylene copolymer, especially section connects copolymer, as the copolymer of Synperonic PE series and Atlas G5000 (can available from Uniqema), and alkyl polysaccharide; Anion surfactant, routine isethionate is as cocoa isethionic sodium (sodiumcocoylisethionate), naphthalene sulfonic acids or s-based succinate.Also can use the mixture of this wetting agent.
If need, can use polymeric dispersant and other dispersants (dispersant that example is traditional, as naphthalene sulfonic acid-formaldehyde condensation product, ligninsulfonate, copolymer-maleic anhydride and through the phenol sulfonic acid of condensation, and the nonionic dispersant, connect copolymer as the EO/PO section) admixture.In this admixture, polymeric dispersant is preferable to account for 25% at least, and more normal is at least 50%, and with at least 75% is good, same, when using other dispersants, it generally is to account for 1 to 75% of total points powder weight ratio, and more normal is 2 to 50%, and is preferably 5 to 25%.
The dispersant total amount of use in suspension of the present invention normally accounts for 3 to 10% of suspension-concentrates weight ratio, particularly accounts for 5 to 8%.Employed polymeric dispersant is preferably and accounts at least 1% of total suspension-concentrates composite weight ratio, and more normal be 2 to 10%, particularly by 5 to 8%.
When using wetting agent, this usage amount normally accounts for 1 to 5% of suspension-concentrates weight ratio, particularly by 2 to 4%, and the part by weight of this dispersant and wetting agent 1:1 to 1:10 normally, be preferably 2:1 to 4:1.Generally speaking, the combined amount of dispersant and wetting agent is to account for 3 to 10% of total suspension-concentrates composite weight ratio, and more normal be 5 to 8%.
The total amount of farmingization active matter generally is to account for 10 to 95% of suspension-concentrates weight ratio, more especially 20 to 90%.When not comprising adjuvant in the suspension-concentrates, the content of farmingization active matter accounts for 40 to 95% of suspension-concentrates weight ratio usually, and more especially 50 to 90%.When comprising adjuvant in the suspension-concentrates, the farmingization active matter account for 10 to 70% of suspension-concentrates weight ratio usually, more especially 20 to 50%, and the content of adjuvant accounts for 10 to 50% of total suspension-concentrates weight ratio, particularly 20 to 40%.In general, in the active matter of every weight portion, the weight portion of adjuvant is 1 to 10, and more normal is 1 to 5.The portfolio ratio of farmingization active matter and adjuvant normally the suspension-concentrates weight ratio 10 to 95%, more especially 20 to 90%.
When using solid support, its consumption is to account for 0.05 to 2 usually in the composition of every weight portion farmingization active matter, adjuvant (when use), dispersant and wetting agent (when use), particularly 0.1 to 1 weight portion.Therefore, employed solid support consumption generally is 0 to 70% of a suspension-concentrates weight ratio, particularly 5 to 50%.
The main consumption of forming part of suspension formulations of the present invention is preferably in the scope shown in the following table:
Form a part consumption
(the weight % of suspension-concentrates)
The broad range preferred range
Farmingization active matter amount 10 to 95 20 to 90
Do not contain adjuvant 40 to 95 50 to 90
Comprise adjuvant 10 to 70 20 to 50
Adjuvant (when containing sometimes) 10 to 50 20 to 40
Dispersant 3 to 10 5 to 8
Polymeric dispersant 1 to 10 3 to 8
Wetting agent (when containing sometimes) 1 to 52 to 4
Dispersant+wetting agent 3 to 10 5 to 8
Dispersant: ratio 1:1 to the 10:1 2:1 to 4:1 of wetting agent
Solid support (when containing sometimes) 0 to 50
Medium to 100
Suspension-concentrates based on water normally is used for the insoluble active component of disperse water, the water that the insoluble active ingredient of this water system directly disperses, or it is interior or be adsorbed on the solid support to be absorbed into solid support, or be the microencapsulation liquid or the solution of active matter.In the present invention, this composite also comprises polymeric dispersant and can comprise other dispersant surfactants.Be preferably this composite and also comprise adjuvant.Generally speaking, when diluting, comprise that the solid of active matter can directly be distributed in the water usually with water.Generally speaking, as described below usually based on the suspension-concentrates constituent of water:
Suspension-concentrates based on oil is used to the insoluble active component of dispersed oil, and it also is that water is soluble simultaneously, or it is the water dissolvable that is included in based in the streaming suspension concentrate of water, or it is not chemical stability in water.In the present invention, this composite also comprises polymeric dispersant and can comprise the dispersant fatty acid surfactant of condensation (particularly through), and also comprises that usually emulsifier makes the carrier fluid phase dilution to water.This composite is preferably and also comprises adjuvant.In the time of in being diluted to water, the insoluble solid active thing of water can directly be distributed in the water or become solid dispersed phase in the oil phase of emulsification (itself and the suspension emulsion fairly similar of dilution, the while is stated as follows).Whole generally based on the composition of the concentrate of oil such as following:
Farmingization suspension emulsion concentrate is to obtain suspending the composite of emulsion behind dilution water (water), that is it comprises at least a liquid (emulsion) disperse phase and at least a solid dispersed phase at successional aqueous phase.This concentrate composite itself can be the suspension emulsion, and in fact it only is through dilution composite (spray) more concentrated (having less water); Or it ties up to the solid dispersed phase of the dispersion in the emulsible concentrate, and it can form emulsion through dilution.It is specially adapted to the farmingization composite, it comprises the active matter (solution with the oil emulsion disperse phase presents) that oil is solvable, and the water of solid soluble (and normally oily insoluble) active matter, promptly solid composition part generally includes the farming active matter (presenting though other composite is formed part solid particle that also can disperse) that presents with dispersed particles.This solid dispersed phase can be dispersed in the emulsion droplet based on oil.The suspension emulsion is normally based on a kind of oil solution of farmingization thing, but comprises that also the insoluble active matter of solid water or other solids that presents with the particle of dispersion form part.Its surfactant (particularly oil-in-water emulsifier) that generally includes as emulsifier is diluted to the emulsion of one section spray concentration with stable through water, and as the dispersant of oil phase and/or aqueous phase solid particle.Suspension emulsion concentrate generally uses as spray to form the suspension emulsion through the water dilution.Generally, the composition of Zheng Ti suspension emulsion concentrate such as following:
Other materials that can be included in the suspension-concentrates comprise:
The antifreeze material, as ethylene glycol or single propane diols, general concentration is 2 to 20% of concentrate composite weight ratio, is preferably 5 to 15%, and particularly contains and have an appointment 10%.
The buffer solution material, as so that be preferably by 4 to 9 through the PH of diluted material, more normal is by 5 to 8 and particularly about 7;
Penetrating agent; Foam inhibitor; Protective agent is as Bitrex; Pigment and/or stain; The agglomeration resistance additive, particularly when any solid is isolated in by suspension, the formation of lowering the caking precipitation; Chelating agent; And adsorbent.
Following embodiment will set forth the present invention.Unless mention especially, all percentages when umber is all by weight.
Material
Dispersant-styrene acrylic copolymer:
Numbering AA/Sty
*MW
The active matter of DS1 2:1 8000 about 40 weight % is in water
The active matter (DS1 is spray-dried) of DS2 2:1 3,800 90 weight %
The active matter of DS3 2:1 42,000 20 weight % is in water
DS4 2:1 3700 anion-modified copolymers
*, 40% active matter is in water
* the mol ratio of acrylic acid and styrene monomer in copolymer
* acrylic acid composition comprises a certain proportion of sulfonation acrylic monomers
The farmingization active matter
The numbering trade name is described
The active matter of Act1 aldrin 99 weight %, routine Novartis (Ciba)
Act2 Cu (OH)
2100% active matter, routine Industrias Quimicas del Valles
The active matter of outstanding grand 96 weight % (at least) of Act3 generation, routine Sanachem
Act4 simazine 89% active matter, routine Syngenta
Act5 iprodione 95% active matter, routine Aventis
Act6 atrazine 97% active matter, routine Dow
Act7 carbaryl 97.5% active matter, routine Aventis
Unclassified stores
342 water 342ppm hardness WHO standard hard water
The water of 1000 water 1000ppm hardness
The single propane diols of MPG
Trade name is described
Surf1 Atlox 4894 pure alkoxide surfactant blend, routine Uniqema
Surf2 Atlox MBA 13/8 pure alkoxide surfactant, routine Uniqema
Surf2 Atlas G5000 polyalkylene glycol ethers, routine Uniqema
The uncle C13/15 alcohol that Surf2 Synperonic A7 POE (7) is synthetic, routine Uniqema
Th1 Kelzan xanthans thickener, routine Kelco
Method of testing
Solid stability-this assessment in water of dispersity (%)-test dispersion is in the test graduated cylinder, and the particle composites of 3 grams are dissolved in 100 milliliters 342 water.With this graduated cylinder reversing 30 times and make and leave standstill 30 minutes.Upper strata with 90% is noted not disturbing leaving standstill thing with the suction pipe sucking-off.Remaining liquid and any thing that leaves standstill are transferred in the evaporating pan and make it to be dried to fixing weight in 50 ℃ baking oven.Powder weighing (y gram) with gained.Dispersity (%) is the concentration of the powder in the water on upper strata 90%, and is expressed as:
[111. (3-y)/3] %[is equivalent to 33. (3-y) %]
Physics suspension (PS) is concentrated composite the measuring the resistance that produces deposition of dilution.In containing the 100ml Nessler pipe of concentrate sample, to estimate it with 19:1 dilution back 1 and 4 hour sediment depth (with mm) with 342 and 1000 water.
Aging:
The assessment mode of the aging effect of this suspension-concentrates sample is in storing under the environment temperature or storing in 50 ℃ baking oven with this concentrate.The assessment of this composite dispersity is when fresh (0) and reevaluate 1 week of example (1W), 10 days (10D), or 1 month (1M) after storing a period of time.
Example 1
Use serves as the suspension-concentrates based on water of farmingization active matter with aldrin (Atrazine), and it is to make via forming part (except that dispersant) mixing and grinding.After grinding, add dispersant.Following table 1 is listed employed inventory and concentrate in dispersity test result fresh and after storing.
Table 1
Example 2
Suspension-concentrates system based on water makes with following composite:
Active ingredient 500 grams
DS3 50 grams
Surf2 20 grams
MPG 100 grams
Water adds to 1 liter
Polymeric dispersant and surfactant are dissolved in the water of a MPG and a part, then, add active component and volume is added to 1 liter with water.This mixture is homogenized and ground with Dyno Mill KDL.If need, can add several situations of foam inhibitor to suppress to bubble in the process that homogenizes based on silicone.The viscosity and the dispersity of measurement concentrate in 342 water and 1000 water, its result is as shown in table 2 below.
Table 2
The farming reactive compound that embodiment 3 usefulness are different also adopts dispersant DS4, and the supending of promptly a kind of anion-modified acrylic acid styrol copolymer concentrates composite.Each batch (300g) with the Warning blender prepares every kind of composite under gentle agitation, adds entry earlier, add the thickener that is dispersed in advance among the MPG again, add surfactant and dispersant again, add farmingization active matter (gas is worn into the particle diameter less than 10 μ m) at last, continue to mix 10 minutes.Concentrate is made into and contains the active farmingization thing of 600g/L.Following table 3a lists used composite, and following 3b lists result of the test.
Table 3a
Table 3b
Claims (16)
1. agrochemical suspension concentrate composite, but its Yu Shuizhong dilution, and be the suspension-type of solid particle, the dispersant that it comprises one or more farmingization active constituents and contains the dispersible styrene of water (methyl) acrylic copolymer, wherein (methyl) acrylic monomers residue and styrene monomer residue mol ratio are 3:1 to 1:2.
2. according to the agrochemical suspension concentrate composite of claim 1, it further comprises:
(1) one or more wetting agents; And/or
(2) one or more adjuvants.
3. according to the agrochemical suspension concentrate composite of claim 1 or 2, wherein (methyl) acrylic monomers in styrene (methyl) acrylic copolymer is acrylic acid, methacrylic acid, butenoic acid or aforementioned two or more mixture, and styrene monomer is the styrene that styrene or alkyl replace.
4. according to the agrochemical suspension concentrate composite of claim 1 or 2, wherein styrene (methyl) (methyl) acrylic monomers residue that acrylic copolymer comprised contains strong acid group.
5. according to the agrochemical suspension concentrate composite of claim 4, wherein said strong acid group comprises sulfonic acid group or its salt.
6. according to the agrochemical suspension concentrate composite of claim 1 or 2, wherein styrene (methyl) acrylic copolymer comprises other monomer residues, and its content is no more than the 25mol% of total monomer in the copolymer.
7. according to the agrochemical suspension concentrate composite of claim 6, wherein said other monomer residues comprise strong acid group.
8. according to the agrochemical suspension concentrate composite of claim 7, wherein said strong acid group comprises sulfonic acid group or its salt.
9. according to the agrochemical suspension concentrate composite of claim 1 or 2, wherein in styrene (methyl) acrylic copolymer, the mol ratio of (methyl) acrylic monomers residue and styrene monomer residue is 3:1 to 1:1.
10. according to the agrochemical suspension concentrate composite of claim 1 or 2, wherein styrene (methyl) acrylic copolymer comprises one or more the residue in methylene-succinic acid, maleic acid or acid anhydrides, alkyl acrylate, acrylic acid hydroxyalkyl acrylate or the vinyl acetate, and its content is no more than the 25mol% of total monomer in the copolymer.
11. according to the agrochemical suspension concentrate composite of claim 10, wherein styrene (methyl) acrylic copolymer comprises one or more the residue in methyl methacrylate, (methyl) butyl acrylate, methacrylic acid hydroxyl ethyl ester or the methacrylic acid hydroxyl propyl ester.
12. according to the agrochemical suspension concentrate composite of claim 1 or 2, its substantial increase in the number of middle peasants active constituent is one or more plant growth regulator, weed killer herbicide and/or agricultural chemicals.
13. the agrochemical suspension concentrate composite of claim 1 or 2, wherein composite has following weight % composition:
Farmingization active constituent 10 to 95
Do not contain adjuvant 40 to 95
Comprise adjuvant 10 to 70
Adjuvant is when containing sometimes 10 to 50
Dispersant 3 to 10
Styrene (methyl) acrylic copolymer 1 to 10
Wetting agent is when containing sometimes 1 to 5
Dispersant+wetting agent 3 to 10
Dispersant: the ratio of wetting agent, when containing sometimes 1:1 to 10:1
Solid support is when containing sometimes 0 to 50
Medium to 100.
14. the agrochemical suspension concentrate composite of claim 13, wherein composite has following weight % composition:
Farmingization active constituent 20 to 90
Do not contain adjuvant 50 to 90
Comprise adjuvant 20 to 50
Adjuvant is when containing sometimes 20 to 40
Dispersant 5 to 8
Styrene (methyl) acrylic copolymer 3 to 8
Wetting agent is when containing sometimes 2 to 4
Dispersant+wetting agent 5 to 8
Dispersant: the ratio of wetting agent, when containing sometimes 2:1 to 4:1
Solid support is when containing sometimes 0 to 50
Medium to 100.
15. a method for preparing the spray mixture wherein will be dispersed in the water as each agrochemical suspension concentrate composite in the claim 1 to 14.
16. a methods for the treatment of plants, wherein said plant or the spray mixture sprinkling that soil is disperseed in water as each agrochemical suspension concentrate composite in the claim 1 to 14 is prepared of surrounding this plant.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0012775A GB0012775D0 (en) | 2000-05-26 | 2000-05-26 | Agrochemical suspension formulations |
| GB0012775.3 | 2000-05-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1430469A CN1430469A (en) | 2003-07-16 |
| CN100469245C true CN100469245C (en) | 2009-03-18 |
Family
ID=9892387
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB018101747A Expired - Lifetime CN100469245C (en) | 2000-05-26 | 2001-05-25 | Agrochemical suspension formulations |
Country Status (5)
| Country | Link |
|---|---|
| CN (1) | CN100469245C (en) |
| AR (1) | AR028112A1 (en) |
| BR (1) | BR0111144B1 (en) |
| CA (1) | CA2407840A1 (en) |
| GB (1) | GB0012775D0 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109414012A (en) * | 2016-05-25 | 2019-03-01 | 拜耳作物科学股份公司 | Agrochemical formulations based on emulsion polymer |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2619227C2 (en) * | 2011-12-15 | 2017-05-12 | ДАУ АГРОСАЙЕНСИЗ ЭлЭлСи | Aqueous suspended concentrate with high concentration of active ingredient |
| JP6592014B2 (en) * | 2014-06-03 | 2019-10-16 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Pesticide Suspoemulsion Formulation Containing Polymer Particles Made from Methyl (meth) acrylate and C2-C12 Alkyl (meth) acrylate |
| ES2924191T3 (en) * | 2015-07-21 | 2022-10-05 | Ceradis Bv | Stable agricultural compositions |
| CN104996419A (en) * | 2015-07-23 | 2015-10-28 | 沈阳新奇日化有限责任公司 | Polycarboxylate dispersing agent special for pesticide suspension concentrate |
| AU2020240213B2 (en) * | 2019-03-18 | 2024-04-18 | Kumiai Chemical Industry Co., Ltd. | Aqueous agrochemical suspension composition and method for spraying same |
| CN115868483A (en) * | 2021-09-27 | 2023-03-31 | 爱发生物科技(大连)有限公司 | Agrochemical suspension concentrate formulations and methods of making and using the same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3304457A1 (en) * | 1982-02-09 | 1983-10-13 | Toagosei Chemical Industry Co., Ltd., Tokyo | Composition for use in agriculture |
| US5089259A (en) * | 1988-12-19 | 1992-02-18 | Dowelanco | Stable concentrates and emulsions of water-insoluble organic pesticides |
| EP0644205A1 (en) * | 1993-09-03 | 1995-03-22 | Rhone-Poulenc Specialty Chemicals Co. | Process for preparing a latex with ultrafine particles |
| WO1995007614A1 (en) * | 1993-09-15 | 1995-03-23 | Dowelanco | Storage and dilution of stable aqueous dispersions |
| US5508035A (en) * | 1988-09-01 | 1996-04-16 | Dowelanco | Stable concentrates and emulsions of water-insoluble organic pesticides |
| WO1999018787A1 (en) * | 1997-10-14 | 1999-04-22 | Huntsman Surfactants Technology Corporation | Method of dispersing an insoluble material in aqueous solution and agricultural formulation |
-
2000
- 2000-05-26 GB GB0012775A patent/GB0012775D0/en not_active Ceased
-
2001
- 2001-05-23 AR ARP010102470A patent/AR028112A1/en unknown
- 2001-05-25 BR BRPI0111144-2A patent/BR0111144B1/en not_active IP Right Cessation
- 2001-05-25 CN CNB018101747A patent/CN100469245C/en not_active Expired - Lifetime
- 2001-05-25 CA CA002407840A patent/CA2407840A1/en not_active Abandoned
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3304457A1 (en) * | 1982-02-09 | 1983-10-13 | Toagosei Chemical Industry Co., Ltd., Tokyo | Composition for use in agriculture |
| US5508035A (en) * | 1988-09-01 | 1996-04-16 | Dowelanco | Stable concentrates and emulsions of water-insoluble organic pesticides |
| US5089259A (en) * | 1988-12-19 | 1992-02-18 | Dowelanco | Stable concentrates and emulsions of water-insoluble organic pesticides |
| EP0644205A1 (en) * | 1993-09-03 | 1995-03-22 | Rhone-Poulenc Specialty Chemicals Co. | Process for preparing a latex with ultrafine particles |
| WO1995007614A1 (en) * | 1993-09-15 | 1995-03-23 | Dowelanco | Storage and dilution of stable aqueous dispersions |
| WO1999018787A1 (en) * | 1997-10-14 | 1999-04-22 | Huntsman Surfactants Technology Corporation | Method of dispersing an insoluble material in aqueous solution and agricultural formulation |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109414012A (en) * | 2016-05-25 | 2019-03-01 | 拜耳作物科学股份公司 | Agrochemical formulations based on emulsion polymer |
| US12108757B2 (en) | 2016-05-25 | 2024-10-08 | Bayer Cropscience Aktiengesellschaft | Agrochemical formulation based on emulsion polymers |
Also Published As
| Publication number | Publication date |
|---|---|
| BR0111144B1 (en) | 2013-02-19 |
| GB0012775D0 (en) | 2000-07-19 |
| AR028112A1 (en) | 2003-04-23 |
| BR0111144A (en) | 2003-04-08 |
| CN1430469A (en) | 2003-07-16 |
| CA2407840A1 (en) | 2001-12-13 |
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