CN1282515A - Method of preparing underwater foamed type solid composition of agricultural chemical product - Google Patents

Method of preparing underwater foamed type solid composition of agricultural chemical product Download PDF

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Publication number
CN1282515A
CN1282515A CN00100921A CN00100921A CN1282515A CN 1282515 A CN1282515 A CN 1282515A CN 00100921 A CN00100921 A CN 00100921A CN 00100921 A CN00100921 A CN 00100921A CN 1282515 A CN1282515 A CN 1282515A
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parts
agricultural chemical
composition
water
mixture
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CN1166292C (en
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加藤进
铃木芸子
中村完治
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Kumiai Chemical Industry Co Ltd
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Kumiai Chemical Industry Co Ltd
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—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
    • A01N25/10—Macromolecular compounds

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

Abstract

A solid agricultural chemical molded composition for paddy fields, as an essential component, includes an agricultural chemical-active ingredient, a foaming component generating a gas in water, a water-soluble polymeric compound solid at the ordinary temperature and a water-repellent agent.

Description

The method of the solid composition of agricultural chemical product of preparation underwater foamed type
The present invention is that the application number on July 8th, 1992 application is dividing an application of 92105653.2 patent application.
The present invention relates to a kind of method for preparing the solid composition of agricultural chemical product of underwater foamed type.
The composition that is used for the agricultural chemical of paddy field comprises the preparation of formulating agricultural chemicals, is designed to that dilute with water uses and is designed to that dilute with water not itself uses by them.The former needs a bulk container to preserve a large amount of water when preparation agricultural chemicals solution, to use or to preserve such agricultural chemicals solution, and the equipment that uses this solution, further, in order to use agricultural chemicals solution equably, must there be a people to carry the apparatus that spreads pesticides and enters into paddy field application by throwing them, the latter, need application specific equipment to handle large-area paddy field, in some cases, must have a people to enter into paddy field and go to use.Under the situation that is granule, might not use equipment and use them by hand, but this need be at one section long time of paddy field work.Like this, it is very arduous to the peasant that agricultural chemical is applied to paddy field, and agricultural chemical in use will to touch skin or be bonded at also be dangerous on the clothes.
In this case, studied safety and to save labour's mode, do not need walking to go into the method for the agricultural chemical of paddy field use, for example, advise a kind of method, a kind of preparation wherein can float in the water, is sprinkled into (Japanese unexamined patent publication No.99327/1978) from the ridge of rice field.Yet this preparation can not all be dispersed in the surface of water, and this composition can waft by wind sometimes cause phytotoxicity to the rice shoot of rice.Further, when used carrier is water-insoluble, carrier continues floating on the water surface, even is dissolved in the water at the active component of agricultural chemical, and these carriers will enter the pollution that the korneforos causes paddy field and river together with water.On the other hand, in the method for having reported, when water is irrigated, flowable preparation is added dropwise to the porch (Japanese seed science, the 27th research association's wall bulletin " by of the control of mobile preparation " and the 28th research association's wall bulletin " by of the control (2) of mobile preparation ") of paddy field to paddy field weed to the paddy field seed.Yet this method exists active component equally distributed problem in paddy field of an agricultural chemical, and is difficult to the herbicidal effect that reaches constant.
On the other hand, suggestion is at insecticides (Japanese unexamined patent publication No.206301/1984), has in agent for removing grass in paddy field granule or tablet (the patent publications No.27939/1972 that Japan examine) and the herbicide for paddy field (Japanese unexamined patent publication No.128301/1991) to contain the foaming agent of being made up of tartaric acid and sodium bicarbonate and join during agricultural chemical fills a prescription.Further, suggestion with stable composition, foam (Japanese unexamined patent slice thing No.56434/1982) add therein viscosity at least the dimethyl polysiloxane of 300CS (siloxanes) or its modified product to prevent foaming capacity variation in the storage process.
It is problematic using these preparations of this blowing agent, for example, insecticides, it is to store a very long time post-foaming ability to be tending towards variation that agent for removing grass in paddy field granule or tablet and herbicide for paddy field have a problem, although demonstrate good foam characteristics in the water of the initial period after making them, further, when their consumption be tens milligrams to several grams, they demonstrate good dispersiveness, but when their consumption in tens whens gram, the expansion rate of agricultural chemical active component and the balance between diffusion rate are tending towards variation, and before the active component of all amounts of agricultural chemical disperses to finish, foam probably and just finish, the active component of agricultural chemical is probably at part local overrich and produce phytotoxicity when using thus, maybe can not obtain suitable effect, insecticides is that water dilutes in use, if it is directly used in paddy field without the water dilution, diffusion is likely inadequate, the aforementioned stable composition, foam is a kind ofly to be used for the oral drug prescription and medically to use or as the cleaning agent of artificial tooth, and will obtain inappropriate dispersion when being used for paddy field when the active component adding of agricultural chemical and with this preparation.In a usual paddy field, can see and stir into mud and the breeding of algae after smooth several days, and this algae covers the surface of water sometimes, if be used for the general composition of paddy field when this stage, the algae that covers water surface has stoped the dispersion of agricultural chemical, and has produced a problem like this in the distribution of agricultural chemical.
These problems before an object of the present invention is to solve in the document also provide a kind of composition of the agricultural chemical of can be safely and using in saving labour mode, put into paddy field from the ridge of rice field, and entering into paddy field, the people who does not need to use this agricultural chemical uses agricultural chemical, and every medicine of mouldable one-tenth from 1 to 200g needed shape and size, another object of the present invention provides a kind of agricultural chemical composition that does not have residual composition in the place of using, even agricultural chemical also can spread well when water surface is covered with algae, and good stability is also arranged storing when performance does not have variation after a very long time.
Like this, the invention provides a kind of solid composite that is used for the agricultural chemical molding of paddy field, it comprises as solvent, a kind of active component of agricultural chemical, a kind of foaming ingredient that can produce gas in water, a kind of is the macromolecular compound and the waterproofing agent of solid at normal temperatures.Under the situation of needs, the agricultural chemical composition of molding can wrap up with water-soluble film further like this.
This agricultural chemical composition that is used for paddy field can be by comprising the active component with agricultural chemical, can in water, produce the foaming ingredient of gas, be that the water-soluble polymer of solid and waterproofing agent mix under the normal temperature, and then prepare with the method for mold pressing; Or be the water-soluble polymer of solid under the heating and melting normal temperature, sneak into the active component and the waterproofing agent of agricultural chemical, cool off this mixture, sneak into the foaming ingredient that in water, can produce gas, and then the method for mold pressing prepares; Or under the heating and melting normal temperature water-soluble polymer of solid, at least in waterproofing agent, be mixed into the foaming ingredient that in water, can produce gas, the active component of agricultural chemical, carbonate and solid, water soluble acidic materials, cool off this mixture then, mix all the other compositions equably, and then the method for mold pressing prepares; Or be the water-soluble polymer of solid under the heating and melting normal temperature, mixing waterproofing agent, the active component of agricultural chemical can produce the foaming ingredient of gas in water, what the method for this mixture of cooling prepared in the molded frame of a curing usefulness then.And,, cover this molding product with water-soluble film if if possible.
By second mode of the present invention, the present invention relates to prepare can be safely and be used for the method for the solid composition of agricultural chemical product of paddy field in saving labour mode.
Recently studied and variously can use the Pestcidal compositions that does not need the people to enter paddy field safely and in saving labour mode, for example, advise a kind of herbicidal active component that contains, surfactant, the composition of carbonate and water soluble acid (Japanese unexamined patent publication No.128301/1991) and a kind of herbicidal active component that contains, the composition of surfactant and adhesive (Japanese unexamined patent publication No.173802/1991).Solid composite for these agricultural chemicals, making to be sprinkled into paddy field and not need the people to enter into paddy field by the composition that some are such uses agricultural chemical to become possibility, so just can avoid agricultural chemical to be bonded on skin or the clothes, and avoid spilling when using agricultural chemical.Like this, this composition makes safety and economizes the labour and use agricultural chemical to become possibility.
This solid composition of agricultural chemical product normally be placed in the mortar by powder with all components and from tens to hundreds of kg/cm 2High pressure under compress.
For by preparing this solid composition of agricultural chemical product in such high pressure lower compression, there are some problems in preparation method and agricultural chemical composition, for example, preparing by commercial scale in the agricultural chemical method for compositions, by the above-mentioned method of compression under high pressure, powder can be infeeded in the mortar continuously, and powder needs the flowability of height.Therefore, preliminary treatment or large-scale equipment need compress by mortar and molding before make the preliminary granulating of powder with cylinder compacting machine or other one-tenth particle machine.Further, after compression molding, composition is designed to unclamp from mortar or operated pressing tool, yet, when containing liquid substance in the agricultural chemical composition, the liquid trend is extruded when compression, and a part of composition then is tending towards being bonded on the mortar, therefore, liquid substance can not add considerable amount.
Outside air can be passed very small space, composition inside and contact with it in the compressed agricultural chemical composition that makes.Therefore, when this composition storage a very long time, the component of the active component of agricultural chemical or some formation compositions may the sex change by for example airborne moisture.
In above-mentioned agricultural chemical compression-moulding compound, comprise material (Japanese unexamined patent publication N0.128301/1991) a kind of and water reaction generation bubble, when composition is sprinkled into paddy field, water infiltrates through the inside of composition by slight void, so, foam fast from the inside of composition, and foaming may precedingly in the active component dispersion entry of agricultural chemical just finish.As a result, the active component of agricultural chemical will have to remain in quite in a large number makes use, just may produce phytotoxicity thus, or is producing inappropriate effect except the place that makes use.
The purpose of second kind of aspect of the present invention is these problems before solving and making safety and saving the labour and use and become the method for possible solid composition of agricultural chemical product of a kind of expansion type under water is provided, and the liquid components that can prepare and contain a large amount of relatively formation agricultural chemical compositions easily.Another object of the present invention provides a kind of method for preparing the high-efficiency agriculture chemical combinations, and each component can sex change in storing a very long time process for this composition, and the dispersion force of agricultural chemical active component is also fine in paddy field.
Like this, by the second way, the invention provides a kind of moisture method of the solid composition of agricultural chemical product of expansion type down for preparing, as base stock, a kind of active component of agricultural chemical, a kind of foaming ingredient and solid, water soluble polymer that can produce gas in water is comprising heating and melting solid, water soluble polymer, when the melting stage, sneak into other component that constitutes the agricultural chemical composition, cooling and solidify this mixture in frame container.
Below, the present invention will be described in detail in conjunction with preferred embodiment.
The typical foaming ingredient that can produce gas in water is a carbonate etc. and the mixture of solid, water soluble acidic materials.
Carbonate of the present invention etc. comprise, as, carbonate, bicarbonate and peroxidating carbonate, carbonate can be as, sodium carbonate, potash, ammonium carbonate, lithium carbonate, calcium carbonate, magnesium carbonate or barium carbonate, bicarbonate can be as, sodium bicarbonate, saleratus, carbonic hydroammonium or sodium sesquicarbonate, peroxidating carbonate can be as, sodium carbonate peroxide or peroxidating potash.Wherein, carbonate and bicarbonate are preferred, and sodium carbonate, potash, sodium bicarbonate and saleratus most preferably, they can two kinds or multiple salt use in compound, as, sodium carbonate and sodium bicarbonate, or potash and saleratus all can be used in the compound.
As for the solid, water soluble acidic materials, inorganic acid material or organic carboxyl acid all can use, for example, and phosphate or acid condensed phosphate, as sodium dihydrogen phosphate, potassium dihydrogen phosphate, acid sodium metaphosphate, the acid potassium metaphosphate, SAPP or acid potassium pyrophosphate, or carboxylic acid or contain oxycarboxylic acid, as oxalic acid, succinic acid, adipic acid, fumaric acid, tartaric acid, citric acid, malic acid, gluconic acid or maleic acid all can use.Wherein, citric acid, tartaric acid, succinic acid, fumaric acid or malic acid are preferred, and two kinds or multiple water-soluble acid material can merge use, for example, at least two kinds of acid, as citric acid and fumaric acid, or tartaric acid and malic acid, all can be used in the compound.The blending ratio of carbonate etc. and water-soluble acid material is preferably from 1: 10 to 10: 1, more preferably from 1: 1 to 3: 1 (mol ratio).Contain this carbonate etc. and the foaming component of solid, water soluble acidic materials and the mixing ratio of whole composition, be not particularly limited, but usually in the scope of 20-90% (weight), 30-90% (weight) preferably, 30-50% (weight) more preferably is as the total amount that can produce the foaming ingredient of gas in water.
Be at normal temperatures solid water soluble (CO) polymers can as, mean molecule quantity is at least 1000 polyethylene glycol, block copolymer containing, as lipophilic group, mean molecule quantity is at least 1000 polyethylene glycol and polypropylene glycol that is obtained by the propylene oxide polymerisation and the ethylene oxide that is contained in both terminal sudden reactions, as hydrophilic radical, or mean molecule quantity is at least 100,000 polyethylene oxide glycol, specific examples comprises that mean molecule quantity is 1000,4000,6000 or 20000 polyethylene glycol, Emalgen PP-290 (the block copolymer of oxygen ethene-oxypropylene, mean molecule quantity: 8000, make by Kao company), Epan 485 (polyoxyethylene-polyoxypropylene block polymer, make by Daiichi KogyoSeiyaku K.K), Epan 680 (the same), Epan 785 (the same), Epan U-105 (the same), Epan U-108 (the same), Newpol PE-68 (polyoxyethylene-polyoxypropylene block polymer, make by Sanyo Kasei K.K.), Newpol PE-78 (the same), Newpol PE-88 (the same), Newpol PE108 (the same), with mean molecule quantity be 100000,300000,1000000 or 4000000 polyethylene oxide.The foaming ingredient of the adding protection composition of this water-soluble polymer is avoided reacting with extraneous air; and waterproofing agent hereinafter described; it can prevent finishing fast of agricultural chemical composition foaming and can guarantee that foaming process obtains the suitable time; the preferred foamed time of agricultural chemical composition is can be based on the type of agricultural chemical active component; the weight of composition; water temperature etc. and change; usually; be from 1 minute to 6 hours; if the level of weight about 1g of composition; preferably from 5 to 20 minutes; if the level of composition about 10g; preferably from 10 to 40 minutes; if the level of composition about 50g; preferably from 20 to 80 minutes; if the level of composition about 100g; preferably from 30 to 120 minutes; if the level of composition about 200g; preferably from 40 to 160 minutes, prolong foamed time, need to add water-soluble polymer; usually the amount that adds is 5-70% (weight); preferably from 10-70% (weight), more preferably from 10-40% (weight), based on the weight of whole composition.
Being used for waterproofing agent of the present invention and being one can water-repellent substance, available as, metallic soap such as calcium stearate, dolomol or aluminum stearate, wax such as n-paraffin, different paraffin, paraffin, microwax, polyolefin-wax or beeswax, mineral oil such as atoleine or n-tetradecane, vegetable oil such as soya-bean oil, Lay oil, cocoa butter, rice bran oil or turpentine oil, animal oil such as butter, whale oil or saualane, silicone oil with silicone oil such as silicone oil or modification, wherein, material proportion be no more than 1 be preferred, proportion is no more than 1 material can be had, as, mineral oil, vegetable oil, animal oil or silicone oil.In proportion was no more than 1 waterproofing agent, the liquid substance that indissoluble is separated the agricultural chemical active component was preferred, and does not wherein dissolve the agricultural chemical active component more preferably.The solvability of agricultural chemical active component preferably is no more than 40% (weight), more preferably is to be no more than 10% (weight).The waterproofing agent that can mention is vegetable oil or silicone oil like this, be no more than in 1 the liquid waterproof agent not dissolving agricultural chemical active component and proportion, it is preferred having the material that viscosity is no more than 200 centipoises, and silicone oil is particularly preferred because it in addition also very effective when a small amount of.The ratio of waterproofing agent that adds composition is usually from 0.1-20% (weight), under the situation of using silicone oil, efficiently can obtain when containing 1-20% (weight).
Being used for agricultural chemical active component of the present invention can be as weed killer herbicide; bactericide; insecticide; miticide or plant growth regulator; concrete can be as 2-(4-ethoxyl phenenyl)-2-methyl-propyl-3-phenoxy benzyl ether (ether chrysanthemum ester); 0; 0-dimethyl 0-4-methyl sulfo---tolyl thiophosphate (MPP); 2-isopropyl phenyl methyl carbamate (MIPC); 4-(methyl sulfo-) phenyl dipropyl phosphoric acid fat (Kayaphos); 2; 3-dihydro-2; 2-dimethyl benzofuran base-7-(two butyl amido thio) methyl carbamate (carbosulfan); S-benzyl-0; 0-two-isopropylthio phosphate (IBP); 1; 2; 5; 6-nafoxidine also [3; 2; 1-ij] quinoline-4-ketone (pyroquilon); α; α, the adjacent toluyl aniline (flutolanil) of α-three fluoro-3 '-isopropoxy, 5-methyl isophthalic acid; 2; 4-s-triazolo [3,4-b] benzothiazoles (tricyclazole), 4-nitrobenzophenone 2; 4; 6-trichlorophenyl ether (CNP), 4-(2,4-two-benzyl chloride base) 1; 3-dimethyl pyrazole-5-toluene-4-sulfonic acid ester (pyrazolate); S-4-benzyl chloride base diethyl thiocarbamate (benthiocarb), 2-chloro-2 ', 6 '-diethyl-N-(2-propoxyl group ethyl) monoacetylaniline (Prethylactol); the basic oxo of 2-[4-morpholinodithio-2-N-methyl N-antifebrin (mefenacet); methyl-α-(4, the basic carbamoyl sulfonamides of 6-dimethoxypyridin base-2)-0-toluic acid ester (benzyl ethyl methyl), 2; 4-two (ethylamino)-6-methyl sulfo--1; 3,5-triazine (symetryne), 1-(1-methyl isophthalic acid-phenylethyl)-3-is right-tolyl urea (daimuron); S-ethyl azepines-1-carbothioic acid ester (ordram); 5-(4, the basic carbamoyl sulfonamides of 6-dimethoxypyridin base-2)-1-methoxyl group pyrazoles-4-carboxylic acid, ethyl ester (pyrazosulfuron), 2-bromo-3; 3-dimethyl-N-(1-methyl isophthalic acid-phenylethyl) butyl amide (Bromobutydo); S-benzyl 1,2-dimethyl propyl (ethyl) thiocarbamate (esprocarb), S-1-methyl isophthalic acid-phenyl ethyl piperidine-1-carbothioic acid ester (Dimepyperate); N-(1; the 2-dimethyl propyl)-N-ethyl-6-methyl sulfo--1,3,5-triazines-2; 4-diamines (diformazan third second is clean); 2-[4-(2, between 4-two chloro--tolyl-1,3-dimethyl pyrazole oxygen-5 bases-oxo]-4 '-methyl acetanilide (benzofenap); 5-tert-butyl-3-(2; 4-two chloro-5-isopropyl phenyls)-1,3,4-oxadiazole-2-(3H)-ketone (Evil humulone); 5-(2; the 4-dichlorophenoxy)-and 2-nitrobenzoic acid methyl esters (bifenox), S-2-benzene sulfonamido ethyl-10,0-two-isopropyl phosphorodithioate (bensulide); 4-(4-chloro-0-toloxyl) ethyl butyrate (Thistrol ethyl ester); N-butoxymethyl-2-chloro-2 ', 6 '-diethyl monoacetylaniline (butachlor), (E)-(RS)-1-(4-chlorphenyl)-4; 4-dimethyl-2-(1H-1; 2,4-triazolyl-1-) base penta-1-alkene 3-alcohol (uniconazole P), or (2RS; 3RS)-1-(4-chlorphenyl) 4; 4-dimethyl-2-(1H-1,2,4-triazolyl-1 base) penta 3-alcohol (paclobutrazol).Yet there is no particular restriction as the active component of agricultural chemical to be used for the present invention.The ratio of the active component of agricultural chemical in composition changes with the type of active component and the effectiveness of composition.And usually it in the scope of 5 to 70% (weight), the active component of agricultural chemical can be separately or two kinds or multiple above-mentioned mixture use.
Composition as for agricultural chemical of the present invention, the surfactant that is generally used for the agricultural chemical composition has, for example: anionic or nonionic surface active agent, as alkyl sulfate, alkylsulfonate, alkylaryl sulfonate, alkylphosphonate, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, poly-(alkylidene) glycol or lignosulphonates; As extender, tiny mineral powder such as clay, talcum, diatomite or calcium carbonate, or water-soluble extender such as urea, ammonium sulfate, sodium sulphate, sucrose, glucose or dextrin; Molecular weight is no more than 1000 polyethylene glycol; Organic solvent such as methyl naphthalene, phenyl silane base ethane, dimethylbenzene or chlorotoluene; And anti-decomposition agent, can add when needed.
The agricultural chemical composition that is used for paddy field by the present invention can directly use or layered product is sprinkled into paddy field, and layered product available water dissolubility film wrapped, make when manual user is used in paddy field with it, can avoid the active component of agricultural chemical directly to contact with skin, if this composition surrounds with little air, when this composition is used for paddy field, it is bubbled through the water column immediately, then after water-soluble film is soluble in water, composition slowly sinks in water, may prevent that thus composition is embedded in the water paddy soil.There is no particular restriction to be used for water-soluble film of the present invention, as, by as polyvinyl alcohol, methylcellulose, mosanom, Sodium Polyacrylate, polyethylene oxide, hydroxypropyl cellulose, hydroxyethylcellulose, carboxymethyl cellulose, the water-soluble film that starch or gum Arabic are made all can use.
Contain from the active component of the agricultural chemical of 5-70% (weight) by agricultural chemical composition of the present invention, summation is for from the foaming ingredient that can produce gas water of 20-90% (weight), and from 5-70% (weight) is the water-soluble polymer of solid and from the waterproofing agent of 0.1-20% (weight) at normal temperatures.This composition prepares through following method, that is, can be the water-soluble polymer and the waterproofing agent pulverize of solid at normal temperatures, then 10 to 300kg/cm by mixing and with the active component of agricultural chemical, can producing the foaming ingredient of gas in water 2Pressure under mold pressing prepare; Or be the polyethylene glycol of solid at normal temperatures by heating and melting, it is mixed with the active component of agricultural chemical, cool off this mixture then and make cure, be blended in the foaming ingredient that can produce gas in the water and waterproofing agent composition to the mixture that solidifies, and then mold pressing prepares; Or heating and melting be that the water-soluble polymer of solid reaches at normal temperatures is the temperature of fusing point at least, the foaming ingredient that can produce gas to the major general in water is blended in the active component of agricultural chemical, waterproofing agent, in water, can produce in the foaming ingredient of gas, cool off this mixture then and make cure, and other raw material sneaked in the mixture that solidifies, carry out mold pressing again and prepare; Or heating and melting is that the solid, water soluble polymer of solid reaches the temperature of fusing point at least at normal temperatures, the compound of mixed melting, the active component of agricultural chemical, waterproofing agent, in water, can produce foaming ingredient and other raw material of gas, then this mixture is introduced in the framework of an enclosed or open type, cooling makes cure.Under the situation of needs, the solid composite that obtains can be enclosed in the water-soluble film.The shape that is used for the agricultural chemical composition of paddy field by the present invention can be spherical, cylindrical shape or egg shape.Yet, manually all can accept as long as Any shape is suitable for removing broadcasting.The size of agricultural chemical composition of the present invention changes with the type of the active component of agricultural chemical or the size of paddy field.Yet the weight of every part of composition is usually from 1 to 200g, preferably from 10 to 100g.The weight of one unit volume is preferably in the scope of 0.5-2.5, more preferably from 1.0-2.0, from sowing efficient.
When agricultural chemical composition during with water-soluble film wrapped, the water-soluble film that has different water miscible two or more types in water all can use, and makes the agricultural chemical composition progressively to become flexible and to spread.For example, the multifunctionality of the agricultural chemical composition molding goods that encase with the water miscible water-soluble film of difference changes along with water temperature, and they also use water-soluble film wrapped further, make that necessary component can be with a certain amount of diffusion in the paddy field of required water temperature.
Suitable effect for agricultural chemical composition of the present invention obtains by a block composition is used in every are of paddy field, and the active component of agricultural chemical can be diffused in the whole paddy field fully like this.Yet, based on the characteristic of agricultural chemical active component, adjustable saving in the umber of paddy field to reach the purpose of being convenient to or reducing the active component diffusion or disperse.Usually use to per 10 ares be 1 to 50 part, preferably from 5 to 30 parts.
Below, first kind of mode of the present invention will describe in detail with comparing embodiment in conjunction with the embodiments.Yet, must understand that the present invention is not intended to be limited to these specific embodiments.
Among below the embodiment and comparing embodiment, unless other specific meanings is arranged, " umber " is meant " parts by weight ".
Embodiment 1
20 parts of polyethylene glycol of heat fused in the time of 60 ℃ (mean molecule quantity: 20000, fusing point: 55 ℃) and 30 parts of benthiocarbs; 1.7 part polyoxyethylene alkane phenyl ether, 0.3 part calcium dodecyl benzene sulfonate, with 5 parts of Lay oil (trade name: Natane Shiroshiboriyu, make by Honen SeiyuK.K, proportion: 0.91, the dissolubility of the agricultural chemical active component that uses: benthiocarb is 30-40%, the benzyl ethyl methyl is no more than 5% for the highest, mefenacet is no more than 5% for the highest, viscosity: 105 centistokes) mix.Further, add 1 part of benzyl ethyl methyl, 6 parts of mefenacets, 24 parts of sodium bicarbonates and 12 parts of tartaric acid also mix, then 50 gram mixtures to be put into diameter be the enclosed spherical frame of 4cm and be cooled to 30 ℃ and make cure, takes out the product that solidifies and obtain composition of the present invention from framework.
Embodiment 2
20 parts of polyethylene glycol (mean molecule quantities: 20000 of heat fused in the time of 60 ℃, fusing point: 55 ℃), with 30 parts of benthiocarbs, 1.7 part polyoxyethylene alkane phenyl ether, 0.3 part calcium dodecyl benzene sulfonate, mix with 5 parts of Lay oil (as mentioned above), cool off this mixture to 30 ℃ acquisition one solid.Further, mix 1 part of benzyl ethyl methyl, 6 parts of mefenacets, 24 parts of sodium bicarbonates and 12 parts of tartaric acid, and it is even to be stirred to mixture.Then, with 50g mixture flaker (Riken power P-16B-028 type is made by Riken Seiki K.K.) 50kg/cm 2Being molded into diameter under the pressure is that the 4cm cylindrical shaped sheet is to obtain composition of the present invention.
Embodiment 3
20 parts of polyethylene glycol (mean molecule quantities: 6000 of heat fused in the time of 60 ℃, 51 ℃ of fusing points), with 2 parts of sodium carbonate, 21 parts of sodium bicarbonates, 10 parts of citric anhydrides, 30 parts of benthiocarbs and 5 parts of atoleine (SILVER REAGENT, make by Wako Junyaku K.K., proportion: 0.88, the solvability of agricultural chemical active component: benthiocarb is 30-40%, and the benzyl ethyl methyl is for being no more than 5%, and mefenacet is for being no more than 5%, viscosity: 120 lis of bubbles) mix, cool off this mixture to 30 ℃ acquisition one solid then.Further, add 1 part of benzyl ethyl methyl, 6 parts of mefenacets, 1.7 part polyoxyethylene alkane phenyl ether, 0.3 part calcium dodecyl benzene sulfonate and 3 parts of clays (Zeeklit e GSM, trade name are made by Zeeklite Kagaku Kogyo K.K.) also mix.Then, the mixture that 50g is obtained like this uses flaker (as mentioned above) at 50kg/cm 2The cylindrical shaped sheet that is molded into diameter under the pressure and is 1.5cm is to obtain composition of the present invention.Embodiment 4
20 parts of polyethylene glycol (mean molecule quantities: 20000 of heat fused in the time of 60 ℃, 55 ℃ of fusing points), with 30 parts of benthiocarbs, 1 part of benzyl ethyl methyl, 6 parts of mefenacets, 1.7 parts of polyoxyethylene alkane phenyl ethers, 0.3 part of calcium dodecyl benzene sulfonate, 0.1 part silicone oil (Toshiba silicone oil TSF 451-50, trade name is made proportion: 0.96 by Toshiba Silico ne K.K, the dissolubility of agricultural chemical active component: benthiocarb is for being no more than 5%, the benzyl ethyl methyl is for being no more than 5%, and mefenacet is for being no more than 5%, viscosity: 50 centistokes), 27 parts of sodium bicarbonates and 13.9 parts of tartaric acid mix.Then, cool off this mixture to 30 ℃ acquisition one solid.Then, the mixture that 10g is obtained like this uses flaker (as mentioned above) at 50kg/cm 2The cylindrical shaped sheet that is molded into diameter under the pressure and is 4cm is to obtain composition of the present invention.
Embodiment 5
20 parts of polyethylene glycol (mean molecule quantities: 20000 of heat fused in the time of 60 ℃, fusing point: 55 ℃) and 30 parts of benthiocarbs, 1 part of benzyl ethyl methyl, 6 parts of mefenacets, 1.7 part polyoxyethylene alkane phenyl ether, 0.3 part calcium dodecyl benzene sulfonate, 0.5 part of silicone oil (Toshiba silicone oil TSF451-50, trade name, make by Toshiba Silicone K.K., as mentioned above), 27 parts of sodium bicarbonates and 13.5 parts of tartaric acid mix.Then, cool off this mixture to 30 ℃ acquisition one solid.Then, the mixture that 50g is obtained like this uses flaker (as mentioned above) at 50kg/cm 2The cylindrical shaped sheet that is molded into diameter under the pressure and is 4cm is to obtain the present composition.
Embodiment 6
20 parts of polyethylene glycol (mean molecule quantities: 20000 of heat fused in the time of 60 ℃, fusing point: 55 ℃) and 30 parts of benthiocarbs, 1 part of benzyl ethyl methyl, 6 parts of mefenacets, 1.7 parts of polyoxyethylene alkane phenyl ethers, 0.3 part calcium dodecyl benzene sulfonate, 2 parts of silicone oil (made by Toshiba Silicone K.K. by Toshiba silicone oil TSF451-50, trade name, as mentioned above), 26 parts of sodium bicarbonates and 13.5 parts of tartaric acid mix.Then, cool off this mixture to 30 ℃ acquisition one solid.Then, the mixture that 100g is obtained like this uses flaker (as mentioned above) at 50kg/cm 2The cylindrical shaped sheet that is molded into diameter under the pressure and is 5cm is to obtain the present composition.
Embodiment 7
20 parts of polyethylene glycol (mean molecule quantities: 20000 of heat fused in the time of 60 ℃, fusing point: 55 ℃), with 30 parts of benthiocarbs, 1.6 part polyoxyethylene alkane phenyl ether, 0.4 part calcium dodecyl benzene sulfonate and 0.5 part of silicone oil (Toshiba silicone oil TSF451-50, trade name is made by ToshibaSilicone K.K., mixes as mentioned above).Then, this mixture is chilled to 30 ℃ and obtains a solid.Further, add 1 part of benzyl ethyl methyl, 6 parts of mefenacets, 27 parts of sodium bicarbonates and 13.5 parts of tartaric acid also are mixed to uniform mixture.Then, use flaker (as mentioned above) at 50kg/cm in the 50g mixture 2The cylindrical shaped sheet that is molded into diameter under the pressure and is 4cm is to obtain the present composition.
Embodiment 8
The composition of 50g embodiment 7 is used by polyvinyl alcohol (Hiceron C-type, trade name, make by Nichigo Film K.K) the water-soluble film parcel made, and heat-sealing (the PS-310 type is made by Fuji Impulse K.K.) film around to obtain composition of the present invention.
Embodiment 9
10 parts of polyethylene oxide (mean molecule quantities: 100000 of heat fused in the time of 60 ℃, fusing point: 65 ℃), add 30 parts of benthiocarbs, 1 part of benzyl ethyl methyl, 6 parts of mefenacets, 1.7 part polyoxyethylene alkane phenyl ether, 0.3 part calcium dodecyl benzene sulfonate, 0.5 part of silicone oil (Toshiba silicone oil TSF451-50, trade name, make by Toshiba Silicone K.K., as mentioned above), 33 parts of sodium bicarbonates are with 17.5 parts of tartaric acid and be mixed to into homogeneous mixture, then, it is that a spherical frame that 5cm has a dozen to uncap is chilled to 30 ℃ and makes cure that the 50g mixture is put into diameter, and solid product is taken out acquisition composition of the present invention from framework.
Embodiment 10
20 parts of polyoxyethylene polyoxypropylene block polymers of heat fused (NewpolPE-108 in the time of 60 ℃, trade name, make by Sanyo Kasei Kogyo K.K., fusing point: 50 ℃) and 30 parts of benthiocarbs, 1 part of benzyl ethyl methyl, 6 parts of mefenacets, 1.7 part polyoxyethylene alkane phenyl ether, 0.3 part of calcium dodecyl benzene sulfonate, 1 part of silicone oil (silicone oil SH 200, trade name, make proportion by Toray Dow Corning: 0.95, the dissolubility of the agricultural chemical active component of use: benthiocarb is for being no more than 5%, the benzyl ethyl methyl is for being no more than 5%, mefenacet is for being no more than 5%, viscosity: 5 centistokes), and 24 parts of sodium bicarbonates, (Kunilite 301 for 12 parts of tartaric acid and 4 parts of diatomite, trade name is made by Kunimine Kogyo K.K.) mix, this mixture is chilled to 30 ℃ obtains a solid.Then, the mixture that 50g is obtained like this uses flaker (as mentioned above) at 50kg/cm 2The cylindrical shaped sheet that is molded into diameter under the pressure and is 4cm is to obtain composition of the present invention.
Embodiment 11
20 parts of polyethylene polyoxypropylene block polymer (Newpol PE-108 of heat fused in the time of 60 ℃, trade name, make by Sanyo Kasei Kogyo K.K., fusing point: 50 ℃), with 30 parts of benthiocarbs, 1 part of benzyl ethyl methyl, 6 parts of mefenacets, 1.7 parts of polyoxyethylene alkane phenyl ethers, 0.3 part of calcium dodecyl benzene sulfonate, 1 part of modified silicon oil (ethanol-modified silicon oil SF 8428, trade name is made proportion: 0.98 by Toray Dow Corning, the dissolubility of agricultural chemical active component: benthiocarb is for being no more than 5%, the benzyl ethyl methyl is for being no more than 5%, and mefenacet is for being no more than 5%, viscosity: 130 centistokes), 27 parts of sodium bicarbonates, 9 parts of citric anhydrides and 4 parts of fumaric acid mix.Then, this mixture is chilled to 30 ℃ and obtains a solid.Then, the mixture that 50g is obtained like this uses flaker (as mentioned above) at 50kg/cm 2The cylindrical shaped sheet that is molded into diameter under the pressure and is 4cm is to obtain composition of the present invention.
Embodiment 12
20 parts of polyethylene polyoxypropylene block polymer of heat fused in the time of 60 ℃ (made by Sanyo Kasei Kogyo K.K. by NewpolPE-108, trade name, fusing point: 50 ℃), with 30 parts of benthiocarbs, 1.7 parts of polyoxyethylene alkane phenyl ethers, 0.3 part of calcium dodecyl benzene sulfonate, with 1 part of modified silicon oil (ethanol-modified silicon oil SF 8428, trade name is made by Toray Dow Corning, mixes as mentioned above), then, this mixture is chilled to 30 ℃ and obtains a solid.Further, add 1 part of benzyl ethyl methyl, 6 parts of mefenacets, 27 parts of sodium carbonate peroxides and 13 parts of citric anhydrides and to be stirred to mixture even.Then, the 50g mixture being put into straight warp is that 5cm has the spherical frame on a dozen tops of uncapping to be chilled to 30 ℃ and to make cure.Then, solidification products is taken out acquisition composition of the present invention from framework.
Embodiment 13
16 parts of polyethylene glycol of heat fused in the time of 60 ℃ (mean molecule quantity: 20000, fusing point: 55 ℃) and 30 parts of sodium bicarbonates and 14 parts of citric anhydrides mixing.Then, mixture is chilled to 30 ℃ and obtains a solid.Further, add 30 parts of pyroquilons, 4 parts of clays (as mentioned above), 1 part of sodium alkyl benzene sulfonate, the sodium salt of 4 parts of extraordinary aromatic sulfonic acid-formalin condensation products and 1 part of silicone oil (Toshiba silicone oil TSF 541-50, trade name, make by Toshiba Silicone K.K., proportion: 0.96,50 centistokes) and mix the solvability of agricultural chemical active component: pyroquilon is for being no more than 5%, viscosity:.Then, the mixture that 50g is obtained like this uses flaker (as mentioned above) at 50kg/cm 2The cylindrical shaped sheet that is molded into 1.5cm under the pressure is to obtain composition of the present invention.
Embodiment 14
With 30 parts of pyroquilons, 30 parts of sodium bicarbonates, 14 parts of citric anhydrides, 16 parts of polyethylene glycol (mean molecule quantities: 20000, fusing point: 55 ℃), 4 parts of magnesia, 1 part of sodium alkyl benzene sulfonate, (Toshiba silicone oil TSF 451-50 mixes as mentioned above) and stirs for the sodium salt of 4 parts of extraordinary aromatic sulfonic acid-formalin condensation products and 1 part of silicone oil.Then, use flaker (as mentioned above) at 150kg/cm in the 50g mixture 2Be molded into the cylindrical shaped sheet that diameter is 4cm under the pressure, the molding product uses the water-solubility membrane look that is made by polyvinyl alcohol (as mentioned above) to wrap up in, and the heat-sealing (as mentioned above) film around to obtain composition of the present invention.
Embodiment 15
20 parts of polyoxyethylene polyoxypropylene block polymer (New-pol PE-108 of heat fused in the time of 60 ℃, trade name, make by Sanyo Kasei Kogyo K.K., fusing point, 50 ℃), add the solution that 15 parts of pyroquilons is dissolved in acquisition in 22.5 parts of 2-phenoxetols (reagent is made by Wako Junyaku K.K.), 23 parts of sodium bicarbonates, 2 parts of sodium carbonate, 10 parts of tartaric acid, 2 parts of malic acid, 1 part of sodium alkyl benzene sulfonate, the sodium salt of 4 parts of special aromatic sulfonic acid-formalin condensation products and 0.5 part of silicone oil (Toshiba silicone oil TSF 451-50, trade name, make by Toshiba Silicone K.K., as mentioned above) and stir.Then, the 50g mixture being put into diameter is that 5cm has the spherical frame on a dozen tops of uncapping and is chilled to 30 ℃ and makes cure.Then, solidification products is taken out from framework to obtain composition of the present invention.
Embodiment 16
24 parts of polyoxyethylene polyoxypropylene block polymers of heat fused (Epan785 in the time of 60 ℃, trade name, make by Daiichi Kogyo Seiyaku K.K., 49 ℃ of fusing points), with 34 parts of IBP, 1 part of modified silicon oil (ethanol-modified silicon oil SF8428, trade name, make by Toray Dow Corning, proportion: 0.98, the IBP of the dissolubility of agricultural chemical active component: 20-30%, viscosity: 130 centistokes), 28 parts of sodium bicarbonates and 13 parts of fumaric acid mix, and this mixture is chilled to 30 ℃ obtains a solid.Then, the mixture that 100g is obtained like this uses flaker (as mentioned above) at 50kg/cm 2The cylindrical shaped sheet that is molded into diameter under the pressure and is 5cm is to obtain composition of the present invention.
Embodiment 17
20 parts of polyoxyethylene polyoxypropylene block polymers of heat fused (Epan785 in the time of 60 ℃, trade name, make by Daiichi Kogyo Seiyaku K.K.), with 34 parts of IBP, 9 parts of surfactant (Sorpol KT, trade name, Co., Ltd makes by the Toho chemistry), with 1 part of modified silicon oil (Toshiba silicone oil SF8411, trade name is made proportion: 0.98 by Toshiba Silicone K.K., the dissolubility of used agricultural chemical composition active component: from the IBP of 10-20%, viscosity: 130 centistokes) mix.This mixture is chilled to 30 ℃ obtains a solid.Add 24 parts of sodium bicarbonates and 12 parts of fumaric acid and be stirred to evenly, then with the 20g mixture with flaker (as mentioned above) at 50kg/cm 2Be molded into the cylindrical shaped sheet that diameter is 2.5cm under the pressure, the molding product water-solubility membrane parcel that makes by polyvinyl alcohol (as mentioned above), and heat-sealing (as mentioned above) film around to obtain composition of the present invention.
Embodiment 18
20 parts of polyethylene glycol (mean molecule quantities: 20000 of heat fused in the time of 60 ℃, 55 ℃ of fusing points) and 9 parts of ether chrysanthemum esters, (Sorpol 3154 for 1 part of surfactant, trade name, Co., Ltd makes by the Toho chemistry), 20 parts of atoleines (made by WakoJunyaku K.K. by reagent, proportion: 0.88, the dissolubility of used agricultural chemical active component: ether chrysanthemum ester is for being no more than 5%, viscosity: 120 centistokes), 30 parts of sodium bicarbonates and 20 parts of citric anhydrides mix.This mixture is chilled to 30 ℃ obtains a solid.Then, the mixture that 50g is obtained like this uses flaker (as mentioned above) at 50kg/ 2The cylindrical shaped sheet that is molded into diameter under the pressure and is 4cm is to obtain composition of the present invention.
Embodiment 19
20 parts of polyethylene glycol (mean molecule quantities: 20000 of heat fused in the time of 60 ℃, fusing point: 55 ℃), with 9 parts of ether chrysanthemum esters, 1 part of surfactant (Sorpol 3154, and trade name is by the manufacturing of Toho chemistry Co., Ltd) and 20 parts of atoleine (reagent, make by WakoJunyaku K.K., proportion: 0.88, the solvability of used agricultural chemical active component: ether chrysanthemum ester is for being no more than 5%, viscosity: 120 centistokes) mix.Then, this mixture is chilled to 30 ℃ and obtains a solid.Further, be mixed into 30 parts of sodium bicarbonates and 20 parts of citric anhydrides.Then, the mixture that 200g is obtained like this uses flaker (as mentioned above) at 50kg/cm 2The cylindrical shaped sheet that is molded into diameter under the pressure and is 7cm is to obtain composition of the present invention.Such product water-solubility membrane parcel that makes by polyvinyl alcohol (as mentioned above), and heat-sealing (as mentioned above) film around to obtain composition of the present invention.Comparing embodiment 1
Mix 10 parts of benthiocarbs, 1 part of benzyl ethyl methyl, 6 parts of mefenacets, 1.7 parts of polyoxyethylene alkane phenyl ethers and 0.3 part of calcium dodecyl benzene sulfonate.Then, in this mixture, sneak into 40 parts of diatomite (as mentioned above).Further, adding 28 parts of sodium bicarbonates and 13 parts of tartaric acid, to be stirred to mixture even.Then, use flaker (as mentioned above) at 50kg/cm in the 50g mixture 2The cylindrical shaped sheet that is molded into diameter 4cm under the pressure is to obtain comparative composition.Comparing embodiment 2
20 parts of polyethylene glycol (mean molecule quantities: 20000 of heat fused in the time of 60 ℃, fusing point: 55 ℃), with 30 parts of benthiocarbs, 1 part of benzyl ethyl methyl, 6 parts of mefenacets, 1.7 part polyoxyethylene alkane phenyl ether and 0.3 part of calcium dodecyl benzene sulfonate, 28 parts of sodium bicarbonates and 13 parts of tartaric acid mix.Then, this mixture is chilled to 30 ℃ and obtains a solid.Then, the mixture that 50g is obtained like this uses flaker (as mentioned above) at 50kg/cm 2The cylindrical shaped sheet that is molded into diameter under the pressure and is 4cm is to obtain comparative composition.Comparing embodiment 3
20 parts of polyethylene glycol of heat fused in the time of 60 ℃ (mean molecule quantity: 20000,55 ℃ of fusing points) and 30 parts of benthiocarbs, 1.7 parts of polyoxyethylene alkane phenyl ethers and 0.3 part of calcium dodecyl benzene sulfonate mix.This mixture is chilled to 30 ℃ obtains a solid, further, sneak into 1 part of benzyl ethyl methyl, 6 parts of mefenacets, 28 parts of sodium bicarbonates and 13 parts of tartaric acid.Then, use flaker (as mentioned above) at 50kg/cm in the 50g mixture 2The cylindrical shaped sheet that is molded into diameter under the pressure and is 4cm is to obtain comparative composition.Comparing embodiment 4
20 parts of polyethylene glycol (mean molecule quantities: 20000 of heat fused in the time of 60 ℃, fusing point: 55 ℃), with 30 parts of benthiocarbs, 1 part of benzyl ethyl methyl, 6 parts of mefenacets, 1.7 parts of polyoxyethylene alkane phenyl ethers and 0.3 part of calcium dodecyl benzene sulfonate, 5 parts of clays (as mentioned above), 25 parts of sodium bicarbonates and 11 parts of tartaric acid mix.This mixture is chilled to 30 ℃ obtains a solid.Then, use flaker (as mentioned above) at 50kg/cm in the 50g mixture that obtains like this 2The cylindrical shaped sheet that is molded into diameter under the pressure and is 4cm is to obtain comparative composition.Comparing embodiment 5
20 parts of polyethylene glycol (mean molecule quantities: 20000 of heat fused in the time of 60 ℃, fusing point: 50 ℃), with 30 parts of benthiocarbs, 1.7 part polyoxyethylene alkane phenyl ether, 0.3 part calcium dodecyl benzene sulfonate and 5 parts of Lay oil (Natane Shiroshiboriyu, trade name is made by Honen Seiyu K.K., mixes as mentioned above).Then, this mixture is chilled to 30 ℃ and obtains a solid.Further, add 1 part of benzyl ethyl methyl, 6 parts of mefenacets and 36 parts of ammonium sulfate.Then, the mixture that 50g is obtained like this uses flaker (as mentioned above) at 50kg/cm 2The cylindrical shaped sheet that is molded into diameter under the pressure and is 4cm is to obtain comparative composition.Comparing embodiment 6
Mix 15 parts of benthiocarbs, 1.7 part polyoxyethylene alkane phenyl ether, 0.3 part calcium dodecyl benzene sulfonate and 1 part of silicone oil (Toshiba silicone oil TSF 451-50, trade name, make by Toshiba Silicone K.K., as mentioned above), this mixture is adsorbed in 15 parts of white carbon (Carplex # 1120, trade name is made by Shionogi Pharmaceuti-cal Co., Ltd) on.Further, add 1 part of benzyl ethyl methyl, 6 parts of mefenacets, 24 parts of sodium bicarbonates, it is even that 12 parts of tartaric acid and 24 parts of ammonium sulfate are stirred to mixture.Then, use flaker (as mentioned above) at 100kg/cm in the 50g mixture 2The cylindrical shaped sheet that is molded into diameter under the pressure and is 4cm is to obtain comparative composition.Comparing embodiment 7
20 parts of polyethylene glycol (mean molecule quantities: 20000 of heat fused in the time of 60 ℃, fusing point: 55 ℃), with 30 parts of benthiocarbs, 1.7 part polyoxyethylene alkane phenyl ether, 0.3 part of calcium dodecyl benzene sulfonate and 0.5 part of silicone oil (Toshiba silicone oil TSF 451-50, trade name, make by Toshiba Silicone K.K., mix as mentioned above), then, this mixture is chilled to 30 ℃ obtains a solid.Further, add 1 part of benzyl ethyl methyl, 6 parts of mefenacets and 40.5 parts of ammonium sulfate also stir.Then, use flaker (as mentioned above) at 100kg/cm in the 50g mixture 2The cylindrical shaped sheet that is molded into diameter under the pressure and is 4cm is to obtain comparative composition.Comparing embodiment 8
20 parts of polyethylene glycol (mean molecule quantities: 20000 of heat fused in the time of 60 ℃, fusing point: 55 ℃), with 30 parts of benthiocarbs, 1 part of benzyl ethyl methyl, 6 parts of mefenacets, 1.7 part polyoxyethylene alkane phenyl ether, 0.3 part of calcium dodecyl benzene sulfonate, 0.5 part of modified silicon oil (amino-modified silicon oil 8417, trade name, make proportion by Toray DowCorning: 0.98, the dissolubility of used agricultural chemical active component: benthiocarb is for being no more than 5%, the benzyl ethyl methyl is for being no more than 5%, mefenacet is for being no more than 5%, viscosity: 1200 centistokes), 27 parts of sodium bicarbonates and 13.5 parts of tartaric acid mix.Then, this mixture is chilled to 30 ℃ and obtains a solid.Then, the mixture that 50g is obtained like this uses flaker (as mentioned above) at 50kg/cm 2The cylindrical shaped sheet that is molded into diameter under the pressure and is 4cm is to obtain comparative composition.Comparing embodiment 9
Mix 6 parts of benthiocarbs, 0.34 part of polyoxyethylene alkane phenyl ether, 0.06 part of calcium dodecyl benzene sulfonate and 4.4 parts of white carbon (Carplex # 80, trade name are made by Sh-ionogi Phramaceutical Co., Ltd) obtain a powder.Further, sneak into 0.2 part of benzyl ethyl methyl, 1.2 part mefenacet, 8 parts of polyvinylpyrrolidones (Luviskol K30, trade name are made by BASF), 4.9 part boric acid, 31.9 part tartaric acid and 43 parts of sodium bicarbonates then, use flaker (as mentioned above) at 50kg/cm in the 50g mixture 2The cylindrical shaped sheet that is molded into diameter under the pressure and is 4cm is to obtain comparative composition.Comparing embodiment 10
20 parts of polyethylene glycol (mean molecule quantities: 20000 of heat fused in the time of 60 ℃, fusing point: 55 ℃), with 30 parts of benthiocarbs, 1.7 part polyoxyethylene alkane phenyl ether, 0.3 part calcium dodecyl benzene sulfonate and 5 parts of dimethylbenzene (reagent, make proportion by Wako Junyaku K.K.: 0.87, the dissolubility of used agricultural chemical active component:
Benthiocarb is at least 100%, and the benzyl ethyl methyl is for being no more than 5%, and Mephenaset is at least 100%, viscosity: 1 centistoke) mix.Further, add 1 part of benzyl ethyl methyl, 6 parts of mefenacets, 24 parts of sodium bicarbonates and 12 parts of tartaric acid also stir.Then the 50g mixture is put into diameter and be the closed spherical frame of 4cm and be chilled to 30 ℃ and make cure.Then, the product that will solidify takes out from framework to obtain comparative composition.Comparing embodiment 11
Mix 0.17% benzyl ethyl methyl, 1% mefenacet, 1% sodium alkyl benzene sulfonate, 2% sodium lignosulfonate, 30% bentonite and 60.83% calcium carbonate powder add entry again, this mixture is kneaded and be 0.8mm by a diameter the hole is extruded into particle.This partical is dry in the time of 90 ℃ to mix 95% this partical also with 16 to 32 mesh sieve branches, and 5% benthiocarb obtains granule.Comparing embodiment 12
Mix 30 parts of pyroquilons, 33 parts of sodium bicarbonates, 16 parts of citric anhydrides, 16 parts of polyethylene glycol (mean molecule quantity: 20000, fusing point: 55 ℃), the sodium salt of 1 part of sodium alkyl benzene sulfonate and 4 parts of extraordinary aromatic sulfonic acid-formalin condensation products also stirs.Use flaker (as mentioned above) at 150kg/cm in the 50g mixture then 2The cylindrical shaped sheet that is molded into diameter under the pressure and is 4cm is to obtain comparative composition.Comparing embodiment 13
20 parts of polyethylene glycol (mean molecule quantities: 20000 of heat fused in the time of 60 ℃, 55 ℃ of fusing points), with 30 parts of pyroquilons, 1 part of sodium alkyl benzene sulfonate, the sodium salt of 4 parts of extraordinary aromatic sulfonic acid-formalin condensation products, 10 parts of chloroform (reagent, make by Wako JunyakuK.K., make a gesture of measuring: 1.48, the dissolubility of used agricultural chemical active component: at least 100% pyroquilon, viscosity: 1 centistoke), 30 parts of sodium bicarbonates and 15 parts of citric anhydrides mix, and then this mixture are chilled to 30 ℃ and obtain a solid.Then, the mixture that 50g is obtained like this uses flaker (as mentioned above) at 50kg/cm 2The cylindrical shaped sheet that is molded into diameter under the pressure and is 4cm is to obtain comparative composition.Comparing embodiment 14
Mix 5% pyroquilon, 1% sodium alkyl benzene sulfonate, 2% sodium lignosulfonate, 30% bentonite and 62% talcum, add entry again, this mixture is kneaded and be to extrude granulating in the hole of 0.8mm by diameter, partical is dry and divide with the acquisition particle with 16 to 32 mesh sieves in the time of 90 ℃.Test implementation example 1
Experiment to barnyard grass (Echinochloa crus-galli) and reed (Scirpus junoides) herbicidal effect
Irrigate 2 ares of paddy fields, stir into mud and through smooth, fertilising then, then, sowing is the seed of barnyard grass and reed down, and is implanted into the rice shoot (kind: Kinnanpu) of the rice in 2-leaf stage.Transplant the degree of depth and reach 3cm, the degree of depth of water remains on from 5-6cm, and the seedling transplantation of rice is after seven days, and each composition of 100g embodiment 1-12 is sprinkled into each piece paddy field.Further, with the composition of 300g comparing embodiment 1, each composition of 100g comparing embodiment 2-10 and the composition of 200g comparing embodiment 6 are sprinkled into corresponding paddy field separately.Further, for the particle of comparing embodiment 11, the 600g particle imposes on paddy field by hand equably.For from being transplanted to the leaf period till 7 days, the rice shoot of rice has the 4-leaf stage, and barnyard grass has the 1-1.5 leaf stage, and reed has the 1-leaf stage.Further, the paddy field till being transplanted to 7 days, algae reproduction has also covered the water surface.Use composition after 30 days, composition just can be found out the effect of rice, barnyard grass and reed, further, in order to test unnecessary effect, go into the seed of barnyard grass and reed from using back sowing till the composition to 30 day, after 15 days, promptly from using composition to 45 day to end, composition just can find out the effect of rice, barnyard grass and reed, further, composition can find out also that with the diffusance of the water surface gained the results are shown in table 1 and 2 under water paddy field.
In table, diffusance is with zero: good, △: inappropriate and *: the difference represent.
To the effect of plant with 11 grades from index 0: promptly undressed situation is to index 10: kill fully and represent.
Table 1
The experimental group compound Phytotoxicity Herbicidal effect
Rice Barnyard grass Reed
After 30 days after 45 days After 30 days after 45 days After 30 days after 45 days
Embodiment 2 embodiment 7 embodiment 8 ????1????0 ????1????0 ????0????0 ????10????9 ????10????9 ????10????9 ????10????9 ????10????9 ????10????9
Comparing embodiment 3 comparing embodiments 5 comparing embodiments 7 comparing embodiments 9 comparing embodiment 1l ????2????1 ????4????3 ????4????3 ????2????1 ????1????0 ????7?????6 ????4?????2 ????4?????2 ????7?????6 ????10????9 ????7?????6 ????4?????2 ????4?????3 ????8?????6 ????10????9
Table 2
Figure 0010092100261
The experiment of executing example 2 control rice blast (Magnaporthe grisea) is bought in test
Irrigate 2 ares of paddy fields, stir into mud and smooth, apply fertilizer then, then be implanted into the rice sprouts (kind: Kinnanpu) in 2-leaf stage.The transplanting degree of depth is 3cm, the degree of depth of water remains on 5-6cm, after the seedling transplantation of rice is gone into 60 days, each composition of 100g embodiment 13 and 14 and the composition of 200g embodiment 15 is sprinkled into paddy field separately, further, 100g comparing embodiment 12 is sprinkled into similar paddy field with each composition of 13.Particle for comparing embodiment 13, with the manual paddy field that imposes on equably of 6009 particles, from using composition to 15 day and till 30 days, effect to rice just can see, day ends from using composition to 30, the rice shoots of five kinds of rice taken out from four angles of each paddy field and central authorities be implanted into the basin, then, the rice blast spore suspension is sprayed an inoculation and cultivation in a greenhouse, end, can check out downright bad damage from cultivating 1O days.The result represents with the control rate that following formula obtains.Gained the results are shown in table 3 and the table 4.
Wherein: A is the spike of rice sum of viewed experiment rice,
B is the spike of rice number that contains rice blast tubercle or rotten bar,
C is the spike of rice number that contains at least 2/3 panicle disease,
D be contain 1/3-2/3 the panicle disease the spike of rice number and
E contains the spike of rice number that is less than 1/3 panicle disease.
Table 3
Table 4
Estimate phytotoxicity based on following standard:
-: normal leaf (plant-less toxicity).
±: the observed phytotoxicity that is not more than about 10% leaf.
+: the phytotoxicity of observed about 10-30% leaf.
++: observed phytotoxicity greater than about 30% leaf.Foaming of test implementation example 3 compositions and diffusion experiment
At diameter is 30cm, height is in the large scale Petri dish of l0cm, pour the 1kg water paddy soil into, put into water then, stirring into the paddy field of mud and smooth simulation let alone to place 3 days, introduce water with the speed of 11/min then, the water on surface is always brought in constant renewal in, for the central authorities in this Simulated Water rice field, with each composition and the comparing embodiment 1-10 of embodiment 1-19,12 and 13, from the landing of the height of 20cm and 100cm, until measuring the time that foaming is finished, and measure foam degrees and diffusance in water, each composition is placed on and spreads out in the glass container that has lid and stored 30 days in the time of 40 ℃, measures foam degrees and diffusance in the water under the similarity condition.Evaluation criterion is as described below, and gained the results are shown in table 5 and 6.
Table 5 Foam degrees
◎: violent foaming, and foaming lasts till that always composition disperses to finish.
Zero: basic foaming, and foaming lasts till that always composition disperses basic the end.
△: basic foaming, but foaming does not last till that composition disperses to finish.
*: do not observe basic foaming.Diffusance
◎: do not remain at landing place composition.Zero: seldom measuring composition in landing place has residue.△: residue is arranged at landing place small number of groups compound.*: at landing place significant quantity composition residue is arranged.
Table 6
Figure 0010092100301
Foam degrees zero: significantly foaming, and foaming lasts till that composition disperses fully.△: less foaming, and foaming does not last till that composition disperses.*: do not observe significant foaming diffusance zero: do not have the remaining residue of composition in landing place.△: residue is arranged at landing place small number of groups compound.*: at landing place significant quantity composition residue is arranged.
The agricultural chemical composition that is used for paddy field by the present invention is a kind of solid composite that is suitable for being sprinkled into from the ridge of paddy field the shape of paddy field that is molded as, thus, the use of agricultural chemical does not need the user to enter paddy field, like this, be not only safety but also economize the labour, composition of the present invention can foam in water, and the active component of agricultural chemical can spread or and bubble dispersion together.The invention provides remarkable result in control expansion rate and near the agricultural chemical active component dispersion water surface, promptly, in paddy field in the agricultural chemical active component diffusion process, gradually with constant speed foaming, so just may avoid the foaming of end fast, make to form inadequate dispersion, and make use agricultural chemical active component that significant surplus be arranged.
Yet, even work as algae propagation on the paddy field surface, diffusion can not be prevented from yet, ought use composition by a place simply simultaneously at paddy field, this will disperse equably, so just can handle the monoblock paddy field with agricultural chemical, further foaming ingredient can not decompose under the air moisture effect in the storage process, thereby composition can be stored segment length's time.
Now, by the second way, the invention provides a kind of method for preparing the solid composition of agricultural chemical product of underwater foamed type, comprise that as this composition of base stock the active component of agricultural chemical can produce the foaming ingredient and the solid, water soluble polymer of gas in water, wherein comprise heating and melting solid, water soluble polymer, in melt stage, sneak into other component and the water-soluble polymer that constitute the agricultural chemical composition, in frame container, cool off and solidify this mixture.
Being used for solid, water soluble polymer of the present invention can be any water soluble compound, as long as be solid and at normal temperatures to insert frame container with the form of mixtures of other component that constitutes the agricultural chemical composition, in frame container, cool off and solidify this agricultural chemical composition, particularly preferably be the water-soluble polymer that fusing point is at least 40 ℃, specific embodiment can be as previously mentioned.Yet, be used for water-soluble polymer of the present invention and be not limited to these specific embodiments, water-soluble polymer can be separately or the mixture of two kinds or multiple their chemical combination use, the ratio of water-soluble polymer in the agricultural chemical composition is 5-70% (weight), 10-70% (weight) preferably, 10-40% (weight) more preferably is based on whole composition.
Being used for foaming ingredient of the present invention can be any blowing agent, as long as it can foam in water, typical foaming ingredient is the compound of analog such as carbonate and water-soluble acid material, yet, if analogs such as carbonate can foam separately, just do not need to add water-soluble acid material, as water-soluble acid material, solid matter is preferred.
Analogs such as carbonate as previously mentioned.
The blending ratio of analogs such as carbonate and water-soluble acid material, preferably 1: 10-10: in 1 the scope, more preferably be 1: 1-3: 1, mol ratio.
Further, as foaming ingredient, hydrogen peroxide addition product and chlorinated isocyanuric acid or permonosulphuric acid all can merge and be used for compound, and the ratio of hydrogen peroxide addition product and chlorinated isocyanuric acid or permonosulphuric acid is preferably 25: 1-1: 5 mol ratios.
The ratio of foaming ingredient in whole composition is based on the type of active component in the agricultural chemical and other component changes, but usually in 20-90% (weight), preferably 30-90% (weight), more preferably 30-50% (weight).
The agricultural chemical active component can be as weed killer herbicide, fungicide, insecticide, miticide or plant growth regulator, as previously mentioned, the ratio of agricultural chemical active component in whole composition is based on the type of active component and its application target changes, but usually in the scope of 5-70% (weight).Further, the active component of agricultural chemical can be separately or the mixture of two kinds or multiple their chemical combination use.
In the method for the invention, surfactant, extender, organic solvent, foaming stabiliser, anti-decomposition agents etc. all can be used for preparing the agricultural chemical composition usually, under the situation of needs, all can add in the composition of the present invention, as previously mentioned.
By preparation agricultural chemical method for compositions, by the second way of the present invention, the heating water-soluble polymer reaches at least to fusing point to obtain the temperature of liquid, yet, before heating, other compositions of the active component of agricultural chemical or the formation agrochemical compositions except water-soluble polymer, as foaming ingredient, can tentatively be added in the water-soluble polymer, heating-up temperature can reach any degree, as long as water-soluble polymer can melt.Viewpoint from operating efficiency, heating-up temperature is preferably in the scope of the fusing point to 100 of polymer ℃, preferably 50-80 ℃, then, also mixed in the residue component adding liquid water-soluble polymer with formation agricultural chemical composition, mixing temperature can be higher than the temperature of heat fused water-soluble polymer, but is lower than the heat fused temperature slightly usually.
Be used for the heat fused water-soluble polymer equipment and be used for mixing the equipment of other component, can be equipment separately, also can be same equipment, be wrapped in electric heater unit around the equipment or steam unit makes temperature can be adjusted on the certain level, be preferred, when liquid mixture has a full-bodied situation, from the viewpoint of efficient, the preferred equipment that many grades of stirring vanes are housed that uses.
Liquid is evenly mixed, in the frame container of packing into then, carry out the nature cooling or force cooling, make liquid mixture cure in frame container, obtain solid composition of agricultural chemical product with cooling device.Usually, a part of component that constitutes the agricultural chemical composition is dissolved in the water-soluble polymer of fusing, subsequently, the phenomenon that fusing point reduces will take place, and therefore, mixture solidifies in the temperature that is lower than the water-soluble polymer fusing point usually.
Except top said, the powder that constitutes all component homogeneous mixtures of agricultural chemical composition can be put into a frame container, and be heated to the temperature of water-soluble polymer fusing with frame container, when water-soluble polymer melted formation one liquid mixture in framework, mixture was with the framework cooled and solidified.
Frame container has one or two depressions to accept liquid mixture, and the size of depression can be accepted 1-200g agricultural chemical composition, and there is no particular restriction for the shape of depression, for example, can be spherical, hemispherical, cylindrical shape, cube, taper shape, polygon taper shape has the cylindrical shape of round bottom, flat polygon cone or taper shape are arranged, pincushion or do not have given shape.
Frame container is made by a material, comprise, for example, glass such as Pyrex or soda-lime glass, metal such as aluminium or stainless steel, insoluble plastics of water such as polyethylene, polypropylene, polystyrene, polyamide, polyester, polyvinyl chloride, ABS (acrylonitrile-butadiene-styrene copolymer) resin, fluororesin, chitosan, polyurethane or polyethers, water-soluble plastics are as gram load (curdran), Bu Lulan (pluran), polyvinyl alcohol, vinyl-vinyl acetate copolymer or polyether rubber such as natural rubber or synthetic rubber, paper such as pulp board or corrugated board, wood is as cork, and mineral material such as gypsum, the framework of plastic material is preferred especially, and this is owing to contain the solid composition of agricultural chemical product that fusing point is at least 40 ℃ water-soluble polymer and be easy to therefrom take out and can be bonded on the container, at used framework equally under the situation as the packing container of agricultural chemical composition, the very easy diffusion of heat when the cooling liquid mixture makes cure, and freezing action at room temperature just can be finished in very short time, just can save the step that moulding compound is taken out from frame container, and the agricultural chemical composition just can make at an easy rate.Further, in used frame container is under the situation about making with water-soluble plastics as agricultural chemical composition packing container, is included in agricultural chemical composition in the frame container and can be sprinkled into paddy field and need composition is taken out from frame container.
Now, the second way of the present invention will be described in further detail with comparing embodiment in conjunction with the embodiments, yet, should be appreciated that the present invention is not intended to be limited to these specific embodiments.
In embodiment and the comparing embodiment, unless other specific meanings is arranged, " umber " is meant " parts by weight " below.
Embodiment 20
At 40 parts of polyethylene glycol of 70 ℃ of heat fused (mean molecule quantity: 4000, fusing point: 53.5-57.5 ℃), under 50 °-60 ℃ temperature and 22 parts of bentazon sodium, 24 parts of sodium bicarbonates and 14 parts of mixedization of citric anhydride.Then, it is that 2.5cm highly is in the cylinder-shaped frame container of 5cm that the homogenous fluid mixture of 100g acquisition is inserted the radius that is made by polyvinyl chloride, keep at room temperature making cure, then, the product that will solidify takes out from frame container to obtain the cylindrical shape composition of agricultural chemical.
Embodiment 21
20 parts of polyethylene glycol (mean molecule quantities: 4000 of heat fused in the time of 70 ℃, fusing point: 53.5-57.5 ℃) and 20 parts of polyethylene glycol (mean molecule quantities: 600), under 50-60 ℃ temperature, with 22 parts of bentazon sodium, 24 parts of sodium bicarbonates and 14 parts of citric acids mix, then, the homogenous fluid mixture that 200g obtains is inserted the cube frame container that the every length of side that is made by polyvinyl chloride is 6cm, keep at room temperature making cure, the product that will solidify from frame container, to take out to obtain the cube composition of agricultural chemical.
Embodiment 22
15 parts of polyethylene glycol (mean molecule quantities: 20000 of heat fused in the time of 70 ℃, fusing point, 60-63 ℃), under 50 °-60 ℃ temperature, with 30 parts of benthiocarbs, 1 part of benzyl ethyl methyl, 6 parts of mefenacets, 27 parts of sodium bicarbonates, 14 parts of citric anhydrides, 4 parts of tartaric acid, 1.7 part polyoxyethylene alkane phenyl ether and 0.3 part of calcium dodecyl benzene sulfonate mix, then, the homogenous fluid mixture that 25g is obtained is inserted in the semicircle frame container that the radius of being made by polypropylene is 2.5cm, similarly, liquid mixture is inserted in the semicircle frame container, the opening portion of two semicircle frameworks is meshing with each other, this set is chilled to room temperature makes cure, the product that will solidify takes out the agricultural chemical spherical set compound that obtains 50g/ part from frame container.
Embodiment 23
15 parts of polyethylene glycol (mean molecule quantities: 20000 of heat fused in the time of 70 ℃, fusing point: 60-63 ℃), under 50-60 ℃ temperature, with 30 parts of benthiocarbs, 1 part of benzyl ethyl methyl, 6 parts of mefenacets, 28 parts of sodium bicarbonates, 14 parts of citric anhydrides, 4 parts of tartaric acid, 1.7 part polyoxyethylene alkane phenyl ether and 0.3 part of calcium dodecyl benzene sulfonate mix, then, the homogenous fluid mixture that 25g is obtained insert by polypropylene make equally as in the framework of filling containers and be molded as the semicircle that radius is 2.5cm, keep at room temperature making cure to obtain the semicircle composition of agricultural chemical, this agricultural chemical composition takes out from frame container when it uses.
Embodiment 24
15 parts of polyethylene glycol (mean molecule quantities: 20000 of heat fused in the time of 70 ℃, fusing point: 60-63 ℃), under 50-60 ℃ temperature and 30 parts of benthiocarbs, 1 part of benzyl ethyl methyl, 6 parts of mefenacets, 28 parts of sodium bicarbonates, 14 parts of citric anhydrides, 4 parts of tartaric acid, 1.7 part polyoxyethylene alkane phenyl ether and 0.3 part of calcium dodecyl benzene sulfonate mix, then, the homogenous fluid mixture that 5g is obtained is inserted in the framework of being made by polypropylene that can be used as packing container equally and is molded as radius is that the height of 1cm is the cylindrical shape of 1.5cm, keep at room temperature making it to solidify the cylindrical shape composition that obtains agricultural chemical, this agricultural chemical composition takes out from frame container when it uses.
Embodiment 25
5 parts of polyethylene oxide (mean molecule quantities: 100000 of heat fused in the time of 80 ℃, fusing point: 65-67 ℃) and 10 parts of polyethylene glycol (mean molecule quantities: 600), under 60-70 ℃ temperature, with 30 parts of benthiocarbs, 1 part of benzyl ethyl methyl, 6 parts of mefenacets, 28 parts of sodium bicarbonates, 14 parts of citric anhydrides, 4 parts of tartaric acid, 1.7 part polyoxyethylene alkane phenyl ether and 0.3 part of calcium dodecyl benzene sulfonate mix, then, the homogenous fluid mixture that 25g obtains is put into the semicircle frame container that the radius of being made by stainless steel is 2.5cm, remain on 0 ℃ the indoor cure that makes, the product that will solidify takes out the semicircle composition that obtains agricultural chemical from frame container.
Embodiment 26
15 parts of polyethylene polyoxypropylene block polymer of heat fused (Evan785 in the time of 70 ℃, trade name, make by Daiichi Kogyo Seika K.K., fusing point: 49 ℃), and under 55 ℃-65 ℃ temperature and by 15 parts of pyroquilons, be dissolved in the solution that 20 parts of 2-phenoxetols are made, 26 parts of sodium bicarbonates, 14 parts of citric anhydrides, 1 part of sodium alkyl benzene sulfonate, the sodium salt of 4 parts of extraordinary aromatic sulfonic acid-formalin condensation products, 5 parts of diatomite (Ku-nilite 301, and trade name is made by Kunimine Kogyo K.K.) mix.Then, it is that 2cm highly is in the same framework as the cylindrical shape filling containers of 4cm round bottom that the homogenous fluid mixture of 50g acquisition is inserted the radius of being made by polypropylene, keep at room temperature making cure to obtain to have the agricultural chemical cylindrical shape composition of round bottom, this agricultural chemical composition can take out from frame container when it uses.
Embodiment 27
35 parts of polyethylene glycol (mean molecule quantities: 2000 of heat fused in the time of 70 ℃, fusing point: 50-53 ℃), under 50-60 ℃ temperature and 15 parts of pyroquilons, 26 parts of sodium bicarbonates, 14 parts of citric anhydrides, 1 part of sodium alkyl benzene sulfonate, the sodium salt of 4 parts of special aromatic sulfonic acid-formalin condensation products, mix with 5 parts of urea, then, the homogenous fluid mixture that 50g the is obtained radius of being made by gypsum of packing into is that 2cm highly is in the cylinder-shaped frame container that round bottom is arranged of 4cm, and remains on 0 ℃ the indoor cure that makes, and the product that will solidify takes out the semicircle composition of acquisition agricultural chemical from frame container.
Embodiment 28
14 parts of polyethylene glycol (mean molecule quantities: 20000 of heat fused in the time of 70 ℃, fusing point: 60-63 ℃), under 50-60 ℃ temperature and 34 parts of IBP, 30 parts of sodium bicarbonates, the phenyl ether of 18 parts of tartaric acid and 4 parts of polyoxyethylene styrene-modifications mixes, then, it is that 2cm highly is in the same framework as the cylindrical shape filling containers of 4cm that the homogenous fluid mixture of 50g acquisition is inserted the radius of being made by polypropylene, keep at room temperature making cure to obtain the cylindrical shape composition of agricultural chemical, this agricultural chemical composition takes out from frame container when it uses.
Embodiment 29
5 parts of polyethylene oxide (mean molecule quantities: 100000-170000 of heat fused in the time of 70 ℃, fusing point: 65-67 ℃), 10 parts of polyethylene glycol (mean molecule quantities: 1540, fusing point: 43-46 ℃), 9 parts of ether chrysanthemum esters, (Sorpol 3154 for 3 parts of surfactants, trade name, Co., Ltd makes by the Toho chemistry) and 18 parts of phenyl xylyl ethane (Hisol SAF-296, trade name, make by Nippon Sekiyu K.K.), under 50-60 ℃ temperature, mix with 36 parts of sodium bicarbonates and 19 parts of citric anhydrides, then, it is that 2cm highly is that 4cm is equally in the framework as cylindrical package containers that the homogenous fluid mixture that 50g is obtained is inserted the radius of being made by polypropylene, keep at room temperature making cure to obtain agricultural chemical cylindrical shape composition, this agricultural chemical is combined in when it uses and takes out from frame container.
Embodiment 30
15 parts of polyethylene glycol (mean molecule quantities: 20000 of heat fused in the time of 70 ℃, fusing point: 60-63 ℃), under 50-60 ℃ temperature, add 30 parts of benthiocarbs, 1 part of benzyl ethyl methyl, 6 parts of mefenacets, 28 parts of sodium bicarbonates, 14 parts of citric anhydrides, 4 parts of tartaric acid, 1.7 parts of polyoxyethylene alkane phenyl ethers and 0.3 part of calcium dodecyl benzene sulfonate.Then, the homogenous fluid mixture that 50g obtains is inserted by polyvinyl alcohol (HycelonS-400, trade name, make by Nichigo Film K.K.) make in the bag shape framework that is of a size of 10cm * 10cm, the import of heat-sealing bag, the mixture of sealing keeps at room temperature making cure to obtain the bag shape solid composite of agricultural chemical, and this agricultural chemical composition can wrap in and be applied to paddy field in the frame container.Comparing embodiment 15
With 22 parts of bentazon sodium, 40 parts of polyethylene glycol (mean molecule quantities: 4000, fusing point: 53.5-57.5 ℃), 24 parts of sodium bicarbonates, 14 parts of citric anhydrides mix, then, the 100g homogeneous mixture is put into radius be 2.5cm highly for the mortar of 15cm with flaker (Riken power P-16B-028 type is made by Riken Seiki K.K.) at 200kg/cm 2Carry out mold pressing under the pressure to obtain comparative composition.Comparing embodiment 16
With 30 parts of benthiocarbs, 1 part of benzyl ethyl methyl, 6 parts of mefenacets, 15 parts of polyethylene glycol (mean molecule quantity: 20000, fusing point 60-63 ℃), 28 parts of sodium bicarbonates, 14 parts of citric anhydrides, 4 parts of tartaric acid, 1.7 parts of polyoxyethylene alkane phenyl ethers and 0.3 part of calcium dodecyl benzene sulfonate mix, then, the 50g homogeneous mixture being put into radius is that 2.5cm highly uses flaker (as mentioned above) at 50kg/cm for the mortar of 15cm 2Carry out mold pressing under the pressure, yet, can not obtain solid composite, this is because of the surface of a large amount of composition bonds at the mortar wall.Comparing embodiment 17
(Carplex 1120 with 20 parts of white carbon, trade name, make by Shionogi Pharma-ceutical Co., Ltd) mix with 30 parts of benthiocarbs, further, with 1 part of benzyl ethyl methyl, 6 parts of mefenacets, 1.7 parts of polyoxyethylene alkane phenyl ethers and 0.3 part of calcium dodecyl benzene sulfonate mix, then, the 50g mixture being put into diameter is that 2.5cm highly uses flaker (as mentioned above) at 50kg/cm for the mortar of 15cm 2Carry out mold pressing under the pressure to obtain comparative composition.Comparing embodiment 18
20 parts of polyethylene glycol (mean molecule quantities: 20000 of heat fused in the time of 70 ℃, fusing point: 60-63 ℃), under 50-60 ℃ temperature and 30 parts of benthiocarbs, 1 part of benzyl ethyl methyl, 6 parts of mefenacets, 41 parts of ammonium sulfate, 1.7 parts of polyoxyethylene alkane phenyl ethers and 0.3 part of calcium dodecyl benzene sulfonate mix.Then, the homogenous fluid mixture that 50g obtains is inserted in the semicircle frame container that the radius of being made by polypropylene is 2.5cm, kept at room temperature making cure, solidification products is taken out from frame container to obtain comparative composition.Comparing embodiment 19
With 15 parts of pyroquilons, 35 parts of polyethylene glycol (mean molecule quantities: 20000, fusing point: 60-63 ℃), 26 parts of sodium bicarbonates, 14 parts of citric anhydrides, 1 part of sodium alkyl benzene sulfonate, the sodium salt of 4 parts of extraordinary aromatic sulfonic acid-formalin condensation products and 5 parts of urea evenly mix, then, the 50g homogeneous mixture being put into radius is that 2.5cm highly uses flaker (as mentioned above) at 50kg/cm for the mortar of 15cm 2Carry out mold pressing under the pressure to obtain comparative composition.Comparing embodiment 20
35 parts of polyethylene glycol (mean molecule quantities: 20000 of heat fused in the time of 70 ℃, fusing point: 60-63 ℃), under 50-60 ℃ temperature and 15 parts of pyroquilons, 1 part of sodium alkyl benzene sulfonate, the sodium salt of 4 parts of extraordinary aromatic sulfonic acid-formalin condensation products, 5 parts of urea and 40 parts of ammonium sulfate mix, then, the homogenous fluid mixture that 50g obtains is inserted in the semicircle frame container that the radius of being made by polypropylene is 2.5cm, keep at room temperature making cure, solidification products is taken out from frame container to obtain comparative composition.The test of foaming of test implementation example 4 compositions and dispersive property
This experiment is carried out as test implementation example 3 identical modes, and experimental result is listed in the table 7.
Table 7
Figure 0010092100401
Table 7 (continuing)
Figure 0010092100411
Foam degrees O: foaming significantly, and foaming lasts till that composition disperses fully.△: less foaming, and foaming does not last till that composition disperses.*: do not observe significant foaming diffusance O: do not have composition residue △: a spot of composition residue is arranged in landing place in landing place.X: the composition residue that significant quantity is arranged in landing place.Test implementation example 5
Test to barnyard grass and reed herbicidal effect
This experiment is carried out as the identical mode of test implementation example l, and test result is listed in the table 8.
In table, diffusance O: good, △: not shell divide and *: difference is represented.
Is undressed situation to index 10 with 11 grades from index zero to the effect of plant: kill fully and represent.
Table 8 The test of test implementation example 6 control rice blast
This experiment is carried out as test implementation example 2 identical modes.Experimental result is listed in the table 9
Table 9
Figure 0010092100431
Estimate phytotoxicity based on following standard:
-: normal leaf (plant-less toxicity);
±: the observed phytotoxicity that is not more than about 10% leaf.
+: the phytotoxicity of observed about 10-30% leaf.
++: observed phytotoxicity greater than about 30% leaf.
By method of the present invention, a kind of solid composition of agricultural chemical product that is used in paddy field from the ridge of paddy field easily, it is safe in utilization and economize the labour and use agricultural chemical to become possibility, and can quite easily prepare.

Claims (4)

1. method for preparing the solid composition of agricultural chemical product of underwater foamed type, comprise as the base stock composition, the active component of agricultural chemical, in water, can produce the foaming ingredient and the solid, water soluble polymer of gas, it is characterized in that, comprise heating and melting solid, water soluble polymer, mix to constitute other component and the water-soluble polymer of agricultural chemical composition in melt stage, and in a frame container this mixture of cooled and solidified.
2. preparation agricultural chemical method for compositions as claimed in claim 1 is characterized in that the fusing point of water-soluble polymer wherein is at least 40 ℃.
3. preparation agricultural chemical method for compositions as claimed in claim 1 is characterized in that, foaming ingredient wherein is the mixture of analogs such as carbonate and solid, water soluble acidic materials.
4. preparation agricultural chemical method for compositions as claimed in claim 1 is characterized in that frame container is wherein made with plastic material.
CNB001009214A 1991-07-08 2000-01-03 Method of preparing underwater foamed type solid composition of agricultural chemical product Expired - Lifetime CN1166292C (en)

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