WO2011065831A2 - Formulations améliorées comprenant des hétéropolysaccharides - Google Patents

Formulations améliorées comprenant des hétéropolysaccharides Download PDF

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WO2011065831A2
WO2011065831A2 PCT/NL2010/050799 NL2010050799W WO2011065831A2 WO 2011065831 A2 WO2011065831 A2 WO 2011065831A2 NL 2010050799 W NL2010050799 W NL 2010050799W WO 2011065831 A2 WO2011065831 A2 WO 2011065831A2
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composition
copper
xanthan
heteropolysaccharide
biocide
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PCT/NL2010/050799
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WO2011065831A3 (fr
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Cornelis Johannes Kok
Wilhelmus Maria Van Der Krieken
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Ceradis B.V.
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Publication of WO2011065831A2 publication Critical patent/WO2011065831A2/fr
Publication of WO2011065831A3 publication Critical patent/WO2011065831A3/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/70—Carbohydrates; Sugars; Derivatives thereof
    • A61K31/715—Polysaccharides, i.e. having more than five saccharide radicals attached to each other by glycosidic linkages; Derivatives thereof, e.g. ethers, esters
    • A61K31/736—Glucomannans or galactomannans, e.g. locust bean gum, guar gum
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/70—Carbohydrates; Sugars; Derivatives thereof
    • A61K31/715—Polysaccharides, i.e. having more than five saccharide radicals attached to each other by glycosidic linkages; Derivatives thereof, e.g. ethers, esters
    • A61K31/716—Glucans
    • A61K31/723—Xanthans
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00—Medicinal preparations containing inorganic active ingredients
    • A61K33/24—Heavy metals; Compounds thereof
    • A61K33/34—Copper; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A61K8/737—Galactomannans, e.g. guar; Derivatives thereof
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/10—General cosmetic use
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/48—Thickener, Thickening system
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/52—Stabilizers

Definitions

  • the present invention discloses formulations for pesticides comprising a biocide, especially a copper-based biocide, and a heteropolysaccharide that have an improved efficacy of the biocide, for example copper-based biocide.
  • the invention relates to concentrated formulations of a heteropolysaccharide with a high dissolution rate in water.
  • Copper is most commonly used in fungicides in the form of copper hydroxide (Cu(OH)2 ), copper oxychloride (CuCb -3Cu(OH) 2 ) and Bordeaux mixture (CuS04.3Cu(OH) 2 .3CaS0 4 ), although a number of other salts and copper complexes of organic compounds are on the market or have been sold in the past.
  • Chelators that specifically bind metal ions like copper are used in various formulations of copper- based fungicides (e.g. USPTO Patent Application 20090136581; and US 6,562,757) and several compositions in which copper is combined with other types of organic molecules like octanoate (Commercial product: Copper SoapTM, Neudorff, USA); napthenate (Commercial product CuNape ⁇ Merichem, USA) or terpenes (US patent 6,849,276).
  • octanoate Common product: Copper SoapTM, Neudorff, USA
  • napthenate Common product CuNape ⁇ Merichem, USA
  • terpenes US patent 6,849,276
  • a group of pesticide formulation ingredients increasingly receiving attention is the class of heteropolysaccharides, polymers of sugars consisting of more than one type of sugar monomer. These heteropolysaccharides are used in pesticide formulations as binders, structuring agents and rheology modifiers.
  • the present invention relates to novel uses of heteropolysaccharides in biocides, for example in combination with the biocidal metal copper and to novel techniques of producing hetero polysaccharide containing
  • the present invention discloses the use of a combination of heteropolysaccharides with biocides such as commonly used copper-based biocides.
  • biocides such as commonly used copper-based biocides.
  • the invention allows a significant dose reduction for biocides, especially copper-based biocides, without loss of efficacy.
  • the invention provides a biocidal composition
  • a biocidal composition comprising at least a biocide, for example a copper-based biocide or a copper-based additive, and a heteropolysaccharide.
  • a heteropolysaccharide that is used in a composition according to the invention comprises succinoglycan and/or xanthan.
  • xanthan refers to the polysaccharide that is produced by fermentation of glucose or sucrose by the Xanthomonas campestris bacterium.
  • Xanthan consists of pentasaccharide repeating units, further containing several organic acids.
  • a typical xanthan produced for industrial purposes comprises glucose, mannose, glucuronic acid, acetate,and pyruvate. Because of its wide applications in the oil, food, textile, agrochemistry, cosmetic and pharmaceutical industries, the output of xanthan gum is now the largest of the natural exopolysaccharides. Xanthan gum is used in food, cosmetics and medical applications as thickener and emulsion stabilizer.
  • xanthan gum is used for suspension stabilization (structuring agent), improved sprayability, drift reduction and for increased cling and permanence of the spray (sticker).
  • xanthan gum is used among others for lubrication or friction reduction in drill-hole, stabilization of drill muds and enhanced oil recovery through reduction of water mobility by increasing viscosity and decreasing permeability.
  • a preferred xanthan is the commercial product Rhodopol® (Rhodia, France) or Kelzan® (Kelco Company, USA).
  • xanthan-like refers to polysaccharides with pentasaccharide repeating units similar to xanthan, but with different levels of glucoronic, acetic and pyruvic acids. Such xanthan-like compounds can be produced by other bacterial species, related to
  • xanthan and "xanthan4ike” includes chemical modifications of xanthan and xanthan4ike gums, respectively.
  • a preferred modified xanthan is a xanthan gum-glyoxal complex comprising the reaction product of xanthomonas gum and glyoxal, and which comprises from about 0.02% to about 5% (w/w) glyoxal based upon the weight of dry xanthomonas gum.
  • succinoglycan refers to a high-molecular-weight polymer composed of repeating octasaccharide subunits, comprising one galactose residue and seven glucose residues, and further comprising acetate, succinate, and pyruvate residues.
  • a typical composition of succinoglycan is glucose, galactose, pyruvate, succinate and acetate in the ratios 7: 1: 1: 1: 1.
  • Certain succinoglycans exhibit rheological properties comparable to those of xanthan gum and are, furthermore, characterized by an increased stability to temperature, acid and basic pHs and strongly saline media (US Patent 5831042).
  • a preferred succinoglycan is the commercial product Rheozan®; Rhodia (France).
  • succinoglycan-like refers to polysaccharides with octasaccharide subunits as succinoglycan, but with different levels of pyruvate, succinate or acetate.
  • succinoglycan-like compounds can be produced by other bacterial species, related to the group of Pseudomonas, Rhizobium, Alcaligenes and Agrobacterium, or by these bacteria, if grown under non-standard conditions (Zevenhuizen, L.P.T.M. (1997) Carbohydrate polymers 33: 139 - 144).
  • succinoglycan and "succinoglycan-like” includes chemical modifications of succinoglycan and succinoglycan-like gums, respectively. Further preferred are mixtures of xanthan and/or xanthan-like heteropolysaccharides and succinoglycan and/or succinoglycan-like heteropolysaccharides. A preferred mixture comprises xanthan and succinoglycan.
  • biocide refers to a chemical substance capable of killing living organisms. Biocides are commonly used in medicine, agriculture, forestry, and in industry where they prevent the fouling of, for example, water, agricultural products including seed, and oil pipelines.
  • a biocide can be a pesticide, including a fungicide, herbicide, insecticide, algicide, molluscicide, miticide and rodenticide; and/or an antimicrobial such as a germicide, antibiotic, antibacterial, antiviral, antifungal, antiprotozoal and/or antiparasite.
  • a preferred biocide is a fungicide.
  • Preferred antifungal compounds or fungicides comprise compounds such as imazalil (Janssen Pharmaceutica NV, Belgium), thiabendazole (e.g. the commercial product TECTO® Flowable SC of Syngenta, USA), benomyl, captan (nonsystemic phthalimide fungicide), prochloraz (N-propyl-N- [2-(2,4,6- trichlorophenoxy) ethyl] imidazole- 1-carboxamide), thioallophanate (e.g. the commercial product TOPSIN® M Cerexagri Inc), orange oil, D-limonene, and fluazinam (commercial product: (SHIRLAN® Syngenta, Switzerland).
  • imazalil Janssen Pharmaceutica NV, Belgium
  • thiabendazole e.g. the commercial product TECTO® Flowable SC of Syngenta, USA
  • benomyl captan (nonsystemic phthalimide fungicide)
  • a further preferred biocide is a pesticide.
  • Pesticidal agents include compounds to combat insects, nematodes, mites and bacteria. Examples of such compounds are imidacloprid (commercial product ADMIRE® Bayer), pirimiphos- methyl (commercial product ACTELLIC® Syngenta, Switserland), Pyrethroids (commercial product BAYGON® (Bayer), bifenazate (e.g. Uniroyal), dichlorvos (e.g. Amvac Chemical Corporation), imidacloprid (e.g. Bayer), fenamiphos (e.g. Mobay Chemical Corporation), orange oil, D- limonene, oxamyl (e.g. Dupont).
  • a most preferred pecticide is pirimiphos -methyl (commercial product ACTELLIC®).
  • Suitable copper-based biocides are copper hydroxide (Cu(OH)2 ), copper oxychloride (CuC12 ⁇ 3Cu(OH)2), tribasic copper sulphate (CuS04.3Cu(OH)2) and Bordeaux mixture (CuS04.3Cu(OH)2.3CaS04).
  • Suitable copper-based additives comprise Bordeaux mixture, Burgundy mixture, Cheshunt mixture, copper acetate, basic copper carbonate, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper silicate, copper sulfate, copper zinc chromate, basic copper sulfate, cufraneb, cuprobam, cuprous oxide, mancopper and oxine-copper.
  • a composition according to the invention comprises two of more biocides, such as two or more fungicides, two or more pesticides, or one or more fungicide and one or more pesticide.
  • a preferred composition according to the invention comprises a copper-based biocide and a further biocide, preferably a fungicide and/or a pesticide.
  • a preferred composition according to the invention is a solid and comprises between 0, 1% and 60% (w/w; based on the total product) of a biocide, preferably between 2 and 10%, most preferred about 3%.
  • a preferred solid composition according to the invention comprises between 1 % and 25 % (w/w, based on the total product) of a
  • a composition according to the invention can be suspended in an aqueous solution, for example water, to a ready to use composition comprising between 0,0001% and 1% (w/w; based on the total product) of a biocide), preferably between 0,001 and 0, 1%, most preferred about 0,01%.
  • a preferred diluted ready to use concentration composition comprises between 0,001 % and 2,5 % (w/w, based on the total product) of a heteropolysaccharide, more preferred between 0,01% and 1 %, most preferred about 0,04 % of a heteropolysaccharide.
  • a preferred composition according to the invention contains one or more
  • a composition according to the invention can be in the form of a dry powder, a tablet, a suspension, a granule, a paste, a concentrates, a dust, an emulsion, or a liquid solution that is made thereof.
  • Said liquid solution preferably is an aqueous solution.
  • the composition comprises at least one additional compound selected from the group consisting of a sticking agent, a surfactant, an emulsifier, a detergent, a preservative, a stabilizer, a spreading agent, an antioxidant, an anti-foam- forming agent, a wetting agent, a thickening agent, a filler, a spray oil, a dispersing agent, and a flow additive.
  • sticking agents comprise, but are not limited to, latex based products like Prolong® (Holland Fyto B.V., The Netherlands) and Bond® (Loveland Industries Ltd), pilonene/terpene based products like Nu-film® (Hygrotech Saad) and Spray- Fast® (Mandops) and long chain polysaccharides like locust bean gum and guar gum.
  • the sticking agent may be a polymer or co-polymer from a type of polymer such as polyacrylate and polyethylene e.g. Neocryl® (DSM, The Netherlands).
  • a composition of the invention may also comprise two or more different sticking agents.
  • surfactants examples include, but are not limited to, anionic tensides such as sodium lauryl sulphate or polyethylene alkyl ethers or polyoxyethylethers, e.g Tween® 60, 61 or 65.
  • useful surfactants are organo silicones, sulfosuccmates, alcohol ethoxylates, fatty acid ethoxylates, fatty acid propoxylates and the commercial product Zipper® (Moodify BV, The Netherlands).
  • a composition of the invention may also comprise two or more different of the above mentioned agents.
  • suitable preservatives comprise, but are not limited to, weak acid preservatives such as sorbic acid, lactic acid, benzoic acid, propionic acid, citric acid, acetic acid, or an alkali metal or alkali earth metal salt thereof; inorganic acids such as hydrochloric acid; imidazoles such as imazalil or any antifungal compound known in the art as a preservative for food products, crop protection or after harvest treatment of fruits, vegetables or cereals; ethyl parabenzoate; borax; calcium bisulfite; calcium disodium EDTA; dehydroacetic acid; isothiazoles (e.g. cit/mit); and antimicrobials capable of preventing bacterial growth in the composition.
  • the composition of the invention may also comprise two or more different preservatives.
  • Suitable stabilizers comprise, but are not limited to, agar, alginic acid, alginate, calcium lactobionate, carrageenan, gellan gum, locust bean gum, and guar gum.
  • a composition of the invention may also comprise two or more different stabilizing agents.
  • antioxidants comprise, but are not limited to, amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazole (e.g. urocanic acid) and derivatives, vitamin C and derivatives (such as ascorbylpalmitate and ascorbyltetraisopalmitate, Mg-ascorbylphosphate, Na-ascorbylphosphate, ascorbyl- acetate), tocopherol and derivates (such as vitamin-E-acetate), mixtures of vitamin E, vitamin A and derivatives (vitamin-A-palmitate and -acetate) as well as
  • amino acids e.g. glycine, histidine, tyrosine, tryptophan
  • imidazole e.g. urocanic acid
  • vitamin C and derivatives such as ascorbylpalmitate and ascorbyltetraisopalmitate
  • Mg-ascorbylphosphate
  • a composition of the invention may also comprise two or more different antioxidants.
  • Suitable anti-foam forming agents comprise, but are not limited to,
  • a composition of the invention may also comprise two or more different anti-foam forming agents.
  • suitable thickening agents comprise, but are not limited to, agar, alginic acid, alginate, carrageenan, gellan gum, guar gum, locust bean gum, acetylated distarch adipate, acetylated oxidised starch, arabinogalactan, ethyl cellulose, methyl cellulose, locust bean gum, starch sodium octenylsuccinate, and triethyl citrate.
  • a composition of the invention may also comprise two or more different thickening agents.
  • suitable fillers comprise, but are not limited to, montmorillonite, kaolin, veegum, bentonite, and talcum.
  • a composition of the invention may also comprise two or more different fillers.
  • a most preferred filler is veegum.
  • suitable dispersing agents include, but are not limited to sulfonated aromatic polymer (commercial product MORWET D-425® Akzo Nobel), Ethylene Oxide/Propylene Oxide Block Copolymer (commercial product: PLURONIC P®; BASF) and organosilicones (e.g. SILWET L-77®; Helena chemical company).
  • a composition of the invention may also comprise two or more different dispersing agents.
  • a most preferred disperging agent is calcium lignosulfonate
  • suitable spray oils comprise, but are not limited to, Banole®, Banole® W, BANOLE® UBV, SprayTex M®, Orchex 692®, sunspray 11 E®.
  • a composition of the invention may also comprise two or more different spray oils.
  • a most preferred spray oil is BANOLE®.
  • suitable flow additives comprise, but are not limited to, kaolin, talcum, polymethylsilsesquioxane (commercial product: Wacker-Belsil® PMS MK),
  • a composition of the invention may also comprise two or more different flow additives.
  • a most preferred flow additive is polydimethylsiloxane.
  • the invention further provides a method for protecting an agricultural plant from a plant disease, preferably a fungal disease, the method comprising applying to said agricultural plant a biocidal composition according to the invention, comprising a biocide and a heteropolysaccharide.
  • Said biocide preferably is a copper-based biocide or comprises a copper-based additive.
  • Said agricultural plant is preferably a crop plant, preferably a vegetable, or a fruit.
  • Said plant disease is preferably a disease that is caused by a pathogen.
  • Said pathogen preferably is a fungus.
  • Said fungus preferably belongs to the order Oomycetes (esp. Phytophthora sp. , Plasmapara viticola).
  • a composition according to the invention may be diluted to a ready to use concentration comprising between 0,01 and 25 gram/liter of a heteropolysaccharide, more preferred between 0, 1 and 10 gram/liter, most preferred about 0,4 gram/liter.
  • the invention further provides a method of producing a composition comprising a biocide with enhanced efficacy, the method comprising adding a heteropolysaccharide to the composition.
  • Said biocide preferably is a copper-based biocide or a biocide comprising a copper-based additive.
  • a limitation to the use of xanthan and xanthan-like gum and of succinoglycan and succinoglycan-like gum is the slow dissolution rate and the tendency of formation of lumps during dissolution although some physical means have been used to improve dispersibility.
  • dissolution process of gums includes two steps (V an Krevelen, D. W. (1976). Properties of polymers— Their estimation and correlation with chemical structure.
  • Another approach is to pre-swell the gum in a polar solvent like ethylene glycol (ethane- 1,2-diol) or mono propylene glycol (propane- 1,2-diol), sometimes combined with heating (Andersson, M., Ciullo, P.A. (2000). SOFW-Journal, 6 (126), 32-36).
  • Pre -swelling in ethylene glycol or mono propylene glycol reduces the formation of lumps as well as the solution time of xanthan or succinoglycan gums, but xanthan and succinoglycan gum do gellify in both ethylene glycol and mono propylene glycol. This implies that the pre- swollen gums have to be diluted shortly after the gums have been added to the swelling agent, thus precluding the option of preparing stock preparations that can be stored for longer periods of time.
  • European patent EP0016640 teaches the use of suspensions of xanthan gum in mineral oil, diesel oil, kerosene, alcohols (six to twelve carbons), vegetable oil, ester- alcohols, polyol ethers, and the like. Additional compounds necessary in these preparations include suspending agents, dispersants, and thinning agents. The xanthan gum in these preparations is not pre-swollen, which means that the dissolution time and lumping are still important issues.
  • Commercial products in which xanthan is suspended in liquid are, for instance, LIQUID FLOWZAN® Biopolymer and GREENBASETM FLOWZAN®
  • the present invention solves the problem of preparing a concentrated heteropolysaccharide suspension. Therefore, the invention provides a composition comprising a heteropolysaccharide and a liquid selected from a water-free surfactant and a hydrophilic aprotic solvent, or a combination thereof.
  • a composition comprising a heteropolysaccharide and a liquid selected from a water-free surfactant and a hydrophilic aprotic solvent, or a combination thereof.
  • heteropolysaccharides comprise xanthan and xanthan-like heteropolysaccharides produced by bacteria comprising the genus Xanthomonas, containing structural units derived from glucose, mannose, glucuronic acid and pyruvic and acetic acid and salts of such acids.
  • Further preferred heteropolysachharides comprise succinoglycan and succinoglycan-like heteropolysaccharides produced, for example, by bacteria of the genera Pseudomonas, Rhizobium, Alcaligenes and
  • xanthan-like and succinoglycan gums can be used in embodiments of the present invention such as, for example, a xanthan gum-glyoxal complex comprising the reaction product of xanthomonas gum and glyoxal, whereby the complex comprises from about 0.02% to 5% by weight of glyoxal based upon the weight of dry xanthomonas gum.
  • xanthan e.g. the commercial products Rhodopol® (Rhodia, France) or Kelzan® (Kelco Company, USA
  • succinoglycan e.g. the commercial product Rheozan®; Rhodia
  • Further embodiments of the invention comprise mixtures of xanthan-like heteropolysaccharides and succinoglycan-like heteropolysaccharides.
  • a preferred mixture comprises xanthan and succinoglycan.
  • a composition according to the invention further comprises a heteropolysaccharide of the galactomannan type, such as fenugreek gum, guar gum, tara gum and locust bean gum or carob gum.
  • a heteropolysaccharide of the galactomannan type such as fenugreek gum, guar gum, tara gum and locust bean gum or carob gum.
  • Heteropolysaccharides of the galactomannan type are known for synergistic interaction with xanthan and succinoglycan, resulting in a higher viscosity of suspensions of mixed heteropolysaccharides than could be expected from the viscosity of suspensions of the heteropolysaccharides by themselves (US Patent 5350524; Casas, J.A. and Garcia-Ochoa (1999). Journal of the Science of Food and Agriculture 79: 25-31; Casa, J. A., Mohedano, A.F. and Garcia-Ochoa (2000) Journal of
  • the relative amount of the heteropolysaccharide in a composition according to the invention is between 10 and 500 g /kg, more preferred between 20 and 250 g /kg, more preferred between 50 and 100 g /kg.
  • Xanthan and succinoglycan gums are used in many applications in which the final product comprises a number of different compounds. Examples are sauces, cremes, pesticide formulations and printing dyes. In such applications, it would be advantageous to have a concentrated preparation containing all ingredients that can be diluted with water to the ready-to-use product.
  • Such concentrated heteropolysaccharide is for instance especially useful for preparing a concentrated formulation for pesticides, comprising a copper-based biocide or a copper- based additive.
  • a pesticide formulation comprising a copper-based biocide or a copper- based additive, a heteropolysaccharide and a liquid selected from a water-free surfactant and a hydrophilic aprotic solvent, or a combination thereof for instance reduces the transport and storage costs.
  • the concentrated pesticide composition can be easily diluted with water prior to use.
  • the invention thus provides a pesticide formulation comprising a copper-based biocide or a copper-based additive, a heteropolysaccharide and a liquid selected from a water-free surfactant and a hydrophilic aprotic solvent, or a combination thereof.
  • the relative amount of the heteropolysaccharide in a pesticide formulation according to the invention is between 10 and 500 g /kg, more preferred between 20 and 250 g /kg, more preferred between 50 and 100 g /kg.
  • concentrations of 20 g /l or more turns into a gel that cannot be poured out of the container.
  • Typical concentrations for use of xanthan gum in final formulations are 0.5— 10 g/ 1 (F. Garcia-Ochoa, V.E. Santos, J.A. Casas, E. Gomez (2000). Biotechnology Advances 18: 549-579). This indicates that useful dilution rates from a composition of the invention are between 50 and 1000 times.
  • Suitable examples of water-free surfactants comprise alcohol alkoxylates (e.g. alcohol ethoxy- propoxylate), sorbitan ester ethoxylates (e.g. POE (20) eorbitan mono-oleate), ethylene oxide / propylene oxide copolymers (e.g. polyoxyalkylene glycol butyl ether), polyglycerol esters of fatty acids and sorbitan esters of fatty acids.
  • a composition comprises two or more different surfactants.
  • aprotic hydrophilic solvents are also suitable solvents for high concentration of a heteropolysaccharide such as xanthan and succinoglycan.
  • Suitable examples of aprotic solvents comprise dimethyl sulfoxide, dimethyl formamide, dimethylacetamide, acetonitrile and methoxy propoxy propanol.
  • a composition of the invention comprises one or more surfactants and one or more aprotic hydrophilic solvents.
  • a composition of the present invention will generally contain 10-500 g /kg of heteropolysaccharide suspended in a suitable surfactant.
  • the heteropolysaccharide is xanthan and the suspension liquid is alcohol ethoxy propoxylate (commercial product:Genapol EP 2584®, marketed by Clariant, Germany).
  • the heteropolysaccharide is xanthan and the suspension liquid is methoxy propoxy propanol (commercial product Acrosolv®; Lyonell, USA).
  • heteropolysaccharide is xanthan and the suspension liquid is a mixture of 50 % (v/v/) Genapol EP 2584 and 50 % (v/v) methoxy propoxy propanol.
  • the heteropolysaccharide is succinoglycan and the suspension liquid is alcohol ethoxy propoxylate (commercial product: Genapol EP 2584®)
  • the heteropolysaccharide is succinoglycan and the suspension liquid is methoxy propoxy propanol.
  • heteropolysaccharide is succinoglycan and the suspension liquid is a mixture of 50 % (v/v/) alcohol ethoxy propoxylate (commercial product: Genapol EP 2584®) and 50 % (v/v) methoxy propoxy propanol.
  • a composition of the invention further comprises one or more of a medicinal compound including, but not limited to, hydrocortisone, acyclovir, propolis and, preferably, natamycin; a colorant including, but not limited to, Brilliant Blue FCF, tartrazine, Sunset Yellow FCF and, preferably, erythrosine; a flavoring compound including, but not limited to, citral, menthol, isoamyl acetate and, preferably, vanillin; a fungicidal or insecticidal compound including, but not limited to, imazalil, thiabendazole, benomyl, natamycin, phosphite and salts of phosphite, orange oil, limonene, Bacillus thuringiensis (Bt) and, preferably, folpet; a bactericidal compound including, but not limited to, benzalkonium chloride, daptomycin, gentamycin and , preferably,
  • metronidazole and/or a nematicidal compound including, but not limited to,
  • phenamiphos oxamyl, aldicarbcarbofuran and, preferably, neem tree oil.
  • the invention provides a method of preparing an aqueous
  • composition comprising a heteropolysaccharide
  • the method comprising diluting a composition according to the invention in water.
  • the high dilution rate in water of between 50 and 1000 times renders a composition of the invention very suitable for storage and transport of the composition from the production site to an end user.
  • the solvent that is used in a composition of the invention is freely miscible with water to allow simple dilution of the concentrated heteropolysaccharide suspension to the desired concentration in water resulting in a fast and lump-free dissolution of the
  • invention provides the use of a composition according to the invention in the preparation of a composition comprising a heteropolysaccharide in water.
  • the invention provides an aqueous composition comprising one of more heteropolysaccharides, water, and a liquid selected from a surfactant and a hydrophilic aprotic solvent, or a combination thereof.
  • a typical aqueous composition comprises between 0.1 and 20 g/1 of one or more heteropolysaccharides, more preferred between 0.5 and 10 g/ 1, more preferred between 1 and 5 g/1.
  • the concentration of the surfactant and/or hydrophilic aprotic solvent is preferably at most 10 % (v/v), more preferred at most 1 % (v/v), more preferred at most 0.5 % (v/v), more preferred at most 0.1 % (v/v), more preferred at most 0.01 % (v/v).
  • the invention provides the use of an aqueous composition according to the invention as thickener or as emulsion stabilizer.
  • a food product, a cosmetic product or a medical application product may comprise a
  • heteropolysaccharide as a thickener or as an emulsion stabilizer, whereby the heteropolysaccharide is applied by the use of an aqueous composition according to the invention.
  • the invention provides the use of an aqueous composition according to the invention for lubrication or friction reduction.
  • a heteropolysaccharide is used in the oil industry for lubrication or friction reduction in drill-hole, stabilization of drill muds and enhanced oil recovery through reduction of water mobility by increasing viscosity and decreasing permeability.
  • the invention provides the use of an aqueous composition according to the invention in a pesticide, bacteriocide, fungicide, or nematocide.
  • a heteropolysaccharide is used in pesticide formulations for suspension stabilization (structuring agent), for improved sprayability, and/or for drift reduction and increased cling and permanence of the spray.
  • the experimental design is a randomized block design with a plot size of 4 m2 per plot and 25 plants per plot.
  • the experiment has 4 replications.
  • the plants are sprayed weekly with a dose rate of 0.8 1/plot, using a backpack sprayer.
  • the composition and the dose rate of the different treatments are given in Table 1.
  • composition and dose rates are adjusted so that each plot receives the same amount of active ingredients and adjuvants (as applicable). To allow detection of synergism
  • the experimental setup includes treatments with each of the copper-based fungicides alone, xanthan alone, and the combination of xanthan with each of the copper fungicides.
  • a control is added that consists of only the adjuvant components (a surfactant and a dispersant).
  • Disease ratings are performed weekly by visual estimation of the fraction of leaf area attacked by the disease.
  • Composition 5 40 a 90 225
  • the experimental setup is the same as shown in example 1.
  • the composition and the dose rate of the different treatments are given in Table 3. Composition and dose rates are adjusted so that each plot receives the same amount of active ingredients and adjuvants (as applicable).
  • sucinoglycan itself is not active against the disease, it strongly stimulates the activity of the different copper fungicides.
  • the experimental design is a randomized block design with a plot size of 4 m 2 per plot and 25 plants per plot.
  • the experiment has 4 replications.
  • the plants are sprayed weekly with a dose rate of 0.8 1/plot, using a backpack sprayer.
  • the composition and the dose rate of the different treatments are given in Table 1. Composition and dose rates are adjusted so that each plot receives the same amount of active ingredients and adjuvants (as applicable).
  • the experimental setup includes treatments with each of the copper-based fungicides alone, xanthan alone, and the combination of xanthan with each of the copper fungicides.
  • a control is added that consists of only the adjuvant components (a surfactant and a dispersant).
  • Disease ratings are performed weekly by visual estimation of the fraction of leaf area attacked by the disease.
  • Data processing is performed as for example 1
  • Composition 5 40 a 90 225
  • the experimental setup is the same as shown in example 3.
  • the composition and the dose rate of the different treatments are given in Table 3. Composition and dose rates are adjusted so that each plot receives the same amount of active ingredients and adjuvants (as applicable).
  • the copper fungicide copper sulfate is formulated with dispersant and surfactant as shown in Table 7.
  • Table 7 composition of formulated copper sulfate- based fungicidal composition (g /kg composition) as used in example 5 and 6.
  • the copper fungicide copper sulfate is formulated with dispersant and surfactant as shown in Table 7 and different binders are added as shown in example 5.
  • Rhodopol 23 (xanthan) 30 A Rhodopol 23 (xanthan) 30 A
  • a suspension is prepared of 50 g of xanthan (commercial product RHODOPOL 23 ®, Rhodia, France) in 50 g of alcohol ethoxy propoxylate (commercial product:Genapol EP 2584®) .
  • the suspension exhibits good pourability without gellification.
  • a suspension is prepared of 50 g of succinoglycan (commercial product Rheozan, Rhodia, France) in 50 g of methoxy propoxy propanol.
  • the suspension exhibits good pourability without gellification. This characteristic is retained after storage at 54 °C for two weeks, which is equivalent to two years of storage at room temperature.
  • Upon mixing with water a fine dispersion of succinoglycan is formed, that dissolved within 2 minutes.
  • a suspension is prepared of 10 g of xanthan (commercial product Rhodopol 23®, Rhodia, France) in 50 g of Polyoxyethylene (20) sorbitan monolaurate (commercial product:
  • xanthan commercial product Rhodopol 23, Rhodia, France
  • methyl oleate derivative of vegetable oil
  • succinoglycan commercial product Rheozan, Rhodia, France
  • suspended at 250 g/1 methyl oleate derivative of vegetable oil
  • xanthan commercial product Rhodopol 23, Rhodia, France
  • mineral oil Bole spray oil (Total)
  • succinoglycan commercial product Rheozan, Rhodia, France
  • suspended at 250 g/1 in mineral oil (BANOLE ® spray oil (Total)
  • the final concentration of the heteropolysaccharides is 10 g /l for all suspensions in water.
  • Natamycin is a polyene anti-mycotic used mostly in food preservation. New applications of natamycin in agriculture have been recently patented. Natamycin is a crystalline product. Therefore natamycin liquid formulations need a structuring agent. Xanthan or succinoglycan have excellent properties as structuring agents for natamycin
  • natamycin used in this example is the commercial product
  • This suspension can be mixed easily.
  • the addition of 40 ml/1 mono propylene glycol results in thickening of the suspension, avoiding deposition of natamycin and xanthan gum.
  • the stock preparation is diluted 500 times in water, resulting in a final concentration of natamycin of 250 mg/1. After mixing with the water and stirring at 500 rpm with a propeller, at 22 °C, the suspension yields a lump-free composition within 4 minutes.
  • Xanthan gum at 0.5 g/1 in the final preparation, functions as a structuring agent for the natamycin suspension, alcohol ethoxy propoxylate (commercial product: Genapol EP 2584®), at 0,96 ml/1 in the final preparation functions as spreader.
  • Genapol EP 2584® commercial product: Genapol EP 2584®
  • Concentrated stock preparation concentrate of an experimental fungicide.
  • An experimental fungicide is made up with succinoglycan as binder.
  • the experimental fungicide is formulated as a suspension concentrate in oil (methyl oleate, containing alcohol ethoxy propoxylate (commercial product:Genapol EP 2584®)and dodecyl benzene sulfonic acid as surfactants.).
  • the succinoglycan is added to the oil formulation as a 50 % (w/w) suspension in alcohol ethoxy propoxylate (commercial product:Genapol EP 2584®).
  • the concentrated stock preparation (suspension concentrate) is prepared as follows:
  • the concentrated stock preparation (suspension concentrate) can be dissolved 200 times in water to the desired concentration of 5 g/1.
  • the ready-to-use dilution yields a clear, lump free solution within 4 minutes of stirring at 500 rpm with a propeller, at 22 °C.
  • the ready-to-use preparation contains 0.52 g/1 of xanthan and 0.68 g/1 alcohol ethoxy propoxylate (commercial product:Genapol EP 2584®), which concentrations are well within the range of, respectively, binder and surfactant concentrations commonly used in spray solutions of pesticides.
  • Genapol EP 2584® A suspension is prepared of 25 g of xanthan (commercial product Rhodopol 23, Rhodia, France) and 25 g guar gum (Brenntag, The Netherlands) in 50 g of alcohol ethoxy propoxylate (commercial product:Genapol EP 2584®).
  • the suspension exhibits good pourability without gellification. This characteristic was retained after storage at 54 °C for two weeks, which is equivalent to two years of storage at room temperature (CIPAC, method MT 46).
  • CIPAC method MT 46
  • heteropolysaccharides is formed, that dissolves within 3 minutes.
  • a suspension is prepared of 25 g of succinoglycan (commercial product Rheozan, Rhodia, France) and 25 g of locust bean gum (Brenntag, The Netherlands) in 50 g of methoxy propoxy propoanol.
  • succinoglycan commercial product Rheozan, Rhodia, France
  • locust bean gum Borenntag, The Netherlands
  • methoxy propoxy propoanol The suspension exhibits good pourability without gellification. This characteristic is retained after storage at 54 °C for two weeks, which is equivalent to two years of storage at room temperature.
  • Upon mixing with water a fine dispersion of succinoglycan is formed, that dissolves within 2 minutes.
  • the experimental design was similar to the experimental design of Example 1.
  • the composition and the dose rate of the different treatments are given in Table 11.
  • composition and dose rates were adjusted so that each plot receives the same amount of active ingredients and adjuvants (as applicable).
  • the experimental setup includes treatments with each of the copper-based fungicides alone, xanthan alone, and the combination of xanthan with each of the copper fungicides.
  • a control is added that consists of only the adjuvant components (a surfactant and a dispersant). The results of the experiment are presented in Table 12.
  • the copper fungicide copper sulfate is formulated with dispersant and surfactant as shown in Table 13.
  • composition 2 of formulated copper sulfate- based fungicidal composition (g /kg composition).
  • Xanthan (commercial product: Rhodopol, Rhodia, France) was added to the spray solution at 5 g/1 (composition 1).
  • Table 14 Effect of adding xanthan to a copper-based fungicide in control of powdery mildew of rose.
  • composition 1 The addition of xanthan to the formulation (composition 1) resulted in reduced severity compared to the control without xanthan (composition 2).

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Abstract

L'invention concerne des compositions biocides comprenant un biocide, de préférence, un biocide à base de cuivre, et un hétéropolysaccharide. Les hétéropolysaccharides préférés de l'invention comprennent le xanthane et/ou le succinoglycane. Des biocides préférés de l'invention sont des fongicides et des pesticides. La présente invention concerne une composition comprenant un hétéropolysaccharide et un liquide choisi parmi un tensio-actif et un solvant aprotique hydrophile, ou une combinaison de ceux-ci, des procédés permettant de préparer cette composition et l'utilisation de cette composition.
PCT/NL2010/050799 2009-11-27 2010-11-29 Formulations améliorées comprenant des hétéropolysaccharides WO2011065831A2 (fr)

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US20130331267A1 (en) * 2012-06-06 2013-12-12 Dow Agrosciences Llc High strength herbicidal suspension concentrates
US20140100196A1 (en) * 2012-10-05 2014-04-10 Red Surcos S.A. Phytosanitary microemulsion and the procedure for obtaining it
WO2015014743A1 (fr) * 2013-07-31 2015-02-05 Dupont Nutrition Biosciences Aps Utilisation de succinoglycane et d'un ou plusieurs glucomannane(s) ou galactomannane(s)
WO2017049141A1 (fr) * 2015-09-16 2017-03-23 Attune Agriculture, Llc Adjuvants améliorés pour produits chimiques agricoles
WO2018126017A1 (fr) * 2016-12-30 2018-07-05 Winfield Solutions, Llc Compositions d'adjuvant de réduction de dérive et procédés pour les utiliser
CN111011382A (zh) * 2020-02-17 2020-04-17 南京理工大学 β-葡聚糖和琥珀酰聚糖在防控土传真菌病害中的应用
CN113244445A (zh) * 2021-05-24 2021-08-13 广州市尚信净化工程有限公司 一种氧化亚铜-氧化刺槐豆胶抗菌凝胶
US11460371B2 (en) 2018-11-21 2022-10-04 Winfield Solutions, Llc Test environments, wind tunnels including the same, and methods of using the same
US11678602B2 (en) 2018-11-21 2023-06-20 Winfield Solutions, Llc Methods of using drift reduction adjuvant compositions
US11678660B2 (en) 2016-12-30 2023-06-20 Winfield Solutions, Llc Drift reduction adjuvant compositions and methods of using same
US11846571B2 (en) 2017-09-11 2023-12-19 Winfield Solutions, Llc Adjustable liquid trap for liquid waste drainage under differential pressure conditions
US11846570B2 (en) 2017-09-11 2023-12-19 Winfield Solutions, Llc Flow diverting wind tunnel
US11910793B2 (en) 2019-01-24 2024-02-27 Winfield Solutions, Llc Multifunctional agricultural adjuvant compositions

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US20130331267A1 (en) * 2012-06-06 2013-12-12 Dow Agrosciences Llc High strength herbicidal suspension concentrates
US20140100196A1 (en) * 2012-10-05 2014-04-10 Red Surcos S.A. Phytosanitary microemulsion and the procedure for obtaining it
WO2015014743A1 (fr) * 2013-07-31 2015-02-05 Dupont Nutrition Biosciences Aps Utilisation de succinoglycane et d'un ou plusieurs glucomannane(s) ou galactomannane(s)
EP3349577A4 (fr) * 2015-09-16 2019-04-17 Attune Agriculture, LLC Adjuvants améliorés pour produits chimiques agricoles
CN108135158A (zh) * 2015-09-16 2018-06-08 艾特恩农业有限责任公司 改善的农用化学品佐剂
AU2016323961B2 (en) * 2015-09-16 2020-10-15 Attune Agriculture, Llc Improved adjuvants for agricultural chemicals
US11297833B2 (en) 2015-09-16 2022-04-12 Attune Agriculture, Llc Adjuvants for agricultural chemicals
WO2017049141A1 (fr) * 2015-09-16 2017-03-23 Attune Agriculture, Llc Adjuvants améliorés pour produits chimiques agricoles
WO2018126017A1 (fr) * 2016-12-30 2018-07-05 Winfield Solutions, Llc Compositions d'adjuvant de réduction de dérive et procédés pour les utiliser
US11612164B2 (en) 2016-12-30 2023-03-28 Winfield Solutions, Llc Drift reduction adjuvant compositions and methods of using same
CN110139560A (zh) * 2016-12-30 2019-08-16 温菲尔德解决方案公司 降漂佐剂组合物及其使用方法
US11678660B2 (en) 2016-12-30 2023-06-20 Winfield Solutions, Llc Drift reduction adjuvant compositions and methods of using same
US11846570B2 (en) 2017-09-11 2023-12-19 Winfield Solutions, Llc Flow diverting wind tunnel
US11846571B2 (en) 2017-09-11 2023-12-19 Winfield Solutions, Llc Adjustable liquid trap for liquid waste drainage under differential pressure conditions
US11678602B2 (en) 2018-11-21 2023-06-20 Winfield Solutions, Llc Methods of using drift reduction adjuvant compositions
US11460371B2 (en) 2018-11-21 2022-10-04 Winfield Solutions, Llc Test environments, wind tunnels including the same, and methods of using the same
US11835427B2 (en) 2018-11-21 2023-12-05 Winfield Solutions, Llc Test environments, wind tunnels including the same, and methods of using the same
US11910793B2 (en) 2019-01-24 2024-02-27 Winfield Solutions, Llc Multifunctional agricultural adjuvant compositions
CN111011382B (zh) * 2020-02-17 2021-09-03 南京理工大学 β-葡聚糖和琥珀酰聚糖在防控土传真菌病害中的应用
CN111011382A (zh) * 2020-02-17 2020-04-17 南京理工大学 β-葡聚糖和琥珀酰聚糖在防控土传真菌病害中的应用
CN113244445A (zh) * 2021-05-24 2021-08-13 广州市尚信净化工程有限公司 一种氧化亚铜-氧化刺槐豆胶抗菌凝胶

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