WO2001083600A1 - Mousse biodegradable a capacite elevee d'absorption d'huile et flottant a la surface de l'eau, procede de production et composition correspondants - Google Patents

Mousse biodegradable a capacite elevee d'absorption d'huile et flottant a la surface de l'eau, procede de production et composition correspondants Download PDF

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Publication number
WO2001083600A1
WO2001083600A1 PCT/JP2001/003662 JP0103662W WO0183600A1 WO 2001083600 A1 WO2001083600 A1 WO 2001083600A1 JP 0103662 W JP0103662 W JP 0103662W WO 0183600 A1 WO0183600 A1 WO 0183600A1
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WIPO (PCT)
Prior art keywords
water
starch
parts
foam
mass
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PCT/JP2001/003662
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English (en)
Japanese (ja)
Inventor
Kinji Tanizawa
Hitoshi Hosoda
Tsuyoshi Hirata
Norio Hishiki
Hiroshi Wadamori
Shigeki Konoo
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Sankyo Company, Limited
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Publication of WO2001083600A1 publication Critical patent/WO2001083600A1/fr

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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
    • A01N25/16—Foams
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • 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
    • 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
    • A01N25/22—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 ingredients stabilising the active ingredients
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • 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
    • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • 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
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/40—Liliopsida [monocotyledons]
    • A01N65/44—Poaceae or Gramineae [Grass family], e.g. bamboo, lemon grass or citronella grass
    • 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
    • A01N2300/00—Combinations or mixtures of active ingredients covered by classes A01N27/00 - A01N65/48 with other active or formulation relevant ingredients, e.g. specific carrier materials or surfactants, covered by classes A01N25/00 - A01N65/48
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2003/00—Use of starch or derivatives as moulding material

Definitions

  • the present invention relates to a biodegradable water-floatable foam having high oil absorption and treated by an extruder containing starch as a main component, a method for producing the same, an agrochemical composition containing the biodegradable water-floatable foam, and a process for producing the same Method and its use.
  • oily liquid substances such as oils and fats and organic solvents according to their uses.
  • powdered force s has been attempted. Since the foam of the present invention can contain an oily liquid substance, is it a force that can be applied in the above fields?
  • the present invention provides an agrochemical composition having excellent properties in which an agrochemical is contained in a foam.
  • Japanese Patent Application Laid-Open No. 7-32441 discloses that starch is used as a raw material, has excellent flexibility and elasticity, is edible and biodegradable, and can be used as a cushioning material for styrofoam substitutes.
  • a biodegradable buffer and a method for producing the same are disclosed.
  • Japanese Patent Application Laid-Open No. 9-192607 discloses a biodegradable starch resin and a method for producing the same. These are characterized by being biodegradable because they contain starch, but they are oil-absorbing and do not float in water, and the crosslinking agent added in the present invention is not added. Therefore, it did not have fine bubbles by adjusting the expansion.
  • Japanese Patent Application Laid-Open No. 5-502347 and Japanese Patent Publication No. 2785490 discloses that cross-linked starch is used or cross-linked starch is used during extruder treatment.
  • Japanese Patent Application Laid-Open Publication No. 5-502304 A discloses that cross-linked starch is used or cross-linked starch is used during extruder treatment.
  • a technique for dissolving the starch is disclosed, it indicates the insolubilization of starch, and does not attempt to control foaming to enhance water floatability or oil absorption as in the present invention. The same applies to Patent Application Publication No.
  • the pesticide such as the pesticidal composition of the present invention
  • the pesticide was adsorbed on the surface of the foam and on the air bubbles, so that when it was put into water, it adhered to the surface Oily component easily separates from foam (good oil separation) Replaces with water and gradually penetrates water to swell foam and release oily components that have been permeated and adsorbed to the outside in a short period of time The medicinal effect appears early.
  • the pesticides themselves are subjected to high-pressure and high-temperature treatment in the extruder, so that there is a possibility of decomposition and volatilization of volatile components, so that there is a problem of environmental pollution.
  • the possibility of denaturation is further increased when a cross-linking agent is mixed.
  • starch foams obtained by extruding starch have a porous structure having large cells, and thus have excellent water absorbability.
  • the foam was dissolved in water, and even if a water-repellent substance was added so as to float in water, a foam having high oil absorbing ability could not be obtained.
  • the inventors of the present invention have conducted intensive studies to solve the above problem, and as a result, added 0.1 to 5 parts by mass of a cross-linking agent to 95.0 to 99.0 parts by mass of a starch-containing substance, followed by extruder treatment.
  • the diameter of the foam is 1 to 5 times the die diameter
  • the bulk specific volume is 1 to 20 m 1 / g
  • it has an oil absorption capacity of 0.3 to 5 times its own weight
  • the diameter of the foam treated is 1 to 5 times the diameter of the die, the bulk specific volume is 1 to 20 m1 g, and has an oil absorption capacity of 0.3 to 5 times its own weight, more than 10 minutes
  • a foam floating in water could be produced, found that this foam-resistant liquid substance could be powdered, and that the foam of the present invention absorbed a pesticide or an oily substance, and in some cases, added powder. It is possible to obtain granules that are Ti-floating and can easily release an oily active ingredient within a short period of time by coating the solid pesticide or its premix or the fine powder of the solid carrier.
  • the present invention has been completed.
  • the starch-containing substances used in the present invention include corn, cornflower, corn lit, rice, rice flour, rice bran, grated tapio, grated sweet potato, potato, satsuma potato, soybean, mung bean, bran, wheat, flour, millet, millet, These include starch that can form a film after gelatinization. Starches include raw starch and processed starch.
  • raw starch such as potato starch, corn starch, high amylose corn starch, sweet potato starch, tapio starch, sago starch, rice starch, amaranth starch, and their modified starch (acid-degraded starch, oxidized starch, dialdehyde-modified starch)
  • Starch etherified starch (carboxymethyl starch, hydroxyalkyl starch, 'cationic starch, methylolated starch, etc.), esterified starch (acetate starch, phosphate starch, succinate starch, octenyl succinate starch, maleic acid starch) And higher fatty acid esterified starch), cross-linked starch, grafted starch and wet heat-treated starch, etc.
  • soft film-forming starch such as oxidized starch, acid-treated starch and lightly cross-linked starch is used. It s preferred. starch crosslinked intensity difficulty foamed in E custo ruder kuna Among these, preferred are flour, corn grits, and corn flour The flour is classified into strong flour, medium flour and light flour, but flour is particularly preferred.
  • the mixture before processing pressure extrusion out in Ekusutoruda of the present invention can be child adding a lipid and power s.
  • the lipids used in the present invention include neutral lipids (fats and oils, which are glycerides of fatty acids, including fatty oils and solid fats which are liquid at normal temperature), waxes (esters of fatty acids and higher alcohols, vaseline, Includes petroleum waxes such as raffin.), And also simple lipids such as esters of sterols Vitamin 8 and D, phospholipids that may contain nitrogen, glycolipids having sugar as a component, and sulfate and Sulfolipids with sulfo groups (Also referred to as lipid lipids), complex lipids such as those having a C-P bond, fatty acids, higher alcohols, sterols, and carotenoids, which are considered to be precursors and metabolites of the above two groups ⁇ Induced lipids such as squalene and fat-soluble
  • fats and oils which are glycerides of fatty acids (lard, semi-fat, palm kernel oil, coconut oil, soybean oil, olive oil, safflower oil, peanut oil, rapeseed oil, white oil, corn oil, cottonseed oil Wax, rice oil, sesame oil, sunflower oil, castor oil, cocoa oil, linseed oil, tung oil, eno oil, marine animal oil), vaseline, paraffin and the like are suitably used.
  • Extrusion requires thermoplasticity. Water must be added and gelatinized to make the starch thermoplastic. However, a foam formed by adding water to starch and gelatinizing contains a large amount of water power s, and therefore, the foam must be further dried in order to increase the oil absorption capacity, which is the object of the present invention. . By adding a small amount of lipid, the amount of water to be added can be minimized or not added, and a low-moisture foam can be extruded smoothly. Further, the thin lipid film strength? Form the foam surface can be increased also floating force to oil absorption ability ⁇ significantly improved water foam.
  • the amount of lipid added is 0.1 to 8 parts by mass. Sometimes the amount of addition can be limited
  • An emulsifier can be added to the mixture before being subjected to the pressure extrusion treatment by the extruder of the present invention.
  • the emulsifier used in the present invention include nonionic surfactants having an appropriate HL ⁇ value, anionic surfactants such as soap, and high-molecular substances such as proteins, and glycerin fatty acid esters and sucrose fatty acids.
  • food additives such as esters, sorbitan fatty acid esters, propylene glycol fatty acid esters, lecithin, stearoyl lactic acid, sodium oleate, morpholine fatty acid salts, and polyoxyethylene higher aliphatic alcohols.
  • the emulsifier is considered to enhance the emulsifying property between the starch-containing substance and the starches and lipids.
  • the internal and surface air bubbles are increased and the oil absorbing ability and the water floating property are improved. It is thought to have contributed to
  • the addition amount of the emulsifier is 0.1 to 5 parts by mass.
  • thermocoagulant used in the present invention refers to protein systems such as wheat protein such as soybean protein and gluten, milk protein such as casein, and thermocoagulable polysaccharides such as curdlan and methylcellulose.
  • the heat-coagulated material becomes a network-like polymer structure when melted and solidifies by heating, and when extruded, it becomes a foam having fine bubbles. Foam strength with hardness by added addition of crosslinking agent? Is formed.
  • the addition amount of the heat-coagulated substance is 1 to 30 parts by mass.
  • crosslinking agent used in the present invention examples include phosphates such as sodium tripolyphosphate, sodium trimetaphosphate, and phosphorus oxychloride, epichlorohydrin, polyepoxy compounds having two or more epoxy groups at terminal ends, formaldehyde, and glyoxal.
  • phosphates such as sodium tripolyphosphate, sodium trimetaphosphate, and phosphorus oxychloride
  • epichlorohydrin polyepoxy compounds having two or more epoxy groups at terminal ends, formaldehyde, and glyoxal.
  • Substances containing two or more functional groups capable of reacting with hydroxyl groups contained in polysaccharides such as starch and other polysaccharides such as starch, amino groups contained in proteins, and carboxyl groups (adipic acid, acrolein, bisethylene urea) , Diisocyanate, melamine resin, melamine-formalin resin, amino resin, polyamine epichlorohydrin resin, water-soluble alkylated amino resin, water-soluble methylated melamine resin, etc.), potassium pyroantimonate, calcium salt , Magnesium salts such as magnesium salts Salts can also be used.
  • non-toxic materials such as food additives are preferred.
  • Each of these cross-linking agents requires and does not require a catalyst (heating only).
  • the catalyst required for the cross-linking reaction is generally used (alkaline catalyst is usually used to obtain the optimum pH). Or an acid catalyst is added). The addition amount is preferably 0.1 to 5 parts by mass.
  • the crosslinking agent is considered to contribute to adjusting the diameter of the foam at the time of foaming, and also to contribute to water floating.
  • the starch-containing substance may contain another natural product or a derivative thereof, for example, a natural product such as a cellulose-based, protein-based or natural gum-based product or a derivative thereof.
  • Examples of the cellulose-based natural product or a derivative thereof include carboxymethylcellulose and its salts, and cellulose derivatives such as methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and hydroxypropylmethylcellulose.
  • protein-based natural products or derivatives thereof examples include gelatin obtained from animal bones, casein and its salts obtained from milk, gluten obtained from wheat, and the like.
  • natural products of the natural gum type or derivatives thereof include derivatives such as pectin, alginic acid and salts and esters thereof, pullulan, xanthan gum, elan gum, guar gum, curdlan and the like.
  • an extruder is composed of a hopper, a feeder, a screw, a barrel, a die, a heating coil, a cooling jacket, and a drive motor, and has one axis and two axes, and preferably has two axes.
  • the barrel temperature is preferably 60 to 250 ° C, preferably 80 to: L60 ° C
  • the screw rotation speed is 50 to 300 rpm, preferably 70 to 2 rpm.
  • Discharge is performed at a speed of 00 rpm, a die temperature of 90 to 200 ° C., preferably 100 to 150, and a die discharge port diameter of 0.5 to 10 mm, preferably 1 to 5 mm.
  • the conditions must be selected so that the foam is 10 times or less, preferably 1 to 5 times the diameter of the die, and has many small cells and a large specific gravity.
  • Barrel temperature is responsible for the gelatinization of the starch and the reactivity of the crosslinker.
  • the screw rotation speed controls the discharge pressure and simultaneously controls the size of the emulsified particles before discharge.
  • Die temperature affects foaming power and is related to internal moisture discharge.
  • the die outlet diameter is appropriately adjusted according to the intended use, but the foam is 10 times or less, preferably 1 to 5 times the die diameter, and contains many small bubbles. The conditions must be selected so that the foam has a high specific gravity.
  • the foam of the present invention is manufactured so as to be a foam having a specific gravity of 1 to 5 times, a large number of small open cells, and a large specific gravity.
  • the foam has a bulk specific volume of 1 to 20 ml / g, preferably 1 to 12.5 mlZg, and has an oil absorption capacity of 0.3 to 5 times, preferably 1 or more times its own weight, and 10 minutes or more, preferably 1 to 1 times. Float in water for more than an hour.
  • Measurement method of bulk specific volume Put 20 g (5 g for light) of sample into 500 m1 (1 L for light) volume graduated cylinder and read scale (m1) of graduated cylinder (high) Take the average of the lower value and the lower value).
  • Oil absorption measurement method Put 10 g of sample in a 200 ml wide-mouth glass bottle, and add a small amount of white squeezed oil. After dropping, cover the bottle and shake the bottle by hand to spread the white oil evenly on the sample.
  • the starch foam thus obtained can be used as a so-called jumbo agent or pack, which is thrown into a paddy field as a package in a water-soluble film, or as a water-floating pesticide granule that can be treated on a water surface without packaging. It can be used as a carrier.
  • Such dosage forms are useful as labor-saving agricultural chemicals, which have been strongly demanded in recent years in the context of agriculture.Particularly, granules containing a liquid concentrate at a high concentration can be prepared. It is characterized by the fact that the liquid drug substance contained therein does not sink while being occluded in the carrier, and is released into water in a short period of time, so there is no risk of harm or insufficient efficacy. are doing.
  • the pesticidal active ingredient used in the present invention is a herbicide, an insecticide, a fungicide, a plant regulator and the like used for water application to paddy fields, and there are no particular limitations on the physical properties of the pesticide itself.
  • benzulfuron-methyl azimusulfuron, imazosulfuron, pyrazosulfuronethyl, ethoxysulfuron, sinosulfuron, cyclosulfamuron, dimipelate, mefenacet, pretilachlor, molinete, pyripiccalp, tenylchlorb, esprocaprobrom Tide, Daimron, Cafuentrol, Synoptop Hopbutyl, Benzophenap, Pyrazolate, Pyrazoxifene, Benfresate, Thiobencalp, Simetrine, Dimethamethrin, Pentoxazone, Edbenzani , Dithiopyr, butachlor, o
  • the insecticidally active ingredient may be any insecticide having systemic transfer properties and an insecticide that is effective against pests inhabiting the water surface, such as rice worms and rice beetles. , Ditenviram, acetamiprid, isoxathione, ethylthiomethone, diazinon, thiocyclam, acephate, and venfuracarb.
  • the fungicidal active ingredient may be any fungicide effective for systemic blast and sheath blight, such as techopen phthalam, olibulite, azoxystrobin, and kyrupulono. Mido, pyroquilon, isoprothiolane, probenazole, thifluzamide, simeconazole, iprobenfos, tricyclazol, fipronil, flutranil, flametopil, mepronil, benomyl, and 7—fluoro-1,2,5,6-tetrahydrol 4 H—pyro mouth [3.2.1—j] quinolin-4-one and the like.
  • fungicide effective for systemic blast and sheath blight such as techopen phthalam, olibulite, azoxystrobin, and kyrupulono.
  • plant regulators include maleic hydrazide and salts thereof, abscisic acid, calcium peroxide, inabenfide, butocrazole, pachinko butolazole, and triconazole. Apentenol and psychocell.
  • pesticidal active ingredient used in the present invention one or more of the above-mentioned herbicides, insecticides, fungicides, and plant regulators can be used. Needless to say, two or more active ingredients can be combined, but two or more completely different kinds of active ingredients can be combined, for example, a herbicide and a fungicide or an insecticide.
  • liquid raw materials such as butachlor, pretilachlor, anilofos, benfrecet, cyhalofopbutyl, dimethamethrin, bensulfuron-methyl, villasulfuronethyl, azimsulfuron, ethoxysulfuron, imazosulfuron, sinosulfuron, cyclo Sulfonylurea herbicides such as sulfamuron (SU agent), cafientrol, oxadiargyl, dimelone, oxadiclomefone, phentorazamide, benzobicyclon, indanophane, pyrimino knock methyl, pyrazogyl, pyrazolate, benzophenap, etc.
  • SU agent sulfamuron
  • cafientrol oxadiargyl
  • dimelone oxadiclomefone
  • phentorazamide benzobicyclon
  • indanophane
  • Pesticides such as herbicides, silafluofundin, cycloprothrin, etofenprox, imidacloprid, ditempiram, acetamiprid, and isoxathione; Lamb, Oriburai DOO, Azokishisu thrombin, Karupuropami de, pyroquilon, isoprothiolane, Purobe Nazoru, Ji Furuzami de, fungicides such as Simeconazole is preferred, can be particularly suitably applied to the liquid conformal or S u herbicides.
  • the mixing ratio of the pesticidal active ingredient used in the present invention is not particularly limited, but is preferably as high as possible within the range that does not hinder the treatment in consideration of economy and labor saving. Usually, it is 0.1 to 80% in the pesticide granule, preferably 0.3 to 70%, more preferably 0.3 to 70%. 5 to 60%.
  • the particulate pesticidal composition having floating property on the water surface according to the present invention is preferably one in which the pesticidal active ingredient is promptly dispersed, emulsified or dissolved in water after expanding the water surface, and which is destroyed when thrown into water.
  • any of non-disintegrating substances may be used, but disintegrating ones are suitable because the pesticidal active ingredient elutes in a short time.
  • the granular pesticidal composition having a water-floating property of the present invention can contain a starch-containing substance or an enzyme acting on starch.
  • the enzymes used in the present invention include amyloglucosidase, "monoamylase, ⁇ -amylase and isoamylase.
  • Amyloglucosidase is a starch-degrading enzyme produced by bacteria and filamentous fungi. It acts on the ⁇ -1,4 bond and ⁇ -1,6 bond of starch to remove one molecule of glucose from the non-reducing end of the glucose chain. It is an exo- type enzyme that separates gradually.
  • a-Amylase is a starch-degrading enzyme produced by bacteria and filamentous fungi and has high heat resistance and pH stability.
  • /?-Amylase is a starch-degrading enzyme obtained from malt, also called malt amylase. Recently, it has also been obtained from bacteria and filamentous fungi. It is an exo-type enzyme that produces / 3-maltose sequentially from the non-reducing end of the glucose chain of 1,4-glucan such as starch, dalycogen, and dextrin. What is produced from malt is a mixture with ⁇ -amylase.
  • Isoamylase is present in yeast, rice, potato, broad bean, malt and the like.
  • An endo-type enzyme that acts on the ⁇ -1,6-glycosidic bonds in starch-based polysaccharides such as ami mouth pectin and glycogen to produce an amylose-like polysaccharide consisting of only ⁇ -1,4 bonds. is there.
  • the particulate pesticidal composition having floatability on the water surface according to the present invention is a cellulosic natural product or a natural product thereof.
  • an enzyme acting on the derivative is cellulase.
  • This enzyme is a complex enzyme composed of at least three kinds of enzymes, and often has a hemicellulase activity acting on hemicellulose, a pentasaccharide polysaccharide.
  • Cellulase hydrolyzes the 1,4-glucan bonds in cellulose to produce soluble polymers and D-glucose.
  • Cellulase is a complex enzyme and has the following activities.
  • Activity An enzyme that breaks natural cellulose.
  • C xl activity Cellulodextrin, cellotriose, celluloose-producing endo-glucanase isolated from molds such as Aspergillus.
  • cx2 activity decomposes cellodextrin produced from cxl to produce glucose.
  • the granular pesticidal composition having floatability on the water surface of the present invention contains a protein-based natural product or a derivative thereof
  • examples of enzymes acting on the protein-based product include bacterial proteases, filamentous proteases, and proteins. Pine and pepsin can be mentioned.
  • Bacterial proteases are enzymes produced by B. subtilis, and are classified into neutral proteases and alkaline lipases according to their working pH. Acts on proteins and peptides, and is used in baking, dry cleaning, household detergents, etc. Filamentous fungal proteases include those of Aspergillus origin, Rhizopus origin, Streptomyces origin, etc., and the properties vary greatly depending on the origin. It has long been used in Japan to break down soy protein in the production of miso and soy sauce. Many are thought to be a mixture of exo-type and endo-type proteases, with different amylase contents depending on the strain. Depending on the strain, cellulase, phosphatase, RNAse, and enzyme are present together.
  • Papain is produced from papaya nuts and used to prevent beer turbidity. It hydrolyzes the binding site of basic amino acids such as peptides, amides and esters, leucine and glycine, etc. It uses immature papaya as a raw material.
  • Pepsin is a peptide adjacent to an aromatic or dicarboxylic L-amino acid residue. Hydrolyze the bond. Does not act on esters or amides. It works even with extremely low ⁇ ⁇ , such as p ⁇ 1.8 to 2.5.
  • proteolytic enzymes used as anti-inflammatory drugs include trypsin, chymotrypsin, plasmin, seaplase, serratiopeptidase, bromelain and the like.
  • vectinase an enzyme acting on the pectin is vectinase. It is used as a fermentation refiner for hemp, as a clarifier for fruit juice and wine.
  • Pectin-degrading enzymes are generally called vectorinases, and are a general term for a group of enzymes involved in the hydrolysis of pectin substances. Triase and the like. Each of these also has an 'endo' type and an 'exo' type.
  • Granular pesticidal compositions force s having buoyant in water of the present invention, when they contain Arugin acid and its salts and E scan ether derivatives such as, the enzyme acts on it, arginase, is ⁇ Pia Luggin Sankai dioxygenase is there.
  • Arginase is present in digestive fluids such as abi, sazae, amefurashi, and parrotfish and produces oligosaccharides, mannuronic acid, di or triuronide.
  • Alginic acid cleaving enzyme is present in Pseudomonas and degrades alginic acid by elimination reaction to produce oligosaccharides with unsaturated bonds of peronic acid as a reducing terminal.
  • enzymes acting on the pullulan include pullulanase and isopluranase.
  • Pullulanase hydrolyzes the ⁇ _1, 6 bond of pullulan, amylopectin, and glycogen to produce maltulose, an amylose-like linear polysaccharide. Acts on pull-run to the end type.
  • Isopluranase hydrolyzes the "1,4 glucosidic bond at the reducing end adjacent to the ⁇ -1,6 glucosidic bond of pullulan to produce isopanose.
  • the water-suspendable particulate pesticidal composition of the present invention is If it contains polysaccharides or mucopolysaccharides, hyaluronidase is an enzyme that acts on them.
  • end (endo) type enzyme force Desirable.
  • exo-type enzymes do not cause any problems, they only act on the end of natural products or their derivatives, so it takes some time to decompose these natural products or their derivatives that act as binders. (It takes time to disperse.)
  • starch-containing substances and starches and the enzymes that act on them are those in which the starch-containing substance and starches are cornflower, corn grit or flour, and the enzyme is an end product.
  • Endo type ⁇ -amylase or isoamylase, more preferably, the natural product or its derivative is flour, and the enzyme is a combination of “endo amylase” or “isoamylase”.
  • the amount of the enzyme varies greatly depending on the types and amounts of the starch-containing substance and the starches and the type and the potency of the enzyme. It is 0.01 to 10 parts by mass, preferably 0.02 to 5 parts by mass, and more preferably 0.01 to 3 parts by mass. In addition, by adjusting the amount of the enzyme, the dissolution or disintegration time of the pesticide formulation in water can be adjusted.
  • the shape of the granular pesticidal composition of the present invention may be cylindrical or irregular.
  • the pesticidal active ingredient When the pesticidal active ingredient is solid, it is ground to a particle size sufficient to exert biological activity. If necessary, it is preferable to add a grinding aid, a wetting agent, a dispersing agent, etc., and dry-grind with a hammer mill, a ditto mill, etc. to obtain a premix containing a high concentration of an agricultural chemical active ingredient. Wet pulverization can also be performed by using an attritor, bead mill or the like.
  • the medium may be absorbed as it is in the carrier of the present invention.However, in the case of using water, it is dried using a suitable dryer such as a spray dryer. If dry pulverization is performed using a hammer mill / jet mill or the like, it can be handled in the same manner as the above dry premix.
  • a non-volatile liquid material suitable for the foam of the present invention prepared in advance is prepared.
  • To obtain the desired floating pesticide granules by coating the pesticidal active ingredient or dissolving the pesticidal active ingredient in an appropriate solvent and absorbing it into the foam of the present invention prepared in advance. .
  • the foam of the present invention prepared in advance is charged into a stirring mixer, a non-volatile liquid substance is added thereto, and the surface is wetted. Then, a powder premix containing a water surface spreader and other auxiliaries may be added, further stirred, and coated on the surface of the particles. Liquid or liquid pesticides can also be used in place of the non-volatile liquid material.
  • a method is generally used in which a foam of the present invention prepared in advance is charged into a stirring mixer, and a pesticidal active ingredient or a concentrated oil premix thereof, which is liquid or liquid, is added and absorbed. It is a target.
  • the surface active agent and, if necessary, other auxiliaries can be incorporated into the powder or oil premix of the pesticidal active ingredient.
  • the active ingredient for pesticides and other auxiliaries must be coated or absorbed and then added last. Is desirable. In this way, the coating or absorption process can be divided into two or more stages, and the power can be controlled.
  • the stirring mixer used is a cement mixer, a Smith mixer, a tote bottle, a Nauta single mixer, a ribbon blender, a rotary mixer. blender, the force s desirable to select a small model of grain Yabu ⁇ be mixed-in low speed, such as a V type mixer.
  • the particle size of the granules if the particle size is small, they tend to sink in water, and as granules for balmaki, they are susceptible to wind resistance. Conversely, if the particle size is larger than 2 O mm, the particles tend to be blown by the wind, and it takes time to elute the liquid ⁇ active ingredient absorbed in the center. However, this may cause uneven distribution of the pesticide active ingredient. Usually, 90% or more is in the 0.7 mm to 15 mm section, and preferably, 40% or more is in the 1 mm to 10 mm section.
  • the active ingredient of the pesticide and the foam of the present invention the water surface spreading agent used for spreading the water surface over a wide area, and other auxiliary agents are used. It can be prepared by blending agents.
  • the water surface spreader of the present invention is formulated to spread the pesticide solid agent over a wide area on the water surface.
  • a carboxylic acid such as acrylic acid or maleic acid, styrene sulfonic acid, or a vinyl group is polymerized.
  • Carboxylic acid type or sulfonic acid type polysoaps such as sodium salt, potassium salt, ammonium salt, etc .; sodium salts such as sodium oleate and potassium stearate; mono- or di-alkyl sulfosuccinates and these Surfactant with alkylene oxide added to sodium chloride, sodium dodecylbenzenesulfonate, alkyl sulfate.
  • Anionic surfactants such as monosulfo fatty acid salts, ⁇ -olefin fatty acid salts, oleyl methyl tauride salts, etc .; polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl ethers, polyoxyethylene arylaryl ethers, Various nonionic surfactants such as alkyl esters of polyoxyerbitan, silicone surfactants, acetylene surfactants, and pull-nick type surfactants; polyoxyethylene alkylaryl ether, polyoxyethylene alkyl ether, polyoxy Ethylene aryl ethers, polyoxyethylene alkyl esters, alkyl esters of sorbitan, etc.
  • phosphoric acid or sulfuric acid esters are used as phosphoric acid or sulfuric acid esters, and in some cases, a surfactant obtained by neutralizing them with a suitable alkali; Various surfactants; amphoteric surfactants; various esters of glycols such as ethylene glycol, propylene glycol, butanediol and their polymers.
  • Mono- or di-alkyl sulfosuccinates and surfactants having an alkylene oxide added thereto include not only di-alkyl sulfosuccinates generally used in pesticides, but also mono-alkyl sulfosuccinates, mono- or poly-monosulfosuccinates.
  • An alkyl ether to which monoalkylene oxide (C 2 -C 4 ) is added is prepared, and one molecule of sulfosuccinic acid includes a salt of one or two molecules reacted with one molecule.
  • Newcol 291 PG manufactured by Nippon Emulsifier Co., Ltd.
  • Neocoll SWC E Neocol SWC
  • Neocol YSK manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • Newcalgen EP-70G Takemoto Yushi Co., Ltd.
  • GEROPONSDS Shionogi Pharmaceutical Co., Ltd.
  • Perex OT-P Kao Co., Ltd.
  • Air Roll CT-1 Toho Chemical Industry Co., Ltd.
  • Genabu SB 197 0 J Hoechst Japan K.K.
  • Ripal 860K Ripal 870E (Lion Corporation), etc.
  • a-olefin sulfonate is a salt of a sulfonate derived from crude oil (petroleum), and has excellent biodegradability, is very safe for skin and eyes, and is resistant to alkali. it Te is stable, has a feature friendly to humans and the environment, such as to have excellent ⁇ aqueous, for example, the C 12 -C 16 "include one O reflex in sulfonate.
  • the salt of the one-year-old fin sulfonate is not particularly limited, and examples thereof include sodium, potassium, calcium, -ammonium and various amine salts. Thorium, ammonium or calcium salts are preferred.
  • ⁇ -olefin sulfonates include, for example, Lipolan L ⁇ —440, Lipolan L L—840, Lipolan PJ—400, K Lipolan PJ—400, Lipolan PB—800, Dt-95 (Rion stock M-3801, M-3801 G (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Hostafar OSB (manufactured by Hoechst Japan KK), and the like.
  • «- sulfofatty acid salts are sulfonated with a natural fat as a raw material, for example, C 10 -C 14 Nohi one sulfo fatty acid salts force s.
  • the salt of sulfo fatty acid salts is not particularly limited, for example, sodium, forces potassium, calcium, Anmoniumu ⁇ Pi include various amine salts such force s, sodium, Anmoniumu or calcium salts force preferred.
  • sulfo fatty acid salts include, for example, FA-615B, FA-616B, FA-617B (manufactured by Lion Corporation), Sunbase, Sunbase FM-2 (manufactured by NOF Corporation), etc. Can be mentioned.
  • O rail methyl tauride salt is a salt but was reacted Orein acid Kurorai de and ⁇ - methyl taurine, as the salt, exemplified particularly limited not force?, For example, Natoriumu force Rushiumu, potassium and Anmoniumu salts force And sodium or calcium salts are preferred.
  • oleyl methyl tauride salts include, for example, Diabon® powder (manufactured by Nippon Yushi Co., Ltd.), Hostapon® powder (manufactured by Hoechst Japan Co., Ltd.), Ark0p0nT powder (Hoechst Japan Co., Ltd.) Manufactured).
  • Alkyl sulfates are commercially available, for example, under the trade names of Radial Sulfate Emal 10 Powder-1 (manufactured by Kao Corporation) and Monogen Powder (manufactured by Daiichi Kogyo Co., Ltd.).
  • Acetylene-based surface active agents include acetylene alcohol, acetylene diol and These include surfactants to which alkylene oxide has been added.
  • Acetylene alcohol is a compound represented by the general formula HOC (R 1 ) (R 2 ) 1 C ⁇ CH (wherein R 1 and R 2 are the same or different and represent an alkyl group of C Cs).
  • R 1 is a methyl group and R 2 is an isobutyl group is surf-inol 61, R 1 and R 2 are both methyl groups, and olefin B, R 1 is a methyl group and R 2 is a
  • a chill group is commercially available under the trade name Orfin P.
  • Acetylene diol is a compound represented by the general formula HOC (R 1 ) (R 2 ) 1 C ⁇ C 1 CRiRSOH (R 1 and R 2 are the same or different and represent an alkyl group of Ci Cg.)
  • methyl R 1 is Moto ⁇ Pi
  • R 2 is is Surfynol 82
  • R 1 is those methyl and R 2 is an isobutyl group Surfynol 1 04
  • R 1 is E Ji Le group ⁇ Pi R ones Echiru group
  • Those having 2 as a butyl group include safinol DF 110, and those having a methyl group as both R 1 and R 2 are commercially available under the trade name Orfin Y.
  • the surfactant obtained by adding an alkylene oxide to the above acetylene alcohol or acetylene diol is, for example, a surfactant obtained by adding ethylene oxide and / or propylene oxide to the above acetylene alcohol or acetylene diol.
  • Agent As an alkylene oxide-added product, for example, a product obtained by adding ethylene oxide to Surfinol 104 is commercially available as Surfynol 400 series.
  • a powdered premix obtained by mixing and grinding Surfinol 104 (wax) and amorphous silicon dioxide at a weight ratio of 40:60 is Surfinol 104S, Surfinol DF110 (boxy) and amorphous
  • a powdery premix made by mixing and crushing silicon dioxide at a ratio of 40:60 is commercially available under the trade name of Surf Inol DF 110S (both manufactured by Air Port Products and sold by Nissin Chemical Co., Ltd.) .
  • the silicone surfactant introduces polyethylene oxide or polypropylene oxide or both into the terminal of methyl or dimethyl polysiloxane and / or a part of the methyl group in the side chain, and in some cases, the terminal A nonionic surfactant containing polyether-modified silicone oil as the main component, obtained by etherifying or esterifying the hydroxyl group of the polymer with an alkyl group.
  • the products are marketed under the trade names of Shikitosha Co., Ltd., Silit Series (Nippon Tunicer Co., Ltd.), Silicone Oil KF Series (Shin-Etsu Chemical Co., Ltd.), Riki Inetic (Helena Chemical Co., Ltd.), etc. .
  • Fluorinated surfactants are surfactants in which some or all of the hydrogen atoms of ordinary anionic, nonionic, cationic or amphoteric surfactants are replaced with fluorine atoms, and are known for their excellent surface tension lowering power.
  • the Unidyne series manufactured by Daikin Industries, Ltd.
  • the MegaFack series manufactured by Dainippon Ink & Chemicals, Inc.
  • the lid series manufactured by Neos Corporation
  • the Surflon series manufactured by Asahi Glass Co., Ltd.
  • the product is sold under the brand names F-top (manufactured by Tokemi Products).
  • Glycol ethers and esters are ethylene glycol, propylene glycol, butanediol, and ethers or esters in which one or both of the terminal hydroxyl groups of these polymers have been substituted with an appropriate alkyl or carboxylic acid group.
  • He G ethylene glycol monohexyl ether, Japan Emulsifier Co., Ltd.
  • He DG dimethylene glycol monohexyl ether, Nippon Emulsifier Co., Ltd.
  • EHG ethylene glycol mono 2-ethylhexyl ether, Nippon Emulsifier Co., Ltd.
  • EHDG dimethylene glycol mono-2-ethylhexyl ether, (Nippon Emulsifier Co., Ltd.).
  • Alkyl esters of carboxylic acids include carboxylic acids such as coconut oil fatty acids, lauric acid, oleic acid, and lactic acid, and methyl esters of polybasic carboxylic acids such as maleic acid, citric acid, fumaric acid, adipic acid, glutaric acid, and phthalic acid.
  • Alkyl esters such as, ethyl, propyl, butyl, hexyl, ethylhexyl, lauryl, and oleyl.
  • exephal MC coconut fatty acid methyl, Kao Corporation
  • exephal M-0L methyl oleate, kao Co., Ltd.
  • Vinicizer 30 Isoptyl oleate, Kao Corporation
  • Vinicizer 124 dialkyl phthalate, Kao Corporation
  • butyl lactate Meatino Chemical Laboratory Co., Ltd.
  • the amount of the water surface spreader used in the present invention depends on the type and content of the active pesticide, although it varies depending on the formulation and dosage form, such as the type of spreading agent and its method of addition, and the type and amount of other components, it is usually 0.1 to 30%, preferably 0.1% in the solid agricultural chemical. It is 3 to 20%, more preferably 0.5 to 10%.
  • the auxiliary agricultural chemicals of the present invention may contain other auxiliary agents such as a non-volatile liquid substance, an emulsifier, a dispersant, a wetting agent, a diluent, a water repellent, a particle growth inhibitor and a stabilizer.
  • a non-volatile liquid substance can be used if necessary.
  • the non-volatile liquid substance does not adversely affect the pesticidal active ingredient, such as particle growth and decomposition, and can uniformly coat the pesticidal active ingredient on the foam of the present invention.
  • the material has a high flash point force s , a low viscosity and a specific gravity of less than 1.
  • most pesticidally active ingredients have a specific gravity of 1 or more.
  • fastening the emulsified particles as possible for a long time in water, in order to widely diffuse in paddy fields, it forces s often specific gravity are use a solvent less low viscosity than one.
  • mineral oils such as low-viscosity liquid paraffin, isoparaffin, machine oil, polybutene, paraffinic, naphthenic, and aromatic high-boiling solvents; vegetable oils such as oak oil, soybean oil, and rapeseed oil; whale oil, sardine oil Animal oils such as silicone oils and derivatives thereof; mono- or polycarboxylic acids such as oleic acid, lactic acid, coconut oil fatty acid, maleic acid, fumaric acid, phthalic acid, adipic acid, and various esters thereof; tributyl Plasticizers such as various esters of phosphoric acid such as phosphitol trichloroethyl phosphate; lactones such as ⁇ - caprolactone and ⁇ -butyral lactone; ⁇ -methylpyrrolidone; Examples thereof include various liquid surfactants, and preferably, low-viscosity liquid paraffin, machine oil, isoparaffin, or various alkyl ethers.
  • Liquid paraffin such as Super Oil Series, Sumoil II Series (Nippon Petrochemical Co., Ltd.), Liquid Paraffin No Series (Chuo Kasei Co., Ltd.); Daphne Oil Series (Idemitsu Kosan Co., Ltd.) ), Etc .; and isoparaffins such as the Isopa series and the Isosol series (manufactured by Nippon Petrochemical Co., Ltd.). Two or more of these can be used in combination.
  • the amount of the non-volatile liquid substance used in the present invention depends on the type of the pesticidal active ingredient and other factors. Although it depends on the type and amount of the auxiliaries, it is preferable that the amount is as small as possible as long as the aging stability and physical properties of the solid pesticide are not affected.
  • the compounding amount is generally 1 to 60%, preferably 2 to 50%, more preferably 3 to 40%.
  • the emulsifier used in the present invention is used as needed to emulsify a liquid pesticidal active ingredient or a solution of the pesticidal active ingredient in water, and an emulsifier for a normal emulsion is selected according to the pesticidal active ingredient and the solvent. You can select and use them in the same way as you do.
  • the compounding amount of the milking agent used in the present invention is generally 0.01% to 30%, preferably 0.03% to 15%.
  • the dispersant used in the present invention is used for suspending and dispersing an agricultural chemical active ingredient in water.
  • examples thereof include lignin sulfonate, (alkyl) naphthalene sulfonate and its condensate, and phenol.
  • Sulfonates and condensates thereof Sulfonates and condensates thereof, styrene sulfonate condensates, salts of maleic acid and styrene sulfonic acid condensates, salts of carboxylic acid condensates such as acrylic acid and maleic acid, alkylbenzene sulfonates, lauryl Salts of sulfates, salts of polyoxyethylene alkyl ether sulfates, salts of polyoxyethylene alkyl ether ether sulfates, borooxyethylene alkyl ether phosphates and their salts, polyoxyethylene alkyl esters
  • Anionic surfactants such as ether phosphates and their salts Phosphates such as sodium phosphite and sodium hexametaphosphate can be mentioned, and nonionic, cationic, and zwitterionic surfactants can also be used by selecting appropriate ones. These dispersants are also useful are the
  • the amount of the dispersant and wetting agent used in the present invention is generally 0.1 to 30%, preferably 0.1 to 20%, and more preferably 0.2 to 15%. is there.
  • the diluent used in the present invention is a diluent for preparing a concentrated premix of a solid pesticidal active ingredient, and includes, for example, bentonite, talc, clay, diatomaceous earth, amorphous silicon dioxide, calcium carbonate, Mineral substances generally used as carriers of agricultural chemicals such as magnesium carbonate ⁇ In addition to powdered powder, various resin powders such as vinyl chloride, vinylidene chloride, polyethylene and polypropylene, and sugars such as glucose, sugar and lactose , Starch and its derivatives, silk crystalline cellulose, wood flour, sawdust, rice bran, bran, rice husk powder, Organic substances such as coffee beans powder, coconut shell powder, activated carbon, cellulose powder, licorice powder, water-soluble inorganic salts such as sodium sulfate, ammonium sulfate, and potassium chloride, and urea.
  • various resin powders such as vinyl chloride, vinylidene chloride, polyethylene and poly
  • the compounding amount of the extender used in the present invention is generally 0.1 to 80%, preferably 0.2 to 50%, more preferably 0.5 to 20%.
  • the water repellent used in the present invention is mainly used when the water solubility of the pesticidal active ingredient is high, so that the elution of the pesticidal active ingredient is suppressed and the water repellent is spread over the surface of the water as widely as possible.
  • fatty acid salts such as magnesium stearate and calcium stearate
  • higher alcohols such as stearyl alcohol
  • higher fatty acids such as stearic acid, silicon oil and its derivatives
  • fluorine-based surfactants, thiothion-based compounds surfactants, hydrophobic silica s like force liquid paraffin ⁇ Pi machine oil.
  • the amount of water repellent agent used in the present invention, agrochemical active ingredient type and physical properties by different ⁇ Ru force s, the amount thereof is generally 0. 0 5-1 0%, preferably 0. 1-5% o
  • the particle growth inhibitor or stabilizer used in the present invention is added if necessary according to the properties of the pesticidal active ingredient.
  • pigments, bittering agents, and various other auxiliaries can be added as necessary.
  • the pesticidal active ingredient After the pesticide granules of the present invention have spread on the water surface, the pesticidal active ingredient must be dispersed, emulsified or dissolved in water promptly, so that the amount of the wetting agent, dispersant, emulsifier, etc. is adjusted. It is desirable that the pesticide granule of the present invention obtained by the above method shows a good water-floating spreadability with a spreadability index of 5 or more by the following method.
  • the “expansion index” is a numerical value of the spreadability of a solid pesticide with floating on the water surface on the water surface in the range of 0 to 15 points (out of 15 points).
  • the water surface spreadability is good, preferably 5 points or more, more preferably 7 points or more, and still more preferably 9 points or more.
  • the test method for the water surface spreadability is as follows.
  • the thus obtained pesticide granules having a water-floating property according to the present invention may be directly dispersed in a paddy field by hand or using a suitable granulator, or may be dispersed in a water-soluble film or sheet. It may be packaged in paper and thrown into rice fields.
  • so-called picture frame treatment is performed along the ridge without entering the paddy field and performing uniform treatment, or without uniform treatment using a granulator. The granules spontaneously spread on the surface of the water alone, and the same effect as that of the uniform treatment can be obtained.
  • the water-soluble paper is made of a water-soluble film or sheet, and has a property of dissolving or dispersing in cold water and releasing the internal granules.
  • examples of such materials include polyvinyl alcohol (PVA), cellulose such as sodium salt of carboxymethyl cellulose, polyether such as polyethylene oxide, and polysaccharide such as pullulan. Any of these can be used in the invention.
  • the water-soluble nonwoven fabric includes not only a water-soluble nonwoven fabric but also a sheet made of a laminated material obtained by laminating a suitable water-soluble film on a water-soluble nonwoven fabric.
  • PVA force film itself has a spreadability properties? Particularly preferred.
  • the preferred PVA has a degree of polymerization of about 1000 to 2000 and a degree of saponification of about 85 to 95%, so that a small amount of carboxylic acid, sulfonic acid, etc. is copolymerized in the polymer.
  • a plasticizer, a stabilizer, a pigment, and the like which are added to a normal PVA film, can be contained.
  • the thickness of these water-soluble films or sheets is preferably from 20 to 100. When the thickness is 2 or less, the strength is insufficient and the film is easily broken, which may cause a problem when used as a packaging bag.
  • the 1 0 0 m becomes more than one time to dissolve in water Karu example, price force? Not a good idea because higher.
  • the weight of one packet is usually from 10 to 200 g, preferably from 20 to 100 g, and more preferably from 25 to 70 g, considering the ease of throwing.
  • the shape of the package is generally a rectangle or a square having a side of 1 to 30 cm, but is not limited thereto, and there is no problem even if it is a polygon, a circle, a sphere, a cylinder, or the like.
  • each side may be sealed with glue, but ultrasonic waves, high frequency waves, heat seals, and the like can be used, and a heat seal is preferable from the viewpoint of workability.
  • thermocompression bonding As a method of heat sealing, for example, a heat sealer is used, and a method of thermocompression bonding at a temperature of 20 to 150 ° C lower than the melting point of the water-soluble paper at a linear pressure of 3 to 100 kg Zcm is used. be able to.
  • the pesticide granule of the present invention spreads widely on the water surface and spreads the active ingredient of the pesticide over a wide range, it is not necessary to forcibly throw the pesticide far away in a normal paddy field, and a few meters from the ridge. It is enough to drop it on the water surface.
  • the obtained solid preparation is packaged in a bag or box, such as a paper bag, a resin bag, or a resin bag with aluminum or glue laminated, or aluminum or copper, so it is stable over time against moisture absorption. It is. Therefore, it is not necessary to pay attention to moisture absorption, but water-soluble paper breaks when exposed to water, so it is desirable to use a water-proof exterior.
  • a bag or box such as a paper bag, a resin bag, or a resin bag with aluminum or glue laminated, or aluminum or copper
  • Table 3 shows the properties of the obtained composition.
  • the oil separability in Table 3 is indicated by a symbol, and is represented by ⁇ , ⁇ , or X in order of the oil separability.
  • the operating conditions of the Extruder (2-axis Extruder “100” manufactured by Suehiro EPM) are as follows: rotation speed: 80 to 160 rpm, ratio of inner diameter to barrel LZD: 12, raw material input: 40 to 80 kg / hr, Pressure: 30-50 kg / cm 2 , Die opening diameter: 2.5 mm (1.5 mm for sample numbers 4 and 12), 10 holes in series, barrel temperature: 80-90 ° C, die temperature: 80- The temperature was 120 ° C.
  • Butachlor raw material (a. I. 90%) 43.75 parts, EHDG (diethylene glycol mono 2-ethylhexyl ether, manufactured by Nippon Emulsifier Co., Ltd.) 3.0 parts, NE-260 9 (Polyoxyethylene polycyclic phenyl ether, manufactured by Nippon Emulsifier Co., Ltd.) 1.5 parts, and 08 (70% calcium dodecylbenzenesulfonate, Nippon Emulsifier Co., Ltd.) 1.50 parts After mixing, an oil premix was obtained.
  • Equisulfuron bulk material (a.i.
  • Example 4 Absorb, add 9.35 parts of powder premix, mix and coat, Further, 2.50 parts of LocaHelp 439 was added and mixed and coated to obtain a pesticide granule of the present invention containing 37.5% of ptacrol and 0.85% of ethoxysulfuron. 40 g of the granules was packaged in Hythelon C-200 (thickness 40 !!! ?? eight film, manufactured by Nichigo Film Co., Ltd.). This product was applied at a rate of 5 packs per 10 a paddy field. (Example 4)
  • An oil premix was obtained by mixing 43.75 parts of a butachlor raw material and 3.00 parts of EHDG. Separately, 0.95 parts of etoquisulfuron bulk material, RocaHelp 43 9 6.40 parts, Vanirex N (sodium ligninsulfonate, manufactured by Nippon Paper Industries Co., Ltd.) 1.00 part and GEROPON SDS (Nato dioctylsulfosuccinate) Lium, Shionogi & Co., Ltd.) 1.00 part was mixed and ground with a hammer mill to obtain a powder premix. The foam of Sample No.
  • Example 7 of Example 2 4 1.40 parts was charged into a Nauta mixer, 46.75 parts of oil premix was added, mixed and absorbed, and 9.35 parts of powder premix was added. The mixture was coated, and 2,50 parts of RocaHelp 439 was added and mixed to obtain an agricultural chemical granule of the present invention containing 37.50% of butachlor and 0.85% of ethoxysulfuron. The obtained granules (40 g) were packaged in Hythelon C-200 to obtain the paddy rice field preparation of the present invention. This product is tossed at a rate of 5 packs per 10 a paddy field.
  • a foamed carrier was produced using the raw material blending recipe shown in Table 6 below and using 2-axle extreux.
  • Table 7 shows the physical properties of the obtained foamed carrier.
  • the operating conditions of the extruder (2-axis extruder ⁇ 100 manufactured by Suehiro EPM) are as follows: rotation speed: 80 to 160 rpm, ratio of inner diameter to barrel L / D: 12, raw material input: 40 Up to 80 kg / hr, pressure: 30 to 50 kgZcm2, die opening diameter: 1.5 mm, 10 holes in series, barrel temperature: 80 to 90 ° C, die temperature: 80 to: L 20 V.
  • rotation speed 80 to 160 rpm
  • ratio of inner diameter to barrel L / D 12
  • raw material input 40 Up to 80 kg / hr
  • pressure 30 to 50 kgZcm2
  • die opening diameter 1.5 mm
  • 10 holes in series 10 holes in series
  • barrel temperature 80 to 90 ° C
  • die temperature 80 to: L 20 V.
  • Butachlor raw material ( a . 90%) 43. 75 parts, EHDG (diethylene glycol mono 2-ethylhexyl ether, manufactured by Nippon Emulsifier Co., Ltd.) 3.00 parts, NE-2609 (polyoxyethylene polycyclic phenyl ether) 0,50 parts, DBC (70% calcium dodecylbenzenesulfonate, manufactured by Japan Emulsifier Co., Ltd.) 0.50 parts and Piocrystase M8 ( ⁇ -amylase, manufactured by Daiwa Kasei Co., Ltd.) 0 20 parts were mixed to obtain an oil premix.
  • EHDG diethylene glycol mono 2-ethylhexyl ether, manufactured by Nippon Emulsifier Co., Ltd.
  • NE-2609 polyoxyethylene polycyclic phenyl ether
  • DBC 50% calcium dodecylbenzenesulfonate, manufactured by Japan Emulsifier Co., Ltd.
  • Example 6 40.20 parts of the foamed carrier of Sample No. 1 was charged into a Nauta mixer, 47.95 parts of an oil premix was added, mixed and absorbed, and 9.35 parts of a powder premix was added and mixed and coated. Further, 2.50 parts of RocaHelp 439 was added and mixed and coated to obtain an agrochemical preparation of the present invention containing 37.50% of butachlor and 0.85% of ethoxysulfuron. 40 g of the obtained preparation was packaged in Hythelon C-200 (a PVA film having a thickness of 40 ⁇ m, manufactured by Nichigo Film Co., Ltd.) to obtain a preparation for casting rice paddy of the present invention. The product is tossed at a rate of 5 packs per 10 a of paddy field.
  • Hythelon C-200 a PVA film having a thickness of 40 ⁇ m, manufactured by Nichigo Film Co., Ltd.
  • Example 7 37.50% of butachlor and 0 of ethoxysulfuron were obtained in the same manner as in Example 1 except that the foamed carrier of Example 6 Sample No. 1 was changed to the foamed carrier of Example 6 Sample No. 2. An agrochemical formulation of the invention containing 85% was obtained. 40 g of the obtained preparation was packaged in Hythelon C-200 to obtain the preparation for throwing rice in the present invention. PC so-called recommendation 662
  • Example 7 Piocrystase 8 was 0.20 part, Piocrystase 8 was 0.10 part, and Protin AS 10 (Proteases, manufactured by Daiwa Chemical Co., Ltd.) 0.10
  • an agricultural chemical formulation of the present invention containing 37.50% of butachlor and 0.85% of ethoxysulfuron was obtained.
  • 40 g of the obtained preparation was packaged in Hythelon C-1200, and the paddy field preparation of the present invention was used. The product is tossed at a rate of 5 packs per 10 a of paddy field. (Example 10)
  • Pesticide formulation containing oxidized starch, corn flour, cellogen ⁇ ⁇ , ⁇ -amylase and cellulase, and formulation for throwing into paddy fields
  • Example 7 Piocrystase 8 contained 0.20 parts, Pioclase Yuichize 8 produced 0.10 parts, and cell mouth syn (Cellulase, manufactured by Hankyu Bio Industries Co., Ltd.).
  • Example 7 Except that the foamed carrier of Sample No. 1 was changed to the foamed carrier of Example 6, Sample No. 3 was changed to 10 parts, and butachlor was changed to 37.
  • An agrochemical preparation of the present invention containing 0% and 0.85% of ethoxysulfuron was obtained. 40 g of the obtained preparation was packaged in Hythelon C-200 to obtain the preparation for throwing into a paddy field of the present invention. The product is tossed at a rate of 5 packs per 10 a of paddy field.
  • Example 4 No granules sinking after 24 hours. Then it begins to sink 10
  • Example 5 No granules sink after 24 hours. Then it begins to sink 12
  • Example 6 The foamed carriers of Example 6 were all non-disintegrating, but the pesticide preparations of Examples 7 to 10 containing these foaming carriers and the enzyme all disintegrated within 30 minutes of the treatment.
  • a foam force s floating on the water surface and having extremely excellent oil absorbing ability can be obtained.
  • a foam can be used, for example, as a paddy throwing agent or a carrier for pesticides applied to rice paddies, and since it can contain a high concentration of a liquid drug substance, the amount of chemicals to be applied to paddy fields can be significantly increased. Can be reduced.
  • Such technology greatly contributes to recent agriculture, which requires labor-saving power due to the aging of farmers.

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Zoology (AREA)
  • Agronomy & Crop Science (AREA)
  • Plant Pathology (AREA)
  • Environmental Sciences (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Pest Control & Pesticides (AREA)
  • Toxicology (AREA)
  • Natural Medicines & Medicinal Plants (AREA)
  • Biotechnology (AREA)
  • Microbiology (AREA)
  • Mycology (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne une mousse obtenue en ajoutant 0,1 à 5 parties en poids d'un agent de réticulation à 95,0 à 99,0 parties en poids d'une substance contenant de l'amidon et en passant le mélange dans un extrudeur dont le diamètre est de un à cinq fois le diamètre de la filière. Cette mousse possède un volume spécifique brut compris entre 1 et 20 ml/g, une capacité d'absorption d'huile comprise entre 0,3 et 5 fois son propre poids et flotte sur l'eau pendant au moins 10 minutes ou plus.
PCT/JP2001/003662 2000-04-28 2001-04-26 Mousse biodegradable a capacite elevee d'absorption d'huile et flottant a la surface de l'eau, procede de production et composition correspondants WO2001083600A1 (fr)

Applications Claiming Priority (2)

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JP2000129040 2000-04-28

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN104177584A (zh) * 2013-05-28 2014-12-03 江苏瑞丰科技实业有限公司 一种油烟高倍吸附净化材料

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KR100768273B1 (ko) * 2005-12-23 2007-10-18 주식회사 영일케미컬 생력화 발포성 농약 조성물의 제조 및 사용방법
CN108479294B (zh) * 2018-04-04 2019-07-05 黄俊龙 一种废气净化方法
CN114467929A (zh) * 2022-02-24 2022-05-13 山西巴盾环境保护技术研究所 一种可长期悬浮在水面并可回收的灭蚊幼材料其制备方法与应用
CN114669271A (zh) * 2022-03-21 2022-06-28 西南石油大学 一种高效持久耐高温高压油水分离材料的制备方法

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JPH05320397A (ja) * 1992-05-19 1993-12-03 Nippon Synthetic Chem Ind Co Ltd:The 崩壊性発泡成形体
JPH06136168A (ja) * 1991-11-15 1994-05-17 Nobuo Shiraishi 澱粉関連物系発泡体の製造方法
JPH06271698A (ja) * 1993-03-19 1994-09-27 Nippon Synthetic Chem Ind Co Ltd:The 崩壊性発泡成形体
JPH0769803A (ja) * 1993-08-26 1995-03-14 Nippon Kayaku Co Ltd 水面拡散型固形農薬製剤
WO1995031899A1 (fr) * 1994-05-24 1995-11-30 Nippon Shinyaku Co., Ltd. Composition de pesticide, preparation pesticide et procede de production
EP0696611A2 (fr) * 1994-08-08 1996-02-14 NOVAMONT S.p.A. Matières plastiques biodégradables sous forme de mousse
JPH0971677A (ja) * 1995-09-07 1997-03-18 Kousui Kagaku Kogyo Kk 生分解性緩衝材およびその製造方法
JP2000007805A (ja) * 1998-06-24 2000-01-11 Toyo Purasuto:Kk 生分解性樹脂発泡体
JP2000053792A (ja) * 1998-08-05 2000-02-22 Sanwa Kako Co Ltd 生分解性樹脂発泡体及びその製造方法
JP2000109592A (ja) * 1998-10-07 2000-04-18 Chisso Corp 膨潤性澱粉系発泡体

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EP0530987A1 (fr) * 1991-08-08 1993-03-10 MITSUI TOATSU CHEMICALS, Inc. Composition de polymère dégradable
JPH06136168A (ja) * 1991-11-15 1994-05-17 Nobuo Shiraishi 澱粉関連物系発泡体の製造方法
JPH05320397A (ja) * 1992-05-19 1993-12-03 Nippon Synthetic Chem Ind Co Ltd:The 崩壊性発泡成形体
JPH06271698A (ja) * 1993-03-19 1994-09-27 Nippon Synthetic Chem Ind Co Ltd:The 崩壊性発泡成形体
JPH0769803A (ja) * 1993-08-26 1995-03-14 Nippon Kayaku Co Ltd 水面拡散型固形農薬製剤
WO1995031899A1 (fr) * 1994-05-24 1995-11-30 Nippon Shinyaku Co., Ltd. Composition de pesticide, preparation pesticide et procede de production
EP0696611A2 (fr) * 1994-08-08 1996-02-14 NOVAMONT S.p.A. Matières plastiques biodégradables sous forme de mousse
JPH0971677A (ja) * 1995-09-07 1997-03-18 Kousui Kagaku Kogyo Kk 生分解性緩衝材およびその製造方法
JP2000007805A (ja) * 1998-06-24 2000-01-11 Toyo Purasuto:Kk 生分解性樹脂発泡体
JP2000053792A (ja) * 1998-08-05 2000-02-22 Sanwa Kako Co Ltd 生分解性樹脂発泡体及びその製造方法
JP2000109592A (ja) * 1998-10-07 2000-04-18 Chisso Corp 膨潤性澱粉系発泡体

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104177584A (zh) * 2013-05-28 2014-12-03 江苏瑞丰科技实业有限公司 一种油烟高倍吸附净化材料

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TWI283256B (en) 2007-07-01

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