WO2007034250A1 - Carrier materials for mosquito-larvae killing pesticides, mosquito-larvae killing products and method of manufacturing the same - Google Patents
Carrier materials for mosquito-larvae killing pesticides, mosquito-larvae killing products and method of manufacturing the same Download PDFInfo
- Publication number
- WO2007034250A1 WO2007034250A1 PCT/HU2006/000076 HU2006000076W WO2007034250A1 WO 2007034250 A1 WO2007034250 A1 WO 2007034250A1 HU 2006000076 W HU2006000076 W HU 2006000076W WO 2007034250 A1 WO2007034250 A1 WO 2007034250A1
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- WIPO (PCT)
- Prior art keywords
- mosquito
- larvae
- carrier
- killing
- carrier material
- Prior art date
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- 241000256113 Culicidae Species 0.000 title claims abstract description 40
- 239000012876 carrier material Substances 0.000 title claims abstract description 25
- 239000000575 pesticide Substances 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- 239000002131 composite material Substances 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 235000013312 flour Nutrition 0.000 claims abstract description 23
- 239000010440 gypsum Substances 0.000 claims abstract description 23
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 23
- 150000004676 glycans Chemical class 0.000 claims abstract description 22
- 229920001282 polysaccharide Polymers 0.000 claims abstract description 22
- 239000005017 polysaccharide Substances 0.000 claims abstract description 22
- 239000011148 porous material Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 17
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 17
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 17
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 17
- 239000010451 perlite Substances 0.000 claims abstract description 17
- 235000019362 perlite Nutrition 0.000 claims abstract description 17
- 239000011230 binding agent Substances 0.000 claims abstract description 16
- 239000008262 pumice Substances 0.000 claims abstract description 15
- 239000004568 cement Substances 0.000 claims abstract description 12
- 239000005667 attractant Substances 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 230000031902 chemoattractant activity Effects 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 229920000881 Modified starch Polymers 0.000 claims abstract description 6
- 235000019426 modified starch Nutrition 0.000 claims abstract description 5
- 239000004368 Modified starch Substances 0.000 claims abstract description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 4
- 235000013601 eggs Nutrition 0.000 claims abstract description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000008187 granular material Substances 0.000 claims description 42
- 239000000463 material Substances 0.000 claims description 19
- 241000209140 Triticum Species 0.000 claims description 13
- 235000021307 Triticum Nutrition 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 238000004026 adhesive bonding Methods 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 5
- 239000001913 cellulose Substances 0.000 claims description 5
- 235000010980 cellulose Nutrition 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- 229920002261 Corn starch Polymers 0.000 claims description 4
- 241000193386 Lysinibacillus sphaericus Species 0.000 claims description 4
- 239000003139 biocide Substances 0.000 claims description 4
- 239000008120 corn starch Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 108700012359 toxins Proteins 0.000 claims description 4
- 239000007900 aqueous suspension Substances 0.000 claims description 3
- 231100000654 protein toxin Toxicity 0.000 claims description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229940105329 carboxymethylcellulose Drugs 0.000 claims 6
- 229910001579 aluminosilicate mineral Inorganic materials 0.000 claims 5
- 239000011734 sodium Substances 0.000 claims 5
- 229910052708 sodium Inorganic materials 0.000 claims 5
- 150000004679 hydroxides Chemical class 0.000 claims 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims 2
- 239000004369 Alkaline modified starch Substances 0.000 claims 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims 1
- 240000005979 Hordeum vulgare Species 0.000 claims 1
- 235000007340 Hordeum vulgare Nutrition 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 240000006394 Sorghum bicolor Species 0.000 claims 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 claims 1
- 240000008042 Zea mays Species 0.000 claims 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims 1
- 150000001342 alkaline earth metals Chemical class 0.000 claims 1
- 235000019427 alkaline modified starch Nutrition 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 235000005822 corn Nutrition 0.000 claims 1
- 238000005516 engineering process Methods 0.000 claims 1
- 229940093476 ethylene glycol Drugs 0.000 claims 1
- 229960005150 glycerol Drugs 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 239000003016 pheromone Substances 0.000 claims 1
- 229940068917 polyethylene glycols Drugs 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 229920001592 potato starch Polymers 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 239000002267 larvicidal agent Substances 0.000 abstract description 44
- 241000255925 Diptera Species 0.000 abstract description 14
- 235000013339 cereals Nutrition 0.000 abstract description 10
- 229920013820 alkyl cellulose Polymers 0.000 abstract 1
- 238000001035 drying Methods 0.000 description 9
- 239000000969 carrier Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000000292 calcium oxide Substances 0.000 description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000003892 spreading Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000012670 alkaline solution Substances 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 241000193830 Bacillus <bacterium> Species 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 235000015110 jellies Nutrition 0.000 description 2
- 239000008274 jelly Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 241000256059 Culex pipiens Species 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000001912 oat gum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- -1 porosity Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/12—Powders or granules
-
- 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
- A01N25/08—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 solids as carriers or diluents
-
- 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
- A01N63/00—Biocides, pest repellants or attractants, or plant growth regulators containing microorganisms, viruses, microbial fungi, animals or substances produced by, or obtained from, microorganisms, viruses, microbial fungi or animals, e.g. enzymes or fermentates
- A01N63/50—Isolated enzymes; Isolated proteins
Definitions
- the subjects of the present invention are carrier materials for mosquito-larvae killing pesticides (carrier composites), and mosquito-larvae killing products containing these carrier composites and one or more known larvicides (larvicide composites) and procedures of their manufacture.
- carrier composites carrier materials for mosquito-larvae killing pesticides
- larvicides larvicides
- the mechanical strength of the low-density carriers is generally low due to the presence of large amount of air pores. Therefore, their spray from air-crafts is not useful due to their low level of stability towards mechanical impacts.
- the subjects of the present invention are the carrier composites, which have lower density than the density of water, containing one or more hydrulic binder, preferebly gypsum or cement or their mixtures, containing one or more foamed aluminosilicate, preferably pumicite or perlite or their mixtures, containing one or more modified polysaccharide, preferably modified starch, modified cereal flour, carboxymethyl cellulose, or (C1-2)alkyl-hydroxy-(C1-2)alkyl-ceIlulose derivatives, and containing both open and closed air-pores, furthermore the larvicide composites which consist of the abovementioned carrier composite and one or more known biological and/or chemical mosquito larvicide.
- hydrulic binder preferebly gypsum or cement or their mixtures
- foamed aluminosilicate preferably pumicite or perlite or their mixtures
- modified polysaccharide preferably modified starch, modified cereal flour, carboxymethyl cellulose
- the carrier composites consist of 0.5-99 %, preferably 20-80 % amount of foamed aluminosilicates, most preferably pumicite or perlite, 0.01-80 %, preferably 0.5-50 % amount of some modified polysaccharide, most preferably 20-40% amount of modified corn starch or wheat flour, 0.1-20% amount of a carboxymethylcellulose derivative, or 0.1-1.5% amount of an alkyl-hydroxyalkylcellulose derivative and one or more hydraulic binder, preferably gypsum or cement.
- the composites have 0.2-0.8 and 0.3-1.0 bulk densities or real densities respectively. Their mechanical strength is excellent.
- the open pores of the carrier composite grains absorb the liquid containing the active larvicide and the closed pore systems, which cannot be filled with water or liquids, ensure the low density of the grains.
- the liquid containing larvicide dissolves out after contact with water during the larvae extermination, the slow dissolution and release of the larvicide containing ,,plug" opens a way before filling up the pores completely with water. At this point, the extermination has already been finished (the larvicide completely dissolved out and killed the larva), and the water-filled pores cause increase in density of the grains.
- the grains sink.
- the time of dissolution of larvicide from the open pores and filling with water (this process cause of controlled sinking of the grains) is between 24-48 h. It is acceptable time to exterminate mosquito larva.
- the use of the multilayer (preferably periodically changing active/inactive layers, with an inactive or active outer most layer) carrier granules and larvicide granules of the present invention, the larva extermination can be retailed or periodical.
- carrier composites can stabilize the larvicide in the larvicide composites
- use of carrier composites and larvicide composites of the present invention provide a possibility to exterminate mosquito larva by using the larvicide composites even spreaded in a previous larva extermination period.
- the dried and re-wetted composites can act again in a second larva-extermination period.
- the attractant preferably wheat flour
- the attractant may be one of the components of the composite or can be carried on surface/in pores of the composite.
- the killer composite may contain a further attractant for the female mosquitoes to lay eggs on it.
- the female mosquitoes will lay eggs on the sites where extermination have been performed and will be performed again in the next season.
- the preparation methods of carrier composites mainly consist of modifying (jellyfying) the polysaccharides (in case of previously modified cellulose derivatives it means dissolution and homogenization in water), addition of gypsum/cement and foamed pumicite/perlite in the appropriate amount to the modified polysaccharide solution, homogenising the mixture and programmed heat-treatment.
- the cold aqueous suspension of polysaccharide is poured into hot water to jellyfy them.
- Another possibility is to perform this jellyfication is to treat the polysaccharides with an alkaline solution/suspension.
- alkaline solutions/suspensions may contain alkali- or alkaline-earth metal-oxide, hydroxide or hydrogencarbonate or alkali-carbonate solutions/suspensions.
- alkaline solutions/suspensions are aqueous calcium oxide or calcium hydroxide suspensions.
- Temperature may be varied between 20 and 100 0 C, the preferred temperature is the ambient temperature.
- the calcium oxide promoted jellyfication can be performed with calcium hydroxide obtained from CaO and water before mixing it with the polysaccharide powder and water, or with reaction of a powder mixture consist of CaO and the polysaccharides.
- the reaction temperature may be varied between 20 and 100 0 C, most preferably the temperature is controlled by the reaction heat of CaO and water.
- An especially preferred form of the present invention is a carrier composite which consists of a nucleus and more than one layers; the larvicide components are held by at least one of the layers (outer or inner).
- the density of the inner solid nucleus is lower than the density of the water which makes the carrier composite to float at least for 48-72 h. It is built up from a material which is mechanically strong and environmentally acceptable.
- a preferred component of this type of nucleus is an ignited foamed clay, e.g. Liapor granulate or any of the above mentioned carrier composites whose density is lower than that of water.
- the properties needed to carry the active larvicide components relate to the outer layer materials (e.g. porosity, larvicide releasing ability, etc.).
- the carrier composite granulates may be multilayered and each layer property may be the same or different.
- a preferable form of the present invention is a special kind of the multilayer carrier/larvicide composite granulates, the grains have an inner solid nucleus and may be built up from one or more outer layers which have larger density than the densitiy of water. The outer layers slowly dissolve/peel off when it comes in contact with the water.
- outer layers consist of one or more hydraulic binder and/or the above mentioned carrier composites having density larger than that of the water. Since the average density of the grains, made up of the inner layer of the lighter density and outer layers of higher density materials, is more than the density of water the larvicide composites sink after spreading.
- the thickness, type and amount of the outer layers control the dissolution/peeling off time. After dissolution/peeling of some of the outer layers, the density of the inner nucleus becomes dominant and the granulates start floating. The release of the larvicides start and the extermination of the mosquito larva begins.
- a preferred use of the larvicide compositions of the present invention is to spread a mixture of floatable and non-floatable larvicide composite granules together.
- One kind of the larvicide composite granules are sunk and will be lifted to release the active larvicide later (see above) and the other part floats immediately and exterminates the larva.
- larvicide composition of the present invention is a granule which has an outer heavy layer containing an active ingredient.
- This kind of the granule can be used to exterminate live larva at the bottom of the ponds because the sunken granules release the active larvacide in the sunken state.
- the other subjects of the present inventions are the methods to prepare the mosquito-larvae killing granules (larvicide composites). This involves combining of one or more biological or chemical mosquito-larvae killing agent as active constituent with the above mentioned carriers.
- the active ingredient could be one or more known biological larvicides or a mixture of one or more known chemical or biological larvicides such as B. Thueringiensis or B. Sphaericus protein toxins.
- One of the possibilities to prepare the larvicide composite granules is to cover the surface of the carrier composite with a glueing material containing the active ingredient or to cover the carrier composite with a pure glueing material and then treating the covered surface with the powder of the active ingredients.
- Another possibility is to prepare granules of the larvicide composite with solutions or dispersions of the active ingredients that are absorbed on the surface or in the pores of the carrier composite granules.
- solvent/glueing agents such as water, polyols or polysaccharides or their mixtures, preferably ethylene glycol, polyethylene glycols, glycerol, sorbitan, carboxymethylcellulose, and starch or alkyl-hydroxethyl cellulose derivatives can be used.
- the absorption of the solutions/dispersions may be performed via immersion, solid/liquid mixing or spraying techniques.
- the larvicide containing dried products can be stored for a long period of time. It is a further advantage of this invention.
- the Bti containing preparation that was used for 24/48 h in larva extermination was dried and later (after 2, 4, or 6 days) it was contacted with water (modeling of consecutive overflows), its efficiency in killing larva was over 80 % at 5-15 g/ha dose.
- Our preparations have excellent mosquito-extermination ability, long-term activity, good mechanical strength, light weight, good spreadability from air-craft as well controlled floating and sinking time, together with excellent degradation without formation of any harmful material.
- example 1 The procedure of example 1 was repeated but 15 kg of portland cement and the same amount of pumicite (Mardetti Bt., Erd ⁇ benye) was used instead of gypsum and perlite. The drying was performed at room temperature, the bulk density was 0.29 kg/dm3.
- pumicite Mardetti Bt., Erd ⁇ benye
- a mixture of 5.5. g wheat flour and 1.4 g of corn starch were added to an aqueous suspension of 0.2 g of calcium hydroxide in 25 ml of water. The mixture was stirred at room temperature for 1 h. 9 g of a mixture of pumicite:gypsum (4:6 in weight) was added. After granulating and drying the granules obtained had a bulk density of 0.43 g/ml and a floating time of 24 h respectively.
- Each of the the above mentioned granule was activated with a Bti (Bacillus Th ⁇ ringiensis Israelensis) (Vectobac WP, 5000 ITU ) powder suspended in an 1 % CMC (carboxymethylcellulose) solution.
- the amount of Bti was 4 % in the dried end- product.
- the drying was performed at 50 0 C.
- the bulk densities were between 0.25 and 0.70 g/ml, diameter and height of the granules were 3 and 4 mm, respectively.
- the floating time varied between 12 - 48 h.
- the efficiency of the larvae-killing was tested on Culex Pipiens larva in 24/48 cycles, with using the carrier prepared following the example 1 and example 9.
- the doses were varied between 5-15 kg/ha, when appropriate or complete efficiencies were observed.
- After two days the granules were collected, kept dry for 2 days and used again to study the efficiency (in order to modelling the drying after the overflown and a new overflown situation). Similar experiments were done after keeping the granules in dry state for 4 or 6 days. The results can be seen in Table 1.
- the killing efficiency was counted in per cent with comparing to the untreated control samples.
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- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Zoology (AREA)
- Engineering & Computer Science (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Plant Pathology (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Biotechnology (AREA)
- Microbiology (AREA)
- Virology (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The subjects of the present invention are carrier materials for mosquito-larvae killing pesticides (carrier composites), and mosquito-larvae killing products containing these carrier composites and a known larvicide (larvicide composites) and procedures of their manufacture. The carrier composites, which have lower density than the density of water, comprising one or more hydrulic binder, preferably gypsum or cement or their mixtures, containing one or more foamed aluminosilicate, preferably pumicite or perlite or their mixtures, containing one or more modified polysaccharide, preferably modified starch, modified cereal flour, carboxymethyl cellulose, or (C1-2)alkyl-hydroxy-(C1-2)alkyl-cellulose derivatives, and containing both of opened and closed air pores. The larvicide composites containing the abovementioned carrier composites and one ore more biological or chemical larvicide, feeding attractant(s) or an other attractant to call the female mosquitoes to lay eggs. Preparation methods are relating to manufacturing the carrier composites and larvicide composites.
Description
CARRIER MATERIALS FOR MOSQUITO-LARVAE KILLING PESTICIDES, MOSQUITO-LARVAE KILLING PRODUCTS AND METHOD OF MANUFACTURING
THE SAME
The subjects of the present invention are carrier materials for mosquito-larvae killing pesticides (carrier composites), and mosquito-larvae killing products containing these carrier composites and one or more known larvicides (larvicide composites) and procedures of their manufacture.
Numerous insecticide preparations have already been developed for exterminating the adult mosquitoes. Several patent specifications, such as, for example, RU2077203; GB1097790; US4855319, DE2126684; EP498720; CN1297680; CH647392; JP57128615 disclosed preparations of this kind. However the resistency and extermination of other useful insects are problematic and there are non-avoidable side-effects.
Since the mosquito-larvae mainly live at water surface their extermination can be limited to the living area of mosquito larva (it is ca. 20 % of the living area of adult mosquitoes). Having realized this fact, a lot of larvicide have been developed and disclosed - for example in the patent specifications of US1831476; US5273967; US 4707359; GB546934 - that used mineral and vegetable oil derivatives to float on the water surface. A common disadvantage of these materials is the environmental damage.
Taking into consideration the environmental damage, some selective biological larvicides have also been developed. For example the followin patent specification provide teaching in this respect: US5830722; US5830722; US4206281 , CN1050667, FR2639959; WO00/62620; EP417906; US4316959; WO98/28984; DE4133889; WO98/39974; EP349769; US4918006; WO92/8354; SU1515425, SU1305916; RU2111667; RI2031579.
Most of these contain the protein toxins of Bacillus Thϋringiensis lsraelensis (Bti) and Bacillus sphaericus. These selectively exterminated the larva of the bloodsucking mosquitoes only, because these could destroy only the inner wall of the special digestion system of the larva of blood sucking insects.
Since the mosquito larva live on water surface, some floating carriers have also been developed to carry these biological larvicides, as it has been described in the following patent specifications: US4650792, GB650132, US 4228614, US4631857,
WO98/28984. The main disadvantages of these carriers are their inability to decompose in the environment due to their artificial polymer content. Some carriers are built up from natural constituents, e.g. from cork, but their structures are heterogeneous and are mechanically not strong enough. The other carriers decompose into different parts after contact with the water and the release of the larvicide from each particulate is not homogeneous. Another kind of carrier is the ice- containing carrier family, but working with ice-containing carriers in a hot climate is very problematic.
The mechanical strength of the low-density carriers is generally low due to the presence of large amount of air pores. Therefore, their spray from air-crafts is not useful due to their low level of stability towards mechanical impacts.
The best known solution for carrying the biological larvicides is given in a Russian patent specification RU 2,113,121 in which the fermentation liquor containing the B. sphaericus toxin is jellyfied with carboxymethylcellulose and the jelly is absorbed on perlite. This composite, however, does not contain any hydraulic or other binder, therefore it cannot be granulated and has not appropriate mechanical strength for spraying from air-crafts. Perlite has open pores, therefore it does not float on water surface even for a short time.
Presently no suitable carrier is available for biological or chemical larvicides which would ensure all of the required abilities such as floating/controlled time floating on water surface, controlled release of larvicide, environmental friendly with selective components, controlled sinking and decomposition time, good storage stability and mechanical strength for homogeneous spraying from air-crafts.
Therefore, we have developed some new carrier materials for mosquito-larvae killing pesticides (carrier composites) and mosquito-larvae killing products (larvicide composites) which fulfill all of the above mentioned requirements and have also developed some appropriate procedures for their manufacture.
During our early experiments a surprising effect of the jellyfied polysaccharides was observed which acted as structure modifying agents in hardening of some hydraulic binders. Modified starch, flour or cellulose derivatives can affect not only on hardening of hydraulic binders but on the properties of the formed composites. Some of these newly developed properties are preferred to reach our demands related to good quality carrier composites of mosquito larvicides.
The subjects of the present invention are the carrier composites, which have lower density than the density of water, containing one or more hydrulic binder, preferebly gypsum or cement or their mixtures, containing one or more foamed aluminosilicate, preferably pumicite or perlite or their mixtures, containing one or more modified polysaccharide, preferably modified starch, modified cereal flour, carboxymethyl cellulose, or (C1-2)alkyl-hydroxy-(C1-2)alkyl-ceIlulose derivatives, and containing both open and closed air-pores, furthermore the larvicide composites which consist of the abovementioned carrier composite and one or more known biological and/or chemical mosquito larvicide.
The relative ratio of the components in the carrier composite depends on the required final parameters of the carrier and the larvicide composite. Generally, the carrier composites consist of 0.5-99 %, preferably 20-80 % amount of foamed aluminosilicates, most preferably pumicite or perlite, 0.01-80 %, preferably 0.5-50 % amount of some modified polysaccharide, most preferably 20-40% amount of modified corn starch or wheat flour, 0.1-20% amount of a carboxymethylcellulose derivative, or 0.1-1.5% amount of an alkyl-hydroxyalkylcellulose derivative and one or more hydraulic binder, preferably gypsum or cement. The composites have 0.2-0.8 and 0.3-1.0 bulk densities or real densities respectively. Their mechanical strength is excellent.
The open pores of the carrier composite grains absorb the liquid containing the active larvicide and the closed pore systems, which cannot be filled with water or liquids, ensure the low density of the grains. The partial filling of open pores with liquids containing the larvicide (Fig.1), which solidify during the drying process of the larvicide composite, provide a barrier for water to fill these pores completely. When the liquid containing larvicide dissolves out after contact with water during the larvae extermination, the slow dissolution and release of the larvicide containing ,,plug" opens a way before filling up the pores completely with water. At this point, the extermination has already been finished (the larvicide completely dissolved out and killed the larva), and the water-filled pores cause increase in density of the grains. When this density becomes more than the density of the water, the grains sink. The time of dissolution of larvicide from the open pores and filling with water (this process cause of controlled sinking of the grains) is between 24-48 h. It is acceptable time to exterminate mosquito larva.
The use of the multilayer (preferably periodically changing active/inactive layers, with an inactive or active outer most layer) carrier granules and larvicide granules of the present invention, the larva extermination can be retailed or periodical. Since the carrier composites can stabilize the larvicide in the larvicide composites, use of carrier composites and larvicide composites of the present invention provide a possibility to exterminate mosquito larva by using the larvicide composites even spreaded in a previous larva extermination period. The dried and re-wetted composites can act again in a second larva-extermination period.
In the present invention, we have also developed a kind of larvicide composite containing a feeding attractant for mosquito larva. The attractant, preferably wheat flour, may be one of the components of the composite or can be carried on surface/in pores of the composite.
Optionally, the killer composite may contain a further attractant for the female mosquitoes to lay eggs on it. In this case, the female mosquitoes will lay eggs on the sites where extermination have been performed and will be performed again in the next season.
Other subjects of the present invention are the methods to prepare the above mentioned carrier and larvicide composite materials.
The preparation methods of carrier composites mainly consist of modifying (jellyfying) the polysaccharides (in case of previously modified cellulose derivatives it means dissolution and homogenization in water), addition of gypsum/cement and foamed pumicite/perlite in the appropriate amount to the modified polysaccharide solution, homogenising the mixture and programmed heat-treatment.
In case of starch or flour derivatives, the cold aqueous suspension of polysaccharide is poured into hot water to jellyfy them. Another possibility is to perform this jellyfication is to treat the polysaccharides with an alkaline solution/suspension. These alkaline solutions/suspensions may contain alkali- or alkaline-earth metal-oxide, hydroxide or hydrogencarbonate or alkali-carbonate solutions/suspensions. Most preferably alkaline solutions/suspensions are aqueous calcium oxide or calcium hydroxide suspensions. Temperature may be varied between 20 and 100 0C, the preferred temperature is the ambient temperature.
The calcium oxide promoted jellyfication can be performed with calcium hydroxide obtained from CaO and water before mixing it with the polysaccharide
powder and water, or with reaction of a powder mixture consist of CaO and the polysaccharides. The reaction temperature may be varied between 20 and 100 0C, most preferably the temperature is controlled by the reaction heat of CaO and water.
During our experiments a surprising effect of temperature on the properties of the formed carrier composite granules was observed. The most important properties, e.g. the floating ability, hardness, and the ratio of closed/opened pores strongly depends on the heat-treatment time and temperature.
When we used cement as hydraulic binder, the drying at the room-temperature gave appropriate results. In case of gypsum as hydaulic binder, when the structure modifying agents were cellulose derivatives, a two-step drying, one at 80 0C for 1 h and then at 180 0C for another hour gave satisfactory results. At higher temperatures or in case of a longer heat-treatment, the bound water is eliminated, the crystal structure is broken and the mechanical strength and floating ability is lost. Using gypsum as hydraulic binder and starch derivatives as structure modifying agents, a simple drying at 80-120 0C gave satisfactory results due to the formation of an inorganic-organic hybrid xerogel structure with appropriate ratio of closed/opened pores.
An especially preferred form of the present invention is a carrier composite which consists of a nucleus and more than one layers; the larvicide components are held by at least one of the layers (outer or inner).
The density of the inner solid nucleus is lower than the density of the water which makes the carrier composite to float at least for 48-72 h. It is built up from a material which is mechanically strong and environmentally acceptable. A preferred component of this type of nucleus is an ignited foamed clay, e.g. Liapor granulate or any of the above mentioned carrier composites whose density is lower than that of water. The properties needed to carry the active larvicide components relate to the outer layer materials (e.g. porosity, larvicide releasing ability, etc.). If the inner nucleus diameter is 2 mm, and the outer layer applied onto this nucleus is also 2 mm thick, then the volume of the outer layer will be 87.5 % of the volume of all the grains, therefore the properties of the composite will be expressed as 87.5 % of the properties of the outer layer. The carrier composite granulates may be multilayered and each layer property may be the same or different.
A preferable form of the present invention is a special kind of the multilayer carrier/larvicide composite granulates, the grains have an inner solid nucleus and may be built up from one or more outer layers which have larger density than the densitiy of water. The outer layers slowly dissolve/peel off when it comes in contact with the water. These outer layers consist of one or more hydraulic binder and/or the above mentioned carrier composites having density larger than that of the water. Since the average density of the grains, made up of the inner layer of the lighter density and outer layers of higher density materials, is more than the density of water the larvicide composites sink after spreading. The thickness, type and amount of the outer layers control the dissolution/peeling off time. After dissolution/peeling of some of the outer layers, the density of the inner nucleus becomes dominant and the granulates start floating. The release of the larvicides start and the extermination of the mosquito larva begins.
It gives a chance to perform the spreading of larva killing granules before vegetation. The granules are sunk in the water after spreading (before vegetation grows). Later (after large growth of vegetation when direct spreading is not possible) the outer layer of the granules are peeled off and these are lifted to the surface, the larvicide composites release the larvicide.
A preferred use of the larvicide compositions of the present invention is to spread a mixture of floatable and non-floatable larvicide composite granules together. One kind of the larvicide composite granules are sunk and will be lifted to release the active larvicide later (see above) and the other part floats immediately and exterminates the larva.
An other possible form of larvicide composition of the present invention is a granule which has an outer heavy layer containing an active ingredient. This kind of the granule can be used to exterminate live larva at the bottom of the ponds because the sunken granules release the active larvacide in the sunken state. Once the outer layer is peeled off the granule becomes lighter than the water and floats to the surface. The inner part now starts to release the larvicide at the surface of the water.
The other subjects of the present inventions are the methods to prepare the mosquito-larvae killing granules (larvicide composites). This involves combining of one or more biological or chemical mosquito-larvae killing agent as active constituent with the above mentioned carriers. The active ingredient could be one or more known
biological larvicides or a mixture of one or more known chemical or biological larvicides such as B. Thueringiensis or B. Sphaericus protein toxins.
One of the possibilities to prepare the larvicide composite granules is to cover the surface of the carrier composite with a glueing material containing the active ingredient or to cover the carrier composite with a pure glueing material and then treating the covered surface with the powder of the active ingredients.
Another possibility is to prepare granules of the larvicide composite with solutions or dispersions of the active ingredients that are absorbed on the surface or in the pores of the carrier composite granules. In this way different kind of materials can be used as solvent/glueing agents such as water, polyols or polysaccharides or their mixtures, preferably ethylene glycol, polyethylene glycols, glycerol, sorbitan, carboxymethylcellulose, and starch or alkyl-hydroxethyl cellulose derivatives can be used.
The absorption of the solutions/dispersions may be performed via immersion, solid/liquid mixing or spraying techniques.
Since our carrier can conserve the efficacy of the larvicides such as Bti carried on surface/in pores of the composites, the larvicide containing dried products can be stored for a long period of time. It is a further advantage of this invention. The Bti containing preparation that was used for 24/48 h in larva extermination was dried and later (after 2, 4, or 6 days) it was contacted with water (modeling of consecutive overflows), its efficiency in killing larva was over 80 % at 5-15 g/ha dose.
Our preparations have excellent mosquito-extermination ability, long-term activity, good mechanical strength, light weight, good spreadability from air-craft as well controlled floating and sinking time, together with excellent degradation without formation of any harmful material.
Without limiting the invention we present several examples of the carrier and larvcide composites and their preparation methods in the following.
Example 1.
20 kg of commercial starch (HUNGRANA Rt, Szabadegyhaza, Hungary) was suspended in 20 liter cold water, next 240 liter hot water was poured into this suspension when a jelly was immediately formed. A mixture of 10 kg of perlite (ALDO Ltd., Tokόl, Hungary) and 20 kg of gypsum (Rudagipsz Ltd, Rudabanya, Hungary)
were added to the jellyfied mixture during intensive stirring, when the mixture was transformed into granules with a special mechanical tool (the granule's height is 4 mm, diameter is 3 mm). The granules were dried at 80 0C, when the hardness was good and the bulk density was 0.25 kg/dm3. The 20 % of the granules was sink after 12 h, 80 % within 24 h and all of them within 36 h.
Example 2.
The procedure of example 1 was repeated but 15 kg of portland cement and the same amount of pumicite (Mardetti Bt., Erdόbenye) was used instead of gypsum and perlite. The drying was performed at room temperature, the bulk density was 0.29 kg/dm3.
Example 3
12 kg of commercial CMC (carboxymethyl cellulose with 36 % water-soluble sodium-salt content, Zoltek Co., Nyergesύjfalu) was dissolved in 50 liter of water which was stirred till CMC was dissolved. The solution was kept for 20 min, then 10 kg of perlite powder (P1 quality, ALDO Ltd., Tδkόl) and 100 kg of gypsum (Rudagipsz Ltd., Rudabanya) were added together with water to ensure the plasticity. After 5 min mixing the mortar-like mixture was granulated, the granules were dried at 80 0C for 1 h then at 180 0C for an other hour.
Example 4
An aqueous solution of 0.7 kg of sodium-salt free carboxymethylcellulose (MAVIBOND CP-O 8000) was added to a mixture of 10 kg of perlite and 20 kg of gypsum. After granulating the mixture, the granules were dried at 80 0C, the bulk density of the product formed was 0.25 g/cm3 With increasing the amount of gypsum up to 25 or 30 kg without changing the other parameters, densities of the formed granules were changed to 0.30 and 0.35 g/cm3 respectively.
Example 5
In analogy with example 4, but using 10 kg of pumicite instead of perlite and 30 kg of gypsum, the product obtained had bulk density of 0.30 g/cm3. Using 20 kg of
cement and 10 kg of gypsum instead of 30 kg of gypsum, the bulk density was increased up to 0.35 g/cm3.
Example 6
In analogy with example 5, 0.7 % hydroxyethylcellulose (Bermocoll E411 , Pointner and Rotschaedl, Baden b. Wien) in a mixture of 30 kg of gypsum and 10 kg of pumicite was used, the bulk density of the obtained product was 0.4 kg/liter.
Example 7
10 g of wheat flour was mixed with 0.5 g of CaO. The mixture was suspended in 32 ml of water, stirred for 3 h and a mixture of 3 g pumicite and 27 g of gypsum was added. Following the above mentioned granulating and drying method, the granules obtained had a bulk density 0.65 g/ml and 48 h floating time.
Example 8
A mixture of 5.5. g wheat flour and 1.4 g of corn starch were added to an aqueous suspension of 0.2 g of calcium hydroxide in 25 ml of water. The mixture was stirred at room temperature for 1 h. 9 g of a mixture of pumicite:gypsum (4:6 in weight) was added. After granulating and drying the granules obtained had a bulk density of 0.43 g/ml and a floating time of 24 h respectively.
Example 9.
Each of the the above mentioned granule was activated with a Bti (Bacillus Thϋringiensis Israelensis) (Vectobac WP, 5000 ITU ) powder suspended in an 1 % CMC (carboxymethylcellulose) solution. The amount of Bti was 4 % in the dried end- product. The drying was performed at 50 0C. The bulk densities were between 0.25 and 0.70 g/ml, diameter and height of the granules were 3 and 4 mm, respectively. The floating time varied between 12 - 48 h.
Example 10.
The efficiency of the larvae-killing was tested on Culex Pipiens larva in 24/48 cycles, with using the carrier prepared following the example 1 and example 9. The doses were varied between 5-15 kg/ha, when appropriate or complete efficiencies
were observed. After two days the granules were collected, kept dry for 2 days and used again to study the efficiency (in order to modelling the drying after the overflown and a new overflown situation). Similar experiments were done after keeping the granules in dry state for 4 or 6 days. The results can be seen in Table 1. The killing efficiency was counted in per cent with comparing to the untreated control samples.
Table 1
Efficiency at 5-15 kg/ha dose (% mortality) Dosage, kg/ha 5 10 15
Time, day 1 80 92 96
2 72 92 100
After two days storage in dry state
1 96 96 98
2 96 100 96 After 4 days storage in dry state
1 90 88 94
2 88 88 96 After six days storage in dry state
1 88 82 82
2 88 80 84
Taking into consideration the abovementioned results, a slow-releasing mosquito-larvae killing composite material has been developed, which has the required environmental, physical, chemical, biological and mechanical properties.
Claims
1. Carrier material for mosquito-larvae killing pesticides, comprising granules having pores, and basically comprising one or more foamed aluminosilicate mineral in 0.5-99 %, one or more polysaccharide in 0.01-80 % and, the residual part is one or more hydraulic binder.
2. The carrier material for mosquito-larvae killing pesticides of claim 1 , comprising one or more foamed aluminosilicate mineral in 20-80 %, one or more polysaccharide in 0.5-50 %, and one or more feeding attractive in 0.5-2 %.
3. The carrier material for mosquito-larvae killing pesticides of claim 1 or 2, further comprising one or more feeding attractive for mosquito larvaes in 0.01-5%.
4. The carrier material for mosquito-larvae killing pesticides of claim 1 or 2, where the foamed aluminosilicate mineral is foamed pumicite or foamed perlite, the hydraulic binder is gypsum or cement, the polysaccharide is natural or chemically modified starch or cellulose derivatives, natural corn starch, carboxymethyl-cellulose or its water-soluble sodium-free derivatives or methyl/ethyl-hydroxyethylcellulose derivatives, and the feeding attractive is wheat flour.
5. The carrier material for mosquito-larvae killing pesticides of any of claims 1-3, where the polysaccharide is a kind of starch or flour or their mixtures which are modified with alkaline compounds, and the feeding attractants is a kind of chemically non-modified wheat flour.
6. The carrier material for mosquito-larvae killing pesticides of any of claims 1-4, where the alkaline-modified starch or flour are alkaline-modified wheat flour, rye flour, sorghum flour, barley flour, corn flour, corn starch, potato starch or their mixtures.
7. The carrier material for mosquito-larvae killing pesticides of claim 1 , comprising granules having pores, and basically comprising 20-70 % pumicite or perlite as foamed aluminosilicate mineral, 0.01-5 %sodium salt-decontaminated carboxymethyl cellulose as polysaccharide, 0-2 % wheat flour as feeding attractive and 10-99 % gypsum or cement as hydraulic binder.
8. The carrier material for mosquito-larvae killing pesticides of claim 7, comprising 20-40 % pumicite or perlite, 0.5-1.5 % sodium salt-decontaminated carboxymethyl cellulose, 0.8-1.2 % wheat flour and 30-70 % gypsum or cement.
9. The carrier material for mosquito-larvae killing pesticides of claim 7, comprising granules having pores, and basically comprising 30-70 %, pumicite or perlite, 0.01-5 % sodium salt-decontaminated carboxymethyl cellulose, and 0-2 % wheat flour and 10- 80 % gypsum or cement .
10. The carrier material for mosquito-larvae killing pesticides of claim 3, comprising granules having pores, and basically comprising 10-70 % pumicite or perlite, 0.01-50 % sodium-containing carboxymethyl cellulose, and 0-2 % wheat flour as feeding attractive and 10-80 % gypsum or cement as hydraulic binder.
11. The carrier material for mosquito-larvae killing pesticides of claim 3, comprising granules having pores, and basically comprising 10-70 % pumicite or perlite as foamed aluminosilicate mineral, 0.01-50 % corn starch as polysaccharide, and 0-2 % wheat flour as feeding attractive and 10-80 % gypsum or cement as hydraulic binder.
12. The carrier material for mosquito-larvae killing pesticides of any of claims 1-11 , comprising granules having pores, and having an inner core of density of 0.3-1.0 kg/dm, which carrier material comprising at least a further outer layer, where the composition of the inner core and at least one outer layer are different in their compositions.
13. The carrier material for mosquito-larvae killing pesticides of any of claims 1-10, wherein the bulk density of the carrier material is 0.2-0.8 kg/dm3 and its density is 0.3- 1.0 kg/dm3.
14. Method for the preparation of the carrier material for mosquito-larvae killing pesticides of any of claims 1-13, in which a polysaccharide powder is mixed with a solid base, or an aqueous solution or suspension of a base, then this mixture is added to water and stirred at 20-100 0C for 0.1-24 hours.
15. The method of claim 14, in which the base material is selected from oxides, hydroxides or carbonates of alkaline metals or oxides or hydroxides of alkaline earth metals.
16. The method of claim 15, in which the base material is selected from hydroxides, carbonates or hydrogen carbonates of potassium or sodium or oxide or hydroxide of calcium.
17. The method of claim 14, in which the polysaccharide and optionally a feeding attractant are dispersed in water, the mixture is allowed to stand for 10-60 min, the foamed aluminosilicate and the hydraulic binder are added to a gel-like polysaccharide-water mixture together with an amount of water required to reach a consistency to granulate the composite to obtain appropriately sized and shaped granules.
18. The method of claim 16 or 17, in which the surface of the granules is covered with a feeding attractant.
19. The method of claim 18, in which the feeding attractant is wheat flour derivatives, or its aqueous dispersions or paste-like derivatives.
20. The method of any of claims 14-19, wherein cellulose-type polysaccharides are jellyfied with water of ambient temperature for 10-60 min, and to jellify starch-type polysaccharides, those are mixed first with cold water than the cold aqueous dispersions are poured into hot water.
21. The method of claims 14, wherein at least one outer layer of different composition is fixed with granulating, a circulating box granulating or other formulating technologies.
22. Mosquito-larvae killing pesticides, which are composed of a carrier of any of claims 1-13 and one or more biological mosquito-larvae-killing material.
23. The mosquito-larvae killing pesticides of claim 22, wherein biological mosquito- larvae-killing material is 0.1-25 % protein toxins of B. thueringiensis israelensis (Bti) or Bacillus Sphaericus or their mixtures.
24. The mosquito-larvae killing pesticides of claim 22, which are composed of a carrier material of any of claims 1-13 and one or more biological or chemical or combined biological/chemical mosquito-larvae-killing material.
25. The mosquito-larvae killing pesticides of claim 22, which are comprising one or more pheromone attracting the adult female mosquitos to lay eggs, or dried and ground mosquito-eggs.
26. Method for the preparation of mosquito-larvae killing pesticides of claims 22-25, in which a carrier according to any of claims 1-13 is covered with a glueing material comprising a biological mosquito-larvae-killing material.
27. The method of claim 26, wherein covering the carrier material is obtained via soaking the carrier with a glueing material and this covered surface is contacted with a powder of the biological mosquito-larvae killing material.
28. The method of claim 26, wherein covering the carrier material is obtained via absorbing the solution/dispersion of a biological mosquito-larvae killing material solution.
29. The method of claim 26, wherein the solvent or glueing materials may be water, polyols, polysaccharides or their mixtures, preferably aqueous ethyleneglycol, polyethyleneglycols, glycerol or sorbitol solutions, or solutions/dispersions of carboxymethylcellulose, alkyl-hydroxyethylcelluloses or starch.
30. The method of claim 26 wherein the carrier material is immersed into a solution/dispersion of the mosquito-larvae killing agent, or the mosquito-larvae killing agent solutions/dispersions are sprayed onto the surface the carrier, or the mosquito- larvae killing agent solutions/dispersions are mixed with the carrier.
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HU0500862A HUP0500862A2 (en) | 2005-09-19 | 2005-09-19 | Carrier materials for mosquito-larvae killing pesticides, mosquito-larvae killing products and process for producing thereof |
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WO2009032325A1 (en) * | 2007-09-06 | 2009-03-12 | Flow Science, Inc. | Shaped items containing a human pheromone component |
WO2010014952A2 (en) * | 2008-07-31 | 2010-02-04 | Clarke Mosquito Control Products, Inc. | Extended release tablet and method for making and using same |
WO2010014952A3 (en) * | 2008-07-31 | 2010-09-16 | Clarke Mosquito Control Products, Inc. | Extended release tablet and method for making and using same |
US8343524B2 (en) | 2008-07-31 | 2013-01-01 | Clarke Mosquito Control Products, Inc. | Extended release tablet and method for making and using same |
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FR2947988A1 (en) * | 2009-07-15 | 2011-01-21 | Ligapal | Support for diffusion of volatile chemical substances e.g. pheromone, comprises a mineral matrix such as sodium aluminosilicate or calcium aluminosilicate (bentonite), unit for hardening mineral matrix, and hydrophobic coating surface |
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WO2021038415A3 (en) * | 2019-08-23 | 2021-04-22 | Fernando Thome Kreutz | Buoyant articles comprising larvicides and methods of using the same |
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HUP0500862A2 (en) | 2009-04-28 |
HU0500862D0 (en) | 2005-12-28 |
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