CN1052377C - Solid agrochemical formulations - Google Patents

Abstract

To obtain a throwing-in type agrochemical preparation capable of application without requiring a special tool or without coming into the paddy field, free from a fear of insufficient medicinal efficacy or chemical injury caused by maldistribution of the active components and excellent in safety to a worker or the environment. A granular nucleus capable of floating on the water surface and containing one or more kinds of materials selected from calcined vermiculite, expanded pearlite, expanded pumiceous sand and cork is coated with agrochemical components or absorbed with agrochemical components. The resultant granular nucleus is subsequently coated with one or more kinds of substances selected from acetylene alcohol, acetylene diol and a surfactant synthesized by adding an alkylene oxide thereto to obtain a solid agrochemical. The obtained solid agrochemical is divided and packaged in spreadable water-soluble paper, preferably a film made of polyvinyl alcohol and/or its derivative, thus producing the objective throwing-in type agrochemical preparation capable of dispersing or dissoling the active components into water. If this preparation is applied to a paddy field, the solid agrochemical floats on the water surface and spread over a wide range. The active components are subsequently dispersed or emulsified in water readily.

Description

Solid agrochemical formulations

The present invention relates to solid agrochemical formulations, or rather, the present invention relates to the novel solid agrochemical formulations, the using method of its preparation method and this class preparation.

So far, agricultural chemicals and other agricultural chemicals are prepared into wieldy various forms in the rice field, as powderous preparations, wettable powder, emulsible concentrate or granular preparation are sprayed on it in rice field or on the rice plants.

But the problem that powderous preparations and wettable powder bring is to cause the producer and user's health affected and cause environmental pollution because of its powdery character.On the other hand, emulsible concentrate has brought toxicity problem, and because of the danger of the caused burning of organic solvent.Granular preparation (though generally do not have these shortcomings) is disadvantageous, and this is not only from distribution and economic aspect but also because the intrinsic effectiveness of some active component is not observed in many cases.

Owing to these reasons, people have developed new preparation such as flowable preparation and dry flowable preparation recently.With the aqueous solution, suspension or emulsion use these preparations behind dilute with water.Preparation does not have dust characteristic because flowable and drying can flow, and has suitable flowability, and therefore, they are counted as solving the preparation of the shortcoming that above-mentioned wettable powder has.But, in order to spray these preparations, at first need they to be dissolved or be dispersed in the water, need operative installations in many cases.Also need in the rice field, walk and spray.For the small-scale peasant that the industry of paying is arranged, this expends economical, and worries safety.This is very difficult, and has to lose time and prepare to be used to dissolve or the groove of the pharmaceutical dispersions operative installations of packing into, and walking is sprayed in the rice field then.Now, for small-scale farm, more depend on the elderly and women, this generic request is unallowed.

Therefore, developed a kind of method that is easy to spray recently, this method does not require special device.A kind of flowable herbicide formulations is packed in the plastic bottle, pour into the rice field by the aperture of bottle cap.The advantage of this method is to be easy to use, without any need for special device.But, the sprinkling of still need in the rice field, walking.In addition, as spray insecticide, learn the author on one's body the time because of spray method and wind direction will be sprayed onto behaviour, the care to safety is drawn in this operation.Therefore, can overcome normal methodical shortcoming fully hardly.In addition, spray the used bottle of post processing and can bring safety and environmental problem.

For example, known as follows at easy floating particles preparation floating on the water surface: (1) uses floatable carrier (Japan Patent discloses clear 48-15613, and Japan Patent discloses clear 47-1240) on the water surface; (2) use carrier such as float stone or vermiculite (Japan Patent discloses clear 44-8600) with some water absorption character; (3) use the granular preparation (Japan Patent discloses clear 49-11421) that contains volatile insecticide; (4) use be loaded with carbamate pesticide and organic compound (with the distribution coefficient of water be 10 ²More than) solid carrier (Japan Patent is openly applied for, flat 2-174702); (5) use by solid carrier, active constituent such as weed killer herbicide, bactericide or plant growth regulator and oil group or composition (Japan Patent is openly applied for, flat 3-193705).And, adopt these preparations, there is not difference with the application method of any conventional particles preparation, there is not to reduce demand to the labour yet.

At present, the herbicide formulations that use in the rice field is existing to be described, (Japan Patent is openly applied for wherein to have added surfactant and blowing agent in active component, flat 3-128301), and tablet or capsule contain active component, surfactant and adhesive (Japan Patent is openly applied for, flat 3-173802).In order to use these preparations, a kind of effective method be with them with water-soluble wrapping paper such as polyvinyl alcohol (hereinafter being abbreviated as PVA) film wrapped, make and a kind ofly can be spread product (Japan Patent is openly applied for, flat 4-226901) in the rice field by throwing.

These preparations that are thrown into paddy fields are favourable because of it is easy to use.But solid pharmaceutical preparation is different from traditional particle and powder formulation disperses inhomogeneous.When in the water that these novel solid preparations are thrown into paddy fields, said preparation is fallen the bottom in rice field, and its active component is distributed in the paddy field water either.Insoluble active component be deposited in landing point around.The active component of having dissolved forms the solution of high concentration on the soil surface around the landing point, it is easy to be absorbed by soil.Owing to these reasons, the active component with suitable highly-water-soluble tends to that high concentration is absorbed on the soil around the landing point.According to rice field and weather conditions, the shortcoming of existence is as because the uneven distribution of active component to crops growing plants toxicity, does not have uniform effectiveness, damages crops afterwards in some cases.

Under many situations,, blowing agent is joined throwing spread in the preparation,, active component is scatter by barbotage so that solid pharmaceutical preparation bursts apart as quickly as possible and disperses in order to prevent the uneven distribution of active component as wide as possible.Blowing agent is made up of organic acid plus carbonate, their formation carbon dioxides that reacts in the presence of water.Yet using this class foaming preparation is fixed with the component of preparation thereupon the problem of bringing, react to each other with carbonate in lay up period acid, and then and the difficulty of coming be as packing expand and when using foaming capacity reduce.Especially, supposing by foaming effect makes active component must be dispersed in the water, even be dispersed in the rice field of lower water temperature, so that dissolving diffusion as quickly as possible, form conforming layer at soil surface, when preparation was spread in throwing, it is insufficiently diffusing that the foaming capacity reduction means that active component collapses, and therefore brought problem.

Some other known preparations comprise: the granular preparation of floatability on paddy field water either, and it contains the anti-effective agrochemistry component of bacterium (Japan Patent discloses clear 48-1179) that causes that the rice dry rot is mashed; The granular preparation of floatability on the water surface, wherein in the perlite of Qi Paoing occlusion insecticide and waterproofing agent (Japan Patent discloses clear 48-1181); Granular preparation, wherein the weed killer herbicide emulsifiable concentrate is in the inorganic carrier of floatability on the water surface (Japan Patent discloses clear 48-1182); The granular agricultural Chemical composition that of floatability on the water surface wherein added cellulose ether or poly-carboxylate type high molecular surfactant, to promote the diffusion (Japan Patent discloses clear 48-15612) of active component; Agrochemical formulations, wherein emulsible concentrate is attracted in the cork powder, and the product dilute with water sprays (Japan Patent is openly applied for clear 56-18902) during use; Comprise bioactivator and the floatability composition prepared on the water surface, wherein biological active component is adhered in the organic or inorganic microporous particles, the proportion of this particle is lower than 1.0, diameter less than 5mm as the 4%MIPC microparticle preparation that uses cork and use expand in vain must rock Shirasu) 5% basudin microparticle formulation (Japan Patent discloses flat 2-56323); The solid pharmaceutical preparation of floatability on the water surface, said preparation are by the agrochemistry component, and solid carrier and polyoxyalkylene silicon compound are formed (Japan Patent discloses clear 64-25702); Emulsible fine powder preparation soluble in water, the liquid technical grade material that wherein contains active component and emulsifier are attracted to by in the bulk material of the rock preparation of thermal expansion (Japan Patent discloses flat 3-76281).But these technology and traditional powder and granular preparation also no difference on using method can not reduce necessary work.

The object of the present invention is to provide a kind of agrochemical composition, the said composition easy operating does not injure the user and destroys environment.

Or rather, the object of the present invention is to provide a kind of preparation and methods for using them that can meet the following conditions:

Do not need special device when (1) using.

Need not in the rice field, to walk when (2) using.

(3) it is safe to user and environment.

(4) container easy operating and cleaning.

(5) can not cause the insufficient and phytotoxicity of agrochemistry effect because of uneven distribution.

(6) said preparation is stable.Can long term storage.

Consider above-mentioned these situations of mentioning, the present inventor is eager to develop a kind of preparation and using method that satisfies above condition.

The invention provides a kind of agrochemical formulations that in the rice field, uses.Said preparation comprises the floating bag of solid floatability mixture.This floatability mixture comprises agrochemistry component and floatability carrier, especially is selected from expansion Shirasu, expanded vermiculite, expanded perlite, or the floating carrier of cork.Mixture is wrapped in the water-soluble film, when this Film Fractionation, mixture is diffused on the water surface.Select the size and the weight of bag, be convenient to throw in the rice field so that make agrochemical formulations be the bag shape.

The present invention is based on following discovery: when in the agrochemistry solid pharmaceutical preparation floating carrier being arranged, solid pharmaceutical preparation can swim on the water surface; Can prevent the uneven distribution of active component in the rice field if this floating agrochemical formulations (when active component is easy to disperse and is dissolved in the water) is wrapped in when also being thrown in the rice field in the film above-mentioned, therefore can reduce phytotoxicity is renderd a service uneven worry.In addition, because the present composition need not contain any blowing agent, the situation of physical property can not appear impairing, as the loss of foaming capacity and the expansion of wrappage.

Bag of the present invention is inequality with above-mentioned known technology in fact, in order to save the labour, to throw in the rice field to tens fine powder mixture bags for several by per 10 ares, this mixture is diffusion as quickly as possible on the water surface of rice field, discharge active component then at short notice, dissolving also is distributed in the water, has prevented the drift on the water surface that causes because of wind.

Embodiment preferred

The floatability mixture that uses in the bag of the present invention comprises the floatability carrier.

Can be used for expansion Bai Xuyan of the present invention and be the material of a kind of porose microparticle to particle, its bulk density is little, is inertia, has good compatibility and flowable.Must be found in the Guinier-Preston zone and quadratic-layer of volcano float stone by rock (being to can be used for the expansion of the present invention raw material of palpus rock in vain) in vain, its volcano float stone is widely distributed, but mainly is distributed in the EMUs for Kyushu of Japan south.A spot of white palpus rock has also been found in Hokkaido in Japan near ten He Tianhu and the area, the Northeast.About 70% is amorphous volcano matter glass in the white palpus rock, the Bai Xuyan that expands and obtain expanding during the high temperature heating.When the white palpus of processing rock under lower temperature, the thickness of its product is 6 μ m, has than higher bulk density, contains the impurity of limited flotation property.When at high temperature handling in vain must rock the time, thickness is about 3 μ m, and the bulk density of product is lower, is easy to swim on the water surface.But, if treatment temperature is higher, micropore breaks, and product is easy to submerged, and product has various grade, this depends on particle size, average grain diameter from little to tens microns to greatly to several millimeters, for each grade, two kinds of bulk densities are arranged, a kind of bulk density height, and another kind of bulk density is low.Expanding in vain, the general porosity of palpus rock is 65～95%.Collect the expansion Bai Xuyan of lightweight part if adopt air elutriation or elutriation, can obtain to have the more expansion Bai Xuyan of high-grade porosity so, in the present invention, the expansion Bai Xuyan of any grade is spendable, this depends on preparation type, as long as it can float on the water.

Vermiculite is the raw material that can be used for expanded vermiculite of the present invention, it is a kind of mica mineral, be distributed in South Africa, the U.S., Russia, Australia, China, other place, comprising Japan, find this mineral in the area, Fukuoka of Japan, in order to expand, heating vermiculite and at the about 1000 ℃ temperature lower calcination of height, to remove its water of crystallization.Simultaneously, the mica layer layering of many stratiforms, mass expanded becomes light mineral.The vermiculite product of these mineral usually is used as construction material, is applied in agricultural and the gardening.Its color difference depends on the origin of rock: South Africa be white, the U.S. be silver gray, Chinese or Japanese arrive golden yellow for brown.According to the particle size of the virgin rock before the calcining, can obtain the expanded vermiculite of size fractionated; By below the 1mm to more than the 5mm.

In most of the cases, floatability in the time will dropping in the water through the vermiculite of calcining.If calcining heat is low, the layering of mica layer is insufficient, generates limited flotation property material.If calcining heat is too high on the other hand, product becomes fragile and easily crushes.If contain very a high proportion of impurity in the virgin rock, mica layer had both made after calcining also not stratified, formed the particle of limited flotation property: in this case, preferably carry out classification to remove this class particle according to air elutriation or elutriation method.

Obsidian, perlite or pitchstone all are the raw materials that can be used for expanded perlite of the present invention, and they are various natural glasses, the volcanic region of the rock stratum that after date is new as a comparison when mainly being distributed in the Tertiary Period.This worldwide distribution in class rock stratum extends to Mediterranean from the western part in U.S. state by Europe and southern Iceland, and the secondary rock stratum of face extends to New Zealand and Australia from Japan.Autumn fields in Japan, mountain side, divides greatly and this kind rock has been found in Hokkaido Fukuoka, Nagano, Saga.In order to expand, heating and calcining obsidian under near 1000 ℃ high temperature, perlite or pitchstone are to remove water of crystallization and volatile component, and Ruan Hua glass promptly expands.This expanded perlite product is a kind of float stone, and there is the hole as pearl in portion within it, is used for building, in insulating materials and the gardening commonly.Have from below the 1mm to the perlite of the various grades more than the 5mm.The kind of virgin rock is depended in the variation of shape of product, density and size distribution, particle size and expansion condition.Usually, pearl rock and pitchstone are used to prepare the expanded perlite of hybrid particles size, and obsidian is used to especially prepare and has the fine grained and the unusual expanded perlite of lightweight.When using obsidian, can obtain the harder pelletized product in garden.

The vermiculite and/or the perlite that require to expand all swam on the water surface before coated material is diffused on the water surface and scatters everywhere at least.It contains many not dispersed components for use, the material of cracked severity and just to have put in the rice field preparation of the material of precipitation just unfavorable, this be because in the landing point active component also with these species precipitate, in addition, at landing point phytotoxicity appears, the inhomogeneities of effect and more residue.On the other hand, from commercial values point, wish the inorganic substances precipitation everywhere in component after scattering on the water surface, the perlite of expansion is poroid not precipitating because of it, still stays on the water surface.What wish most is the vermiculite that expands, because its precipitates and As time goes on becomes not noticeable, this is owing to only contain the air layer cause between the mica layer of layering.

In addition, these inorganic substances are lightweight normally, so when with water-soluble film this product being rolled into parcel, this bag can be greatly to throwing.The oily adsorptivity of expanded vermiculite is very big, can use a large amount of liquid adhesive coating agricultural chemical activity components like this, because it can make liquid adhesive be retained in this product, can prepare smaller bag.Only for this point, the vermiculite of expansion also is better than the perlite that expands.

Can be used for cork of the present invention is prepared by The cork oak tree.They mainly are grown in Portugal, with bark grind into powder or particle, obtain being used for the material of bottle stopper, plate and combustible.Have the cork of various grades to can be used as raw material, the mixing ratio of the cork slag that returns can be different, and the cork of any grade all can be used for the present invention, are easy to use less than the cork of about 1cm than the cork of larger particles size but it is ground to particle diameter.

In the present invention, the agrochemistry component is mixed with floatable material, mix with other additive in case of necessity in addition, or molded in case of necessity to obtain suitable solid mixture.

Will to be enough to that preparation is swum in waterborne for the amount of floatability carrier in the solid mixture.Although rely on the kind of floatability carrier to some extent, the kind of active component and the kind of additive and consumption are more than 15%, to be preferably 30～90% in order to reach floating general necessary amounts.Because the floatability of cork is bigger than other carrier, therefore, required cork minimum is about 3%.

So, the solid floatability mixture that obtains is wrapped in the water-soluble film.Each parcel for example can be put into the rice field in the aisle between the rice field during use.When putting into preparation in the rice field, water-soluble film scatters and dissolves, and the agrochemistry solid mixture in the film is diffused on the water surface equably, and the active component dispersing and dissolving forms conforming layer on soil surface in water like this.Thereby the uneven distribution of active component on soil surface is decreased to actually as far as possible ignores.

Water-soluble film is film or the thin slice that himself is easy to be dispersed or dissolved in the water, and it can make parcel agrochemistry solid mixture within it be diffused on the water surface.Above-mentioned PVA or PVA derivative film are the examples of this class water-soluble film.

Can be prepared with plasticizer, stabilizing agent and other component in a small amount by polyvinyl alcohol and can be used for PVA film of the present invention, the degree of polymerization of polyvinyl alcohol is 1000～2000, and saponification degree is 85-95%.Suitable PVA product comprises and contains in a small amount carboxylate or other copolymer film.This film must have enough mechanical strengths, cold resistance and water-soluble.If the degree of polymerization of original polyvinyl alcohol and saponification degree are too high, this film is inappropriate, and this almost is insoluble in cold water because of it.Though the thickness of spendable film is 25-70 μ m, consider that the intensity of film requires its dissolution time simultaneously, the thickness of film is preferably 30～50 μ m.

If the agricultural chemical activity component is an insecticide, mildewcide or bactericide, it has system activity to rice plants then is preferred.Yet even it does not have this type systematic activity, but it can resist the insect that colonizes in the water or on the water surface effectively, or the mould of being infected by the water surface.In this case, this compound should have low phytotoxicity, under the situation of weed killer herbicide, consider its intrinsic property and service time thereof, it is particularly preferred selecting the low compound of phytotoxicity, need not consider whether this active component is soluble or insoluble,practically in water, or solid or liquid.Solid mixture of the present invention can contain two or more active components.

Spendable preferred active ingredient comprises among the present invention: as insecticide, insecticide such as karphos with systemic effect, Kayaphos, DEP, basudin, disulfoton, the peace fruit, Rogor, nuvacron, orthen, carbosulfan, thiocyclarn, Padan, Benfuracard micro (benfuracarb), furathiocarb (furathiocarb), sevin, Buprofezin; Osbac; unden; Imidacloprid (imidacloprid) and TI304 and pyrethroids are as ring prothrin and ether chrysanthemum ester (etofenprox); they are effectively anti-colonize in the water or the water surface near insect, as rice water weevil and the chrysomelid worm of rice; As bactericide, be used for the bactericide such as the probenazole of blight of rice, Fujione, IBP, tricyclazole and piloquinone; Those that are used for the sheath fusarium wilt are as flutolanil (flutolanil), mebenil, and MON240 and S658: and tecloftalam (tecloftalam): as weed killer herbicide; Weed killer herbicide such as the pyrazoles acid esters that use in the rice field, benzofenap, pyrazoxyfen, pyributicarb (pyributicarb), bromobutide, mefenacet, bensulfuron-methyl, butachlor, the third careless amine, benthiocarb, Mo 9 granular, chlomethoxyfen daimuron, bifenox, naphthoxy Phenylpropionamide, oxadiazon, bentazone, standing grain Tian Jing, croak grass phosphorus, dimepiperate (dimepiperate), esprocarb (esprocarb), dithiopyr (dithiopyr), imazosulfuron (imazosulfuron), benfuresate (benfuresate), how quinone kills, cinmethylin, second first 4 monoxones, quinclorac, pyrazosulfuron, KPP 314, N-[2-(3-methoxyl group) thienyl methyl]-N-chloroethene ester-2,6-dimethyl N-anilide (NSK850), 1-(2-benzyl chloride base)-3-(α, α-Er Jiajibianji)-urea (JC 940), ether yellow grand (cinosulfuron) and N-[4,6-dimethoxypyridin-2-yl) aminocarbonyl]-3-methyl-5-(2-chloro-2,2-difluoroethoxy)-4-isothiazole sulfonamides.Also can use plant growth regulator such as inabenfide, paclobutrazol, uniconazole P and triapenthenol.

Particularly preferred component is that its solvability in water is higher than and is the compound of solid under 10ppm and the normal temperature.If being used in the water is quite soluble these active components, all form the solution of high concentration so at landing point by any preparation of jettisoninging of already mentioned common technology preparation, active component is absorbed by the soil around the high concentration landing point, is easy to occur the uneven distribution of component.On the other hand, if use agrochemical formulations of the present invention, solid mixture itself can spread on the water surface everywhere, begins to discharge active component then.Because this release is subjected to suitable control, its advantage is to prevent the uneven distribution of active component in soil as much as possible that the compound with this class advantage comprises;

(1) is selected from weed killer herbicide such as the bensulfuron-methyl that use in the rice field of sulfonylurea, imazosulfuron (imazosulfuron), pyrazosulfuron, ether yellow grand (cinosulfuron) or N-[4,6-dimethoxypyridin-2-yl)-amino carbonyl)-3-methyl-5-(2-chloro-2,2-difluoroethoxy)-4-isothiazole sulfonamides.

(2) be selected from the insecticide that use in thiocyclarn or Padan's rice field;

(3) be selected from the bactericide that use in the rice field of piloquinone, tricyclazole, Fujione and probenazole.

If but active component is a compound soluble in water hardly, agrochemistry solid mixture of the present invention can not stop release, but because active component at a good pace is dispersed in the water, has quickened release.Can obtain the desirable preparation that is used to jettisoning, the uneven distribution of said preparation active component is little more a lot of than the common dosage forms that adopts blowing agent.

After parcel was thrown into the rice field, active component must be dissolved or disperse, and in the water that is diffused into the rice field at short notice, demonstrated biological effect.If active component is confined in the zone for a long time, the much less insufficient and phytotoxicity of trouble that may occur such as effect.Therefore, even the solvability of active component in water is very high, when being solid, it preferably it can be ground into certain degree.If active component is dissolved in the water hardly, especially that it is levigate so usually, adopt the dry grinding of hammer-mill or jet mill, preferably adopt sand mill or attrition mill wet-milling.When if active component is the technical grade material of liquid, it is dissolved in the suitable solvent or emulsifier in case of necessity and (is absorbed in then in the floatable carrier), and/or have in the thinner of suitable oil absorption, or be molded into molded mixture in advance comprising other component of floatability carrier, make such preparation, can adsorb above-mentioned liquid active substance or solution, can obtain for floatability target agrochemistry solid mixture on the water surface of throwing usefulness.

In order to improve the diffusivity of agrochemistry solid mixture of the present invention on the water surface, this agrochemistry solid mixture can comprise water surface diffusant in case of necessity.

As preferred water surface diffusant, can mention; Polycarboxylic acid salt's polysoap comprises the sodium of carboxylic acid such as acrylic acid or maleic acid, potassium or ammonium salt, the copolymer salt of carboxylic acid and styrene sulfonic acid or vinyl; Polysulfonate type polysoap such as kayexalate, potassium or ammonium; Soap class such as enuatrol and potassium stearate; Anion surfactant such as dialkyl group sulfo-sodium succinate, the detergent alkylate sodium phosphate, Sodium Laurylsulfate and perfluoro carboxylic acid sodium: non-ionic surface active agent such as polyoxyethylene aryl aryl ether, polyoxyethylene alkyl ether, polyxyethylated ester and alkyl sorbitol dehydration ester; Various other listed the non-ionic surface active agent of block copolymer (pluronic) series of silicon series, ethyl group or oxirane one expoxy propane in, in addition, this class non-ionic surface active agent in the surfactant further neutralizes with suitable alkali under some situation with phosphoric acid or Sulfation again; Fluorine-containing surfactant; Various cations and amphoteric surfactant; The mineral oil such as white oil and the naphthalene that comprise high boiling solvent; Low viscous polybutene and silicone oil; Various animal and plant oil; Various resins such as pine resin; Camphorated oil; Australene; Camphor; And naphthalene.

In these surfactants, acetylene is surfactant such as acetylene alcohol and acetylenic glycol, and oxirane adduction product is special Dai Xuan as the water surface diffusant.

The amount of water surface diffusant can change, and this depends on the kind and the consumption of active component, the kind of water surface diffusant and the kind of other component and consumption, but its consumption is 0.1～10% usually, is preferably 0.3～5%, more preferably is 0.5～3%.

In the time of in the parcel preparation is thrown into paddy fields, active constituent swims on the water surface and diffusion everywhere.Disperse then, emulsification also is easy to be dissolved in the water, and fast as far as possible is distributed in the whole rice field.If particularly this component is water-soluble hardly, the active component particle swims on the water surface for a long time, and active component has been quickened the part of active component and assembled with wind drift under some situation.So, need to add suitable wetting agent and dispersant or emulsifier so that active component is suspended or emulsification in water.For this purpose, can add suitable filler and additive in case of necessity and be easy to a kind of like this curing mixture moistening and that disperse with the preparation active component.As the additive that can be used for this purpose can be the waterproofing agent of mentioning, disintegrating agent, dispersant, wetting agent, adhesive, filler, solvent, emulsifier, lubricant prevents germination agent or stabilizing agent, in these additives, disintegrating agent, dispersant, wetting agent and emulsifier are for preventing that the concentrated sinking of active component is important in the solid mixture.

Preferred spendable dispersant comprises anion surfactant such as the plain sulfonate of art; (alkyl) naphthalene sulfonate and its condensation product; Phenolsulfonic acid and its condensation product; The condensation product of styrene sulfonate; The condensation product of maleic acid and styrene sulfonate; The salt of the condensation product of carboxylic acid such as acrylic acid or maleic acid; Alkylbenzenesulfonate, dialkyl sulfosuccinates, lauryl sulfate; Polyoxyethylene alkyl ether sulfate salt; Polyoxyethylene alkylaryl ether sulphate, polyoxyethylene alkyl ether phosphate: polyoxyethylene alkylaryl ether phosphate; With phosphate such as sodium phosphate trimer and calgon.If it is solid is not a powder, many in these additives also as disintegrating agent with as the moistening of mixture agent.

Dispersant and wetting agent can be those materials mentioned above, also can be any suitable nonionic, cation or amphoteric surfactantes.In addition, after suction, have the material such as the starch of swelling properties, carboxymethyl cellulose, carboxymethyl starch, and salt, the bridging compound of polyvinylpyrrolidone, microcrystalline cellulose are particularly useful as with the resin with very strong water absorbing capacity and are disintegrating agent and dispersant.

The molded of floating carrier, active component and other additive can be used adhesive, obtains powder formulation such as particle, sheet and the agglomerate of solid.As preferred adhesive, what can mention is low-molecular-weight dextrin, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose, gum Arabic, polyethylene glycol and derivative thereof.Lignosulphonates and carboxylic acid type or sulfonate type polysoap especially can be used as filler, and especially lignosulphonates can be used as filler, and this is because its price is quite low.

Any of these adhesive can apply the floating carrier with active constituent and other additive with water, then, just can obtain product after the dried if necessary.Another kind method, the proper adhesive that can use suitable liquid adhesive maybe can liquefy.This adhesive can evaporate after coating or owing to a kind of adhesive of evaporated liquid hardly that uses (or liquefaction adhesive) is stayed in the product.The latter's advantage is to save drying steps.Preferred adhesive does not influence germination and division, and applies the floating material with active component equably.Generally, have high boiling point, hypotoxicity, low inflammability, low viscosity, proportion be lower than 1 and wherein its active constituent to have limited deliquescent solvent be preferred.Solvent as the adhesive with this class feature can be mentioned: low viscous mineral oil such as atoleine, machine oil or butylene; Silicone oil or radical derivative; Plasticizer comprises: list or dicarboxylic ester, and as oleic acid, coco-nut oil fatty acid, maleic acid, fumaric acid, the ester of phthalic acid or adipic acid, and phosphate; Ethylene glycol such as 1,2 ethylene glycol, two-1,2 ethylene glycol, polyethylene glycol, propane diols or butanediol and its ester and/or ether; Lactone such as 6-caprolactone or gamma-butyrolacton; N-Methyl pyrrolidone and liquid surfactant.Atoleine in these solvents, machine oil, polybutene or carboxylate are preferred, and this is because the great majority in them are more cheap, does not influence active constituent, is stable, and volatility is low.

Filler can be used to active constituent is diluted to suitable concentration and regulates the amount that is easy to throw.Can mention as preferred filler: generally use the inorganic substances powder of used as pesticides filler such as bentonite, talcum, clay, imvite, amorphous silica, calcium carbonate and magnesium carbonate: organic substance comprises carbohydrate such as glucose, sucrose and lactose; Carboxymethyl cellulose and its salt; Starch and derivative thereof; Microcrystalline cellulose; Wood powder, rice chaff, wheat bran and powdered rice hulls; Water-soluble inorganic salt such as sodium sulphate, ammonium sulfate and potassium chloride; And urea.

In this respect, atoleine and low-molecular-weight polybutene are particularly preferred.

Use solvent dilution liquid technical grade material in case of necessity, perhaps the technical grade material is made low-melting-point liquid.So, select the solubilized industrial material, do not influence the stability of industrial material, have high boiling point, hypotoxicity and low flammable solvent.The proportion of many pesticide industry stage materials generally is higher than 1.Therefore, for the particle that makes own emulsification is retained in the water as far as possible for a long time so that make active component in the rice field everywhere the diffusion, in most of the cases use proportion be lower than 1 and the low solvent of viscosity be most preferred.

Emulsifier can be used to liquid active component or the active component solution in the emulsified water.According to active constituent and solvent, as selecting to select emulsifier the emulsifier with regard to EC.Different with the situation of general EC, need not to carry out artificial or mechanical agitation.Therefore, preferably select natural and surfactant that have the well emulsify characteristic, its addition is more bigger than general EC.

Can add lubricant film-making and agglomerate in case of necessity adheres on the wall of device for molding preventing.Preferred lubricant is a magnesium stearate, calcium stearate, and talcum, polyethylene glycol, fatty and oily, surfactant, sugar ester, glyceride and iron oxide.

When active constituent is very easily water-soluble, in order to control the release of active constituent, after being diffused on the water surface as far as possible widely, it is dissolved in the water, mainly add waterproofing agent.Can comprise as preferred waterproofing agent: soap such as dolomol, calcium stearate and enuatrol; Higher alcohol such as octadecanol; Higher fatty acid such as stearic acid, silicone oil and its derivative; Fluorine-containing surfactant: cationic surfactant: hydrophobic silica: or atoleine and machine oil.

Characteristic according to active component can add prevention germination agent and stabilizing agent in case of necessity.In addition, various additives such as dyestuff and bitters can be added in the solid mixture in case of necessity.

In case of necessity blowing agent is added in the agrochemistry solid mixture, floating to impel, diffusion, division and dispersed activity component.Common mode is possible use the mixed-powder of organic acid plus carbonate.Citric acid, malonic acid, succinic acid, fumaric acid, oxalic acid, or tartaric acid is the preferred organic acid of mentioning; Sodium bicarbonate, sodium carbonate, concentrated crystal soda, potash, saleratus or calcium carbonate are the preferred carbonate of mentioning.

Can be with active component, floating carrier and other additive mix, and use suitable moulding press to be molded as solid pharmaceutical preparation in case of necessity.Solid pharmaceutical preparation such as pulvis, wettable powder, particle, ball, ball, sheet or agglomerate are preferred.

In order to obtain this class preparation,, it is levigate according to dry method or wet method if active material is a solid.If adopt wet method to pulverize, can with through slurry that wet-milling obtains or at the additive dispersant after the slurry that wet-milling obtained adopts as sprays dried device drying.But mix with float carrier and any other additive by slurry then and be molded as solid pharmaceutical preparation drying.Another kind method is mixed this slurry in advance with part or all of floating carrier and any other additive, be dried after the granulation in case of necessity.The solid product of resulting drying can use or adopt moulding press that it is molded as solid pharmaceutical preparation like this.

If required solid mixture is a powder, but the levigate material that produces is mixed with float carrier and any other additive, or use suitable cracker to grind, obtain solid mixture.If required solid mixture is solid pharmaceutical preparation such as particle, ball, ball, sheet or the agglomerate of no powder, levigate material can be mixed with floatability carrier and other additive, by dry method or wet method it is molded as required preparation then.Basket Squeezinggranulator, mixing granulation machine, fluidized bed pelletizer or drum change comminutor and can be used as wet moulding press: and roller type press, flaker, agglomerating machine or hydraulic pressure moulding press all can be used as dried moulding press.When the employing roller type press, flaker, when agglomerating machine or the compacting of hydraulic pressure moulding press, if hypertonia, molded product does not swim on the water surface, at this moment needs pressure to be reduced or regulate by sneaking into a kind of material with cushioning effect.

If active material is liquid or liquefied material, can be absorbed by floating carrier or oil suction supporting mass according to this active material of the method for having mentioned, adopt with the solid material similar approach and be made into solid mixture.Another kind method is in advance floating carrier and any other additive to be molded as required form, makes it to absorb the material of liquid active component or liquefaction, obtains required solid mixture.

If this mixture is the solid pharmaceutical preparation of non-powder,, as a rule, when the surface at non-powder solid preparation has diffusant to exist, present bigger effect though the water surface diffusant has some effect.So in order to reach bigger effect, at first preparation contains active component, the non-powder solid preparation of floating carrier and any other additive, water diffusion into the surface agent applies the preparation that obtains then, or makes its preparation absorb the water surface diffusant.

Be used in this agrochemistry solid mixture of film wrapped that spreads on the water surface, this parcel can be need not walking from ridge and be administered in the rice field.

Because preparation of the present invention is to be thrown in the rice field outside the rice field, so it must have weight to a certain degree.

When being rolled into parcel, when the weight of each parcel is 30-150g, be easy to it is launched.Even child, women and the elderly also are easy to the parcel that each is such and put into impact point in the 15m.If the weight of each bag is heavier, thrown with regard to difficulty, use just difficult for the large tracts of land rice field.If the weight of each bag is lighter, because the influence of wind can not arrive impact point.

Generally need not to throw at a distance parcel in common rice field, is that 2-3m is just enough from the ridge between the rice field with the distance that parcel is thrown into the water surface.But must consider remote the throwing, as under following situation: if the rice field is wide, if because stopping of a large amount of rice field plants causes improper ventilation to reduce moving of water; If owing to the too much growths of marine alga and pasture and water makes on the water surface diffusion insufficient; If perhaps the active component utmost point is insoluble in water or is difficult to diffusion owing to being absorbed by soil too much.The most normally be because floating carrier is light, the very big influence that is subjected to wind easily of bag sometimes.

In this case, gain in weight parcel is made be easy to and throw by regulating its proportion.Can use the water-soluble substances or the water-insoluble materials of high bulk density as the material of regulating proportion.Can comprise the inorganic substances particle that grinds such as silica, clay as water-soluble substances, calcium carbonate, bentonite or talcum, or with suitable ratio by the molded solid of these materials; Bead; Alumina balls; Or iron powder.Can comprise organic substance such as sugar as water-soluble substances, loaf sugar or crystal sugar, or its molded solid; Inorganic substances such as potassium chloride, ammonium sulfate, urea or sodium sulphate, or its molded solid.

The size and the relative quantity of regulating the material of proportion are not crucial, correspondingly depend on needed purpose.The material of its interpolation can add before being distributed into parcel in the mixture, perhaps packed in the parcel with this mixture individually, promptly so-called two reinforced packings.

If the parcel number of throwing in the rice field is too many, throwing them is troubles, does not save the labour, also unfavorable economically.If very little, solid pharmaceutical preparation can not spread fully everywhere.Generally, this number can be per 10 ares several to dozens of, 5-20 preferably.

Solid agrochemical mixture of the present invention should scatter on the water surface, then active component is disperseed and is dissolved in the water, therefore, measure as the method that adopts according to following EXPERIMENTAL EXAMPLE 2, preferably the amount of floating active component is lower than 50% on back 20 minutes waters surface of input.For this purpose, can regulate wetting agent, the consumption of dispersant and disintegrating agent.

Prepared parcel can further be packaged in the bag of being made by paper, film of synthetic resin or box, or in the bag or box with the aluminium foil layering.When mixture of the present invention does not contain blowing agent, be more stable As time goes on: do not need careful isolated moisture as the preparation that contains blowing agent to humidity.But, since can be diffused on the water surface water-soluble film with break after water contacts, so should use suitable waterproof bag.

The present invention will be for a more detailed description by following embodiment and experimental example, but these embodiment do not limit the scope of the present invention.

In this embodiment with reference to the accompanying drawing of listing, wherein

Fig. 1 shows by the active component release test of experimental example 3 and measures, the result of embodiment 1 and comparative example 7 preparations:

Fig. 2 shows by the active component release test of experimental example 3 and measures, the result of embodiment 9 and comparative example 9 preparations;

Fig. 3 shows by the active component release test of experimental example 3 and measures, the result of embodiment 22 and comparative example 7 preparations;

Fig. 4 shows by the active component release test of experimental example 3 and measures, the result of embodiment 30 and comparative example 8 preparations.

Embodiment 1

With 24 parts of industrial piloquinones, 3 parts of talcums (Japanese Pharmacopoeia) and 1 part of amorphous silica (Carplex # 80, Shionogi pharmaceutical companies) mix, and adopt hammer-mill that it is pulverized, and obtain premix.With 57 parts of average grain diameters be 75 μ m expansion Bai Xuyan (PB03 product, Silax Co. Ltd) pack in the mixing screw, with 13 parts of thick atoleines (Superoil C, Nippon Petrochemicals Co., Ltd.), should in vain must rock surface with coating.Add 28 parts of premixs and also mix, and then (Ltd.) coating should white palpus rock surface for Surfynol 104 S, Nisshin Chemical Ind.Co. to add 2 portions of hexin non-ionic surface active agents.The product that has applied contains 24% piloquinone.The resulting coating product of a 50g installed to (Hi-SelonC-200, Nippon Gohsei Film Co. is in the parcel that Ltd.) makes by the thick PVA film of 40 μ m.

When parcel to be put into area be center in 2m * 2m artificial rice field, parcel swam on the water surface, PVA film dissolving simultaneously, and the particle in it is diffused on the water surface, and active component is dispersed in the water.

Embodiment 2

With 24 parts of industrial piloquinones, 2.5 part waterproof silica (Aerosil R 972, Japan Aerosil Co. is Ltd.) with poly-surfactant (the Toxanone50 P of 5 parts of poly-carboxylation object heights, Sanyo Chemical Ind.Co. Ltd.) mixes and the employing hammer-mill is pulverized.With the expansion Bai Xuyan of 53.5 parts of average grain diameter 0.42mm (PB 10, and SilaxCo. Ltd) packs in the Polythene Bag, add 15 parts of thick atoleines (Superoil C) with wetting white must the rock surface, add the mixture of 31.5 parts of pulverizing then and mix.This coating product contains 24% piloquinone, according to the step that is similar to embodiment 1 this product is divided with every bag 50g to install in the parcel.

When parcel being put into area is center in 2m * 2m artificial rice field, and this parcel swims on the water surface, PVA film dissolving simultaneously, and the particle in it is diffused on the water surface, and active component is dispersed in the water.

Embodiment 3

(PB 02 with the expansion Bai Xuyan of 40 parts of average grain diameters, 37 μ m, Silax Co., Ltd), 8 parts of calcium carbonate powder (Ashidachi Lime Co., Ltd) and 7 parts of dextrin (Amicol No.1, Nippon Starch Chemical Co., Ltd) pack into kneading machine (Fuji Paudal Co., Ltd) in and mix.In mixture, add 10 parts of aqueous solution that contain 40% anion surfactant (Toxanone GR 31A, SanyoChemical Industries Co., Ltd) in, add an amount of water and knead.Adopt Squeezinggranulator (Fuji Paudal Co., Ltd, Eck Pelleter Exk-1) to be pressed through the 1.2mm mesh sieve and make the product granulation of having kneaded.(Midget-Drier) at 130 ℃ of dry these particles of following air, the collecting granules size obtains particulate vector for the part of 1-3mm for Fuji Pauddal Co., Ltd. to adopt fluid bed dryer.59 parts of particulate vectors that obtain are packed in the Polythene Bag, add 10 parts of atoleines (extra-pure grade) coating particle surface.Piloquinone premix with 28 parts of embodiment 1 applies this particle, adds 3 parts of surfactants then and then mixes acetylene class non-ionic surface active agent (Surfynol104S) coated surfaces a little.Resulting coating product contains 24% piloquinone.Be distributed into parcel according to the step coating product that is similar to embodiment 1 with every bag 50g.

When parcel being put into area and be the center of artificial rice field of 2m * 2m, parcel swims on the water surface, PVA film dissolving simultaneously, and the material of granule interior spreads on the water surface, and active component is dispersed in the water.

Embodiment 4

With 1.5 parts of technical grade bensulfuron-methyls, 6 parts of technical grade pyributicarbs (Pyributicarb), 4.5 part technical grade daimuron, 3 parts of anion surfactant (Neopelex No.6F, KaoCorporafion), 8 parts of granular calcium carbonate (K-3, Sankyo Seifun Co., Ltd), (Vanilex N, Sanyo-Kokusaku Pulp Co. Ltd) mix with 3 parts of Aerosil R 972 10 parts of sodium lignosulfonates, (SeishinEnterprise Co. is Ltd.) with feed rate and the 6kg/cm of 2kg/hr to adopt Jet-o-Mizer type 101 ²Air pressure grind 2 times, obtain the premix of technical grade material, with 35 parts of premixs, 40 parts of expansion Bai Xuyan (Silax PB 03) mix in 11 parts of calcium carbonate powders and 7 parts of dextrin (Amicol No.1) kneading machine of packing into.In mixture, add the 10 parts of aqueous solution (Toxanone GR 31A) and an amount of water that contain 40% anion surfactant, this mixture of kneading.(Kikusui Co. Ltd.) is pressed through the 1.5mm mesh sieve with the resulting product granulation of kneading to adopt basket Squeezinggranulator.Adopt fluid bed dryer at 60 ℃ of dry these particles of following air.Collection cut size is the part of 1.5-5mm, obtains granular preparation.97 parts gained granular preparation is packed in the Polythene Bag, add 3 portions of hexin non-ionic surface active agents (Surfynol 104S) and mix, allow surfactant coating particle surface a little.The resulting granules preparation contains 0.5% bensulfuron-methyl, 6% pyributicarb (Pyributicarb) and 4.5%daimuron.

According to the step that is similar to embodiment 1 this product is distributed into parcel.When parcel being put into area and is the artificial rice field center of 2m * 2m, parcel swims on the water surface, PVA film dissolving simultaneously, and the material of granule interior spreads on water surface, active component is dispersed in the water, along with the division of particle obtains almost suspension uniformly.

Embodiment 5

The knead product identical with embodiment 4 components made ball, under reduced pressure obtain the heavy 1g of each ball, contain 0.5% bensulfuron-methyl, the spherical preparation of 6% pyributicarb (Pyributicarb) and 4.5%daimuron in 60 ℃ of dryings.

According to the step that is similar to embodiment 1, resultant spherical preparation branch is installed in the parcel of being made by the PVA film.When parcel being thrown into area and is the artificial rice field center of 2m * 2m, this parcel swims on the water surface, PVA film dissolving simultaneously, and spherical preparation materials inside spreads on the water surface, active component is dispersed in the water, along with the division of particle obtains almost suspension uniformly.

Embodiment 6

Technical grade material premix with 35 parts of embodiment 4,50 parts of expansion Bai Xuyan (Silax PB03), 1 part of anion surfactant (Emalo that key component is a lauryl sodium sulfate, Kao Corporation), 5 parts of polyocarboxy acid type polysoaps (Demol EP, Kao Corporation) and 9 parts of microcrystalline cellulose (Avicel Tg 101, AsahiChemical Industry Co. Ltd) mixes and adopts miniature roller type press non-slurry pelletizing.Particle is crossed the 1cm purpose and is sieved and become uniform.Resulting granules contains 0.5% bensulfuron-methyl, 6% pyributicarb (Pyributicarb) and 4.5%daimuron.

According to the step that is similar to embodiment 1, this particle branch is installed in the parcel.When parcel was thrown into area and is the artificial rice field center of 2m * 2m, parcel swam on the water surface, PVA film dissolving simultaneously, and the granule interior material spreads on the water surface, and active component is dispersed in the water, along with the division of particle obtains almost suspension uniformly.

Embodiment 7

With 2 parts of polyoxyethylene aryl aryl ether be non-ionic surface active agent (Newcol 702 X, Nippon Nyukazai Co., Lyd) be dissolved into 10 parts atoleine (No.30, Chuo Kasei Co., Ltd) in.With 53 parts of expansion Bai Xuyan (Silax PB03) pack into the quick-action kneading machine (Showa Giken Co., Ltd) in, add paraffin solution, mix to apply the surface of expansion Shirasu a little.The premix that adds the technical grade material of 35 parts of embodiment 4.The product of this coating contains 0.5% bensulfuron-methyl, 6% pyributicarb (Pyributicarb) and 4.5%daimuron.According to the step that is similar to embodiment 1 this particle branch is installed in the parcel.

When parcel being thrown into area and be the artificial rice field center of 2m * 2m, parcel swims on the water surface, PVA film dissolving simultaneously, and the granule interior material spreads on the water surface, and active component is dispersed in the water, along with particle spliting, obtains almost suspension uniformly.

Embodiment 8

The preparation emulsifier mixture comprises:

Non-ionic polyoxyethylene aryl aryl ether surfactant,

(Newcol?2609，Nippon?Nyukazai?Co.，Ltd.)

45％

Non-ionic surface active agent, (TP 6618, Nippon Nyukazai Co., Ldt)

25％

Calcium dodecyl benzene sulfonate (Nippon Nykazai Co., Ltd. product)

30％

With 50 parts of technical grades, the third careless amine, 40 parts of liquid side cured (chuokasei NO.30) and 10 parts of emulsifier mixtures mix, and obtain spontaneous emulsification and the emulsifiable concentrate lighter than water.(PB20, SilaxCo. Ltd.) pack in the Polythene Bag with 82 parts of average grain diameters expansion Bai Xuyan that is 0.62mm.By adding the mixture of 18 parts of spontaneous emulsifications, then mix and absorb, obtain containing the solid mixture of the 9% the third careless amine.According to the step that is similar to embodiment 1 this solid mixture branch is installed in the parcel.

When parcel being thrown into area and be the artificial rice field center of 2m * 2m, parcel swims on the water surface, PVA film dissolving simultaneously, and the internal solids mixture discharges on the water surface, and active component is emulsified in water, obtains almost emulsion uniformly.

Embodiment 9

With 12 parts of technical grade thiocyclarns, 3 parts of oxalic acid and 10 parts of clays mix, and adopt hammer-mill to pulverize, and obtain the premix of thiocyclarn.The Bai Xuyan (silaxPB03) of 54 parts of expansions and 5 parts of cork powders are packed in the mixing screw, add 11 parts of atoleines (sup-eroilc), mix the surface that coating in vain must rock.Add 25 parts of thiocyclarn premixs then, then add 5 portions of acetylene class non-ionic surface active agents (Surfynol 104S) coated surfaces.The coating product of gained contains 12% thiocyclarn.The product that will apply by the step that is similar to embodiment 1 is distributed in the parcel.

When parcel being thrown into area and be the artificial rice field center of 2m * 2m, parcel swims on the water surface, PVA film dissolving simultaneously, and the solid mixture in it is distributed on the water surface, and active component is dispersed in the water.

Embodiment 10

According to the step that is similar to embodiment 1, just with 21, the white palpus of the pure and mild expansion of 2-ethylene rock replaces the non-ionic surface active agent (Surfynol 104 S) of rubble wax oil (Superoil C) and acetylene class respectively, resulting coating product does not have diffusibility on the water surface, this product contains 24% piloquinone.According to the step that is similar to embodiment 1, this coating product branch is installed to each bag in the parcel of 50g.

Embodiment 11

(Newcol 714, and Npp-on Nppon Co. Ltd.) is dissolved in 10 parts of two-1,2 ethylene glycols with two parts of non-ionic polyoxyethylene aryl aryl ether surfactants.Use this solution to replace the atoleine solution that uses among the embodiment 7, according to the solid pharmaceutical preparation that the step that is similar to embodiment 7 obtains applying, said preparation contains 0.5% bensulfuron-methyl, 4.5%daimuron and 6% pyributicarb (pyributicarb).This solid mixture branch is installed in the parcel.

Embodiment 12

According to the step that is similar to embodiment 9, just with two-1, the pure and mild anion surfactant of 2-ethylene (Neopelex NO.6F) replaces thick liquid stone body wax (Superoil C) and Surfynol 104 S respectively, obtain containing the coating solid mixture of 12% thiocyclarn, this mixture branch is installed in the parcel

Embodiment 13

According to the step that is similar to embodiment 9, just with two-1, the white palpus of the pure and mild expansion of 2-ethylene rock replaces the non-ionic surface active (surfynol104 S) of thick atoleine (Superoil C) and acetylene class respectively, the coating product that obtains does not have diffusibility on the water surface, this product contains 12% thiocyclarn, will apply the product branch and install in the parcel.

Embodiment 14-17

According to the step that is similar to embodiment 1.The coating product branch that embodiment 10 is obtained installs in the parcel, and this parcel all derives from Aicello Chemical Co. by thickness 40 μ m PVA films (Solublon KC #40 and Slublon PH 30), and Ltd. corresponds respectively to embodiment 14 and 15); Thick 30 μ m PVA films (embodiment 16 for Solublon KD 30, AicelloChem-ical Co.LTD.) and 35 μ m PVA films (Toslon ET-20#35, Tohcello Co., Ltd. embodiment 17) make.For embodiment 14-17, the parcel that whenever comprises 2.0g coating product will be packed.

Embodiment 18-21

According to the step that is similar to embodiment 1, to install in the parcel by the coating product branch that embodiment 13 obtains, this parcel is by thickness 40 μ m PVA film (Solublon KC # and Solublon PH 30, correspond respectively to embodiment 18 and 19): thick 30 μ m PVA film (Solublon KD 30, embodiment 20) and the PVA film (ToslonET-20 # 35, embodiment 21) of thick 35 μ m make.For embodiment 18-21, the parcel that each comprises 2.0g coating product will be packed into.

Embodiment 22

With 24 parts of technical grade piloquinones, 3 parts of talcums (Japanese Pharmacopoeia) and 1 part of amorphous silica (Carplex # 80) mix, and adopt hammer-mill to be ground into premix.(Hilcon S-1, Hil-uishi Chem.Ind.Co. Ltd.) pack in the mixing screw, add the wetting vermiculite of 35 parts of thick atoleines (Superoil C) surface with 35 parts of particle sizes calcining vermiculite that is 2.5-0.3mm.Add and be divided into 28 parts of premixs of 4 minutes.After mixing, the non-ionic surface active agent (Surfynol 104 S) that adds 2 parts of acetylene classes further applies the surface of vermiculite.The product of coating contains 24% piloquinone.The gained coating product of every part of 50g is installed in the parcel of being made by the PVA film of thickness 40 μ m (Hi-Selon C-20).

When the bag that will apply product was thrown in the water, this bag swam on the water surface, and diffusion is so that be distributed in the water active component soon.Especially, when this bag being thrown in the artificial rice field that area is 2m * 2m, parcel is floating, PVA film dissolving simultaneously, and the particle in it is diffused on the water surface, and active component is dispersed in the water.

Embodiment 23

(Surfynol 61 by the fast class non-ionic surface active agent of 1: 1 second in employing, Niss-hin Chemical Ind.Co. Ltd.) mixes with amorphous silica (Carplex # 80) through pulverizing the acetylene class non-ionic surface active agent (Surfynol 104 S) that 50% premix for preparing replaces use among the embodiment 22.The step that employing is similar to embodiment 22 obtains parcel.Lu is produced in the gained coating and parcel plays embodiment 22 in water.

Embodiment 24

(Surfynol 440 by 1: 1 acetylene class non-ionic surface active agent in employing, Ni-sshin Chemical Ind.Co. Ltd) mixes the acetylene class non-ionic surface active agent (Surfynol 104 S) that makes use among the 50% premix replacement embodiment 22 through pulverizing with amorphous silica (Carplex # 80).The step that employing is similar to embodiment 22 obtains parcel, and gained coating product and parcel play embodiment 22 effects in water.

Embodiment 25

According to the step that is similar to embodiment 22, just, obtain parcel with the acetylene class non-ionic surface active agent (Surfynol 104 S) among poly-carboxylate class Polymer Surface activating agent (Toxanone 50 P) the replacement embodiment 22.Gained coating product and parcel play embodiment 22 in water.

Embodiment 26

Employing mixes the acetylene class non-ionic surface active agent (Surfynol 104 S) that makes use among the 50% premix replacement embodiment 22 through pulverizing by the non-ionic surface active agent (Newcol 702 x) of 1: 1 polyoxyethylene distyrene tolyl ethers with amorphous silica (Carplex # 80).The step that employing is similar to embodiment 22 obtains parcel.Gained coating product and parcel play embodiment 22 in water.

Embodiment 27

According to the step that is similar to embodiment 22, be acetylene class non-ionic surface active agent (Surfynol 104 S) among non-ionic surface active agent (Emal o) the replacement embodiment 22 of dodecyl sodium sulfate just with key component, obtain parcel.Gained coating product and parcel play embodiment 22 in water.

Embodiment 28

According to the step that is similar to embodiment 22, be non-ionic surface active agent (the Neopelex NO.6 F Powcler of neopelex just with key component, Kao Corpora-tion) the acetylene class non-ionic surface active agent (Surfynol 104 S) among the replacement embodiment 22 obtains parcel.Gained coating product and parcel play embodiment 22 in water.

Embodiment 29

The preparation blended emulsifier is as follows:

Non-ionic surface active agent (Newcol 2609) 45%

Non-ionic surface active agent (TP 6618) 25%

Calcium dodecyl benzene sulfonate (Nippon Nyukazai) 30%

With 50 parts of technical grades, the third careless amine, the emulsifier of 40 parts of atoleines (Chuokasei No.30) and 10 parts of mixing obtains having spontaneous emulsification and the mixture lighter than water.With 38 parts of particle sizes is that 2.5～0.3mm is contained in the Polythene Bag through the vermiculite (Hilcon S-1) of calcining, the mixture and the blended absorbent that add 12 parts of emulsifications, the solid pharmaceutical preparation that obtains containing the 12% the third careless amine wraps up the solid pharmaceutical preparation that this obtains according to the method that is similar to embodiment 22.When throwing into this solid pharmaceutical preparation in the water, said preparation swims on the water surface, but its diffusibility is very weak.But the effect that should wrap embodiment 22.Because solid product swims on the water surface.Active component emulsification in water obtains uniform emulsion.

Embodiment 30

With 12 parts of technical grade thiocyclarns, 3 parts of oxalic acid and 10 parts of clays mix, and adopt hammer-mill to pulverize the premix that obtains thiocyclarn.(Ltd.) mixing screw of packing into adds 30 parts of rubble wax oils (Superoil C), the surface of mixing moistening vermiculite for Hilcon S-0, Hiruishi Chem.Ind.Co. with 40 parts of particle sizes calcining vermiculite that is 1.2～0.3mm.Then, add 25 parts of thiocyclarn premixs, then add 5 portions of acetylene class non-ionic surface active agents (Surfynol 104 S), apply this surface.Gained coating product contains 12% thiocyclarn.To apply product according to the step that is similar to embodiment 22 and make parcel.Gained coating product and parcel play embodiment 22 in water.

Embodiment 31

With 0.5 part of technical grade bensulfuron-methyl, 6 parts of technical grade pyributicarbs (Pyributicarb), 4.5 part technical grade daimuron, 3 portions of anion surfactants (Neoplex No.6 F), 3 parts of granular calcium carbonates (Sanhyo Seifun K-3), 10 parts of sodium lignosulfonates (Vani-lex) and 3 parts of Aerosil R 972 mix, adopt Jeto-Mizer type 101 (SeishinEnterprise Co., Ltd products) with the feed rate of 2kg hr at 6kgcm ²Air pressure under pulverize 2 times, obtain premix.In calcining vermiculite (Hilcon S-0) mixing screw of packing into 38 parts of particle size 1.2-0.3mm, adding that 30 parts of two-1,2 ethylene glycols are moistening should the surface, then adds the premix of 30 parts of (being divided into four parts) industrial materials.With this mixture mixed after, add 2 portions of acetylene class non-ionic surface active agents (Surfynol 104 S), mix coating vermiculite surface.Gained coating product contains 0.5% bensulfuron-methyl, 6% pyributicarb (Pyributicarb) and 4.5%da-imuran.According to the step that is similar to embodiment 22, will apply the product branch and install in the parcel.This coating product and parcel play embodiment 22 in water.

Embodiment 32

In 42 parts of particle sizes calcining vermiculite (Hilcon S-1) mixing screw of packing into that is 2.5～0.3mm, add 30 part two-1,2 ethylidene glycols mix moistening vermiculite surface, add 28 parts of premixs that (being divided into four parts), embodiment 22 obtained then, coating vermiculite surface.The resulting coating product of 50g branch is installed in the parcel that is made by PVA film (Hi-Selon C-200).When throwing into this parcel in the water, the coating product swims on the water surface, and active constituent disperses in water, but does not find the particle diffusion.The gained parcel plays embodiment 22 in artificial rice field.

Embodiment 33-38

Obtain parcel by the step that is similar to embodiment 22-27, with 55 parts of particle sizes expanded perlite (perlite L that is 1.2-0.5mm, Hattori Co.Ltd.) replaces the Hilcon S-1 that uses among the embodiment 22-27, the consumption of rubble wax oil (Superoil C) is changed to 15 parts.Coating product and parcel play embodiment 22 in water.

Embodiment 39

With 82 parts of particle sizes is that 1.2～0.5mm expanded perlite (perlite L) replaces the Hilcon S-1 that uses among the embodiment 29, makes the consumption of emulsifying mixt into 18 parts, obtains containing the solid pharmaceutical preparation of the 9% the third careless amine according to the step that is similar to embodiment 29.Solid pharmaceutical preparation divided as described above install in the parcel.This solid pharmaceutical preparation and parcel play embodiment 29 in water.

Embodiment 40 and 41

Use 55 or 53 parts of particle sizes to replace the Hilcon S-0 of use among the embodiment 30 and 31 as the expanded pearlite (perlite L) of 1.2-0.5mm, with paraffin or two-1, the consumption of 2 ethylidene glycols makes 15 parts into, step by embodiment 30 and 31 prepares solid pharmaceutical preparation, then it is distributed into parcel as described above.This solid pharmaceutical preparation and parcel play embodiment 30 and 31 respectively in water.

Embodiment 42

With 57 parts of particle sizes is the Hilcon S-1 that 1.2-0.5mm expanded perlite (perlite L) replaces use among the embodiment 32, with two-1, the consumption of 2-ethylidene glycol makes 15 parts into, step according to embodiment 32 prepares solid pharmaceutical preparation, like that its branch is installed in the parcel as mentioned above then, solid pharmaceutical preparation and parcel play embodiment 32 in water.

Embodiment 43

With 40 parts of particle sizes is that 1.2-0.5mm expanded perlite (perlite L) and 7 parts of dextrin (Amicol No.1) mix, with its fluidized bed pelletizer of packing into (Spir-A-Flow, Industrial Co., Ltd.) in.Mixture is flowed, add 10 portions of poly-carboxylate class Polymer Surface activating agents (Toxanone GR 31A, SanyoChemical Ind.Co., Ltd.) and an amount of water granulation, dryly then obtain the particle that particle size is 0.3-3mm.51 parts of particles are put into mixing screw, add moistening this particle surface of 18 parts of rubble wax oils (Superoil C), add premix and the mixing mentioned among 28 parts of embodiment 22.At last, add 3 portions of acetylene class non-ionic surface active agents (Surfynol 104S), mix this particle surface of coating.Obtain the parcel of made coating particle according to the step that is similar to embodiment 22, this product plays embodiment 22 in water.

Embodiment 44

With 56 parts of expanded perlites (perlite L), premix and 7 parts of dextrin (Amicol No.1) that 30 parts of embodiment 10 obtain mix, and mixture is packed in the fluidized bed pelletizer (Spir-A-Flow).Mixture is flowed, add 10 parts of poly-carboxylation surface-active agents (Toxanone GR 31A) and an amount of water granulation, to obtain particle size be the 0.3-3mm particle to drying then.97 parts of particles are packed in the Polythene Bag, add the surface that 3 portions of acetylene class non-ionic surface active agents (Surfynol 104S) apply this particle.Obtain parcel according to the step that is similar to embodiment 22 by the coating particle of making.This product plays embodiment 22 in water.

Embodiment 45-48

The coating product that embodiment 32 is obtained installs in the parcel according to the step branch that is similar to embodiment 22, this parcel is by the thick PVA film of 40 μ m (Solublon KC #40.) embodiment 45), the PVA film that 35 μ m are thick (Toslon ET-20 #35, embodiment 46), the PVA film that 30 μ m are thick (Solublon PH #30, embodiment 47) and the thick PVA film (Solublon KD #30, embodiment 48) of 30 μ m make.Each embodiment packs the parcel that becomes to contain 2.0g coating product with each among the embodiment 45-48.

Embodiment 49-52

The coating product that embodiment 42 is obtained installs to respectively in the parcel that the PVA film as embodiment 45-48 makes.Each embodiment packs each the parcel that becomes to contain 2.0g coating product among the embodiment 49-52.

Embodiment 53

With 0.5 part of technical grade bensulfuron-methyl, 6.0 part technical grade pyributicarb (Pyributicarb), 4.5 part technical grade daimuron, 3.0 portion anion surfactant (Neopelex No.6F), 8.0 part granular calcium carbonate (Sankyo Seifun K-3), 10.0 part sodium lignosulfonate (SanyoKokusaku Pulp Vanilex N) and 3.0 parts of Aerosil R 972 mix, and adopt feed rate and the 6kg/cm of Yet-o-Mizer type 101 with 2kg/hr ²Air pressure is pulverized 2 times, obtains the premix of technical grade material.With 35 parts of premixs, 35.0 part following cork of particle diameter 0.5mm, 3.0 portion acetylene class non-ionic surface active agent (Surfynol 104S), 20.0 part potato starch (Matsutani Chem, Co., Ltd. product) and 3.0 parts of dextrin (Amicol No.1) blender of packing into (Spartan-Ryuzer, Fuji Paudal Co mix in Ltd).Add 10 portions of anion surfactants (Toxaanone GR 31A) and an amount of water mixing granulation.The particle that adopts fluid bed dryer drying (at 60 ℃ of air that heat down) to make, sieving obtains the part of particle size 2-10mm.The granular preparation that makes contains the phonetic sulphur of 0.5% benzyl, and 6.0% pyributicarb (Pyributicarb) and 4.5%daimuron. install to the 50g granular preparation in the thick PVA parcel of 40 μ m (Hi-Selon C-200).

When parcel being thrown into area and be the center of artificial rice field of 2m * 2m, parcel swims on the water surface, PVA film dissolving simultaneously, and the particle in it spreads on the water surface, and active component is disperseed in water, along with particle spliting obtains uniform suspension.

Embodiment 54

With the technical grade material premix that obtains among 35 parts of embodiment 53,20.0 a part particle diameter is the cork of 2-0.3mm, 3.0 portion anion surfactant (Emalo), 5.0 portion anion surfactant (Demol EP), 18.0 (Hodaka level, Hojun Kogyo Co. Ltd.) mix for part potato starch and 19.0 parts of bentonite in powder, and adopt miniature roller type press (Freund Industry Co., Ltd.) non-slurry pelletizing.Adopt two kinds of sieves, a kind of is the 1cm order, and another kind is the 2mm order, and particle is sieved makes it become even product.Made particle contains 0.5% bensulfuron-methyl, and 6.0% pyributicarb (Pyributicarb) installs to particle in the parcel according to the step that is similar to embodiment 53.

During center in parcel being thrown into the artificial rice field that area is 2m * 2m, parcel swims on the water surface, PVA film dissolving simultaneously, and the particle in it spreads on the water surface, and active component is disperseed in water, because particle spliting obtains uniform suspension.

Embodiment 55

The premix of the technical grade material that 35 parts of embodiment 53 are obtained, 30.0 parts of corks that particle diameter 0.3mm is following, 15 parts of microcrystalline celluloses (Avicel TG 101).17.0 part potato starch and 1 part of dolomol mix.(Hata IronWorks Ltd.) makes the sheet that diameter 2cm weighs 1g to adopt pelleter.98 parts of sheets of making are packed in the plastic sack, mix, mix the surface of this tablet of coating with 2.0 portions of acetylene class non-ionic surface active agents (Surfynol 104S).The tablet that obtains contains 0.5% bensulfuron-methyl, and 6.0% pyributicarb (Pyributicarb) and 4.5%daimuron pack tablet in the parcel into according to the step that is similar to embodiment 53.

During center in parcel being thrown into the artificial rice field that area is 2m * 2m, parcel swims on the water surface, PVA film dissolving simultaneously, and this tablet spreads on the water surface, because the tablet division, active component dispersion face in water obtains uniform suspension thereupon.

Embodiment 56

(Newcol 702 x Ltd.) are dissolved in 17 parts of atoleines (Chuo No.30) with 3 portions of non-ionic surface active agents.In mixer,, apply the surface of this cork with cork and the mixing of paraffin solution of 45 parts of particle diameter 5-2mm.The premix that adds the technical grade material that obtains among 35 parts of embodiment 53 then makes it mix slight coating cork surface with this premix.The mixture that obtains contains 0.5% bensulfuron-methyl, 6.0% pyributicarb (Pyribucarb) and 4.5%daimuron.According to the step that is similar to embodiment 53, this mixture is packed in the parcel.

When parcel being thrown into area and be the center of artificial rice field of 2m * 2m, parcel swims on the water surface, PVA film dissolving simultaneously, and the mixture in it spreads on the water surface, and active component disperses to obtain uniform suspension in water.

Embodiment 57

The preparation emulsifier mixture comprises:

Non-ionic polyoxyethylene aryl aryl ether surfactant,

(Newcol?2609，Nippon?Nyukazai?Co.，Ltd.) 45％

Non-ionic surface active agent

(TP?6618，Nippon?Nyukazai?Co.，Ltd.) 25％

Calcium dodecyl benzene sulfonate

(Nippon Nyukazai Co., Ltd. product) 30%

With 30 parts of technical grades, the third careless amine, the emulsifier of 60 parts of atoleines (Chuo No.30) and 10 parts of mixing obtains having spontaneous emulsification and than the light concentrate of water.The cork of 70 parts of particle diameter 10-5mm is inserted in the rotary evaporator.After under reduced pressure adding 30 parts of emulsification concentrates, pressure is transferred to normal pressure absorb, obtain containing the solid pharmaceutical preparation of 9 part of third leather amine.According to the step that is similar to embodiment 53, the solid mixture branch of making is installed in the parcel.

When parcel being thrown into area and be the center of artificial rice field of 2m * 2m, parcel swims on the water surface, PVA film dissolving simultaneously, and solid mixture spreads on the water surface, and active component emulsification in water obtains uniform emulsion.

Embodiment 58

With the piloquinone of 24 parts of industry, 2.5 parts of aerosils (Aerosil R972), 5 portions of anion surfactants (Toxanone 50 P) and 3 parts of camphors mix, and adopt hammer-mill to pulverize.In Polythene Bag, with 34.5 parts of milling products and 65.5 parts of softwood mix that particle diameter is 3-1mm, the mixture of powders of making contains 24% piloquinone.According to the step that is similar to embodiment 53, the weight fraction of mixture with every part of 50g installed in the parcel.

When parcel being thrown into area and be the center of artificial rice field of 2m * 2m, parcel swims on the water surface, PVA film dissolving simultaneously, and the powder in it spreads on the water surface, and active component is disperseed in water.

Embodiment 59

Cork powder and the 6 part dextrin (AmicolNo.1) of 90 parts of particle diameters below 0.3mm are put into blender (Spartan-Ryuzer).When blend mixture, add 10 portions of anion surfactants (Toxanone GR 31A) and an amount of water granulation.The dried particles product, sieving obtains the particle that particle diameter is 0.3-3mm.In addition with 24 parts of technical grade piloquinones.5 parts of sodium lignosulfonates (Pearlex NP), 5 parts of talcums (J.P.) and 2 parts of amorphous silicas (Carplex #80) mix, and adopt Jet-o-Mizer type 101 crackers to obtain the premix of technical grade material.In mixing screw, 47 parts of granulation corks are mixed with 15 parts of thick atoleines (Superoil C), to apply the surface of this particle.The premix that adds 36 parts of (being divided into 3 parts) technical grade materials then allows this premix coating particle surface.At last, 2 portions of acetylene class non-ionic surface active agents of adding (Surfynol 104S) and mixing obtain coating particle.This particle contains 24% piloquinone, according to the step that is similar to embodiment 53, this particle is packed in the parcel.

When parcel being thrown into area and be the center of artificial rice field of 2m * 2m, parcel swims on the water surface, PVA film dissolving simultaneously, particle spreads on the water surface since particle spliting and thereupon active component be dispersed in the water.

Embodiment 60

Cork powder below 30 parts of particle diameter 0.25mm and 70 parts of bentonite powder (Hojun Kogyo Hodaka level) are mixed and mix 110 parts of water and mediate this mixture.(Eck Pelleter EXK-1, Fuji Paudal Co. Ltd) are pressed through the 1.2mm mesh sieve, should mediate the product granulation to adopt Squeezinggranulator.(Midget-Drier, Fuji Paudal Co. carry out the air drying in Ltd) under 100 ℃, cross the 1.70mm mesh sieve then, remove any fine grained after the 0.3mm mesh sieve, obtain particulate vector at fluid bed dryer with this particle.In blender (Nauta Mixer, HosokawaMicron Coporation), mix 49.5 parts of resulting granules carriers, and add 13 parts of thick atoleines (Superoil C), mix the surface of coating particle.Adding the technical grade material premix that obtains among 36 parts of (being divided into three parts) embodiment 59 then allows this premix apply this particle surface.The premix that adds 1.5 portions of 50% non-ionic surface active agents pulverized (Surfynol G1) and amorphous silica (Carp/ex #80) at last mixes the granulate mixture that obtains applying.The particle that makes contains 24% piloquinone.According to the step that is similar to embodiment 53 the particle branch is installed in the parcel.

When this parcel being thrown into area and be the center of artificial rice field of 2m * 2m, parcel swims on the water surface, PVA film dissolving simultaneously, and particle spreads on the water surface, after about 5 minutes, particle spliting, bentonite and active component are dispersed in the water.

Embodiment 61

With 20 parts of cork powders and 30 parts of bentonite powder (these two kinds of materials used in embodiment 60), 30 parts of calcining vermiculites (Hilcon No.0) that particle size is 1.2-0.3mm, 18 parts of calcium carbonate powder (Calfine, Ashidachi LimeIndustry Co., Ltd) and 2 parts of dextrin (Amicol No.1) mix and mix 70 parts of water and mediate.According to the step that is similar to embodiment 8, obtain particulate vector by mediating product.In the Nauta blender, mix 80 parts of particulate vectors that make, and add 22 parts of thick atoleines (Superoil C), mix the coating particle surface.Add the technical grade material that obtains among 36 parts of (being divided into 3 parts) embodiment 59 then, allow its premix coating particle surface.At last, add 2 portions of non-ionic surface active agents (Surfynol 440) and 50% premix of amorphous silica (Carpex #80), mix obtaining coating particle through pulverizing.The coating particle of making contains 17.1% piloquinone.Every part is packed in the parcel of being made by PVA film (Hi-Selon C-200) for the 70g particle.

When parcel being thrown into area and be the center of artificial rice field of 2m * 2m, parcel is floating on the water surface, PVA film dissolving simultaneously, and particle spreads on the water surface, after about 5 minutes, particle spliting, bentonite and active component are dispersed in the water.

Comparative example 1-3

The coating product that obtains among the embodiment 10 with every part of 2.0g is respectively charged in the various water-solubility membrane parcels, this parcel respectively by 40 μ m thick by polyoxyethylene oxide derivative (Flexinu, of Dai-Ichi Kogyo Seiyaku Co., Ltd.) water-solubility membrane that makes, by carboxymethyl cellulose and cellulose (Dissolvo Wap, MishimaPaper Co., Ltd.) the pullulan film that water-soluble paper that makes or 30 μ m are thick (Ohsaka Kagaku-Gohkin Co., Ltd. product) makes.

Comparative example 4-6

The coating product that obtains among every part of 2.0g embodiment 13 is respectively charged into the various thick water-solubility membranes of 40 μ m (Flexinu) that made by polyoxy cyclic ethylene oxide derivative, the water-soluble paper and the thick pullulan film of 30 μ m (Ohsaka Kagaku-Gohkin) that make by carboxymethyl cellulose and cellulose (Dissolvo Wap).

Comparative example 7

With the premix of the technical grade material among 28 parts of embodiment 1,29.2 parts of succinic acids, 21.5 parts of sodium bicarbonates, 12.8 part sodium carbonate and 5.5 parts of sanlose (Cellogen PR, Dai-Ichi Kogyo Seiyaku Co. Ltd.) mixes, and adopts hammer-mill to pulverize.Adopt the roller type press dry method with this milling product granulation, obtain homogeneous granules by the 2mm mesh sieve.With 97 parts of sized granules and 3 parts of PEG6000 powder (Dai-Ichi Kogyo Seiyaku Co., Ltd product) mixing, adopt the pelleter film-making, obtaining each sheet diameter is the foaming tablet of the heavy 0.5g of 1cm.The tablet of making contains 24% piloquinone.According to the step that is similar to embodiment 1, this tablet is distributed into parcel with the heavy 50g of every bag.Along with parcel dissolves in water, the tablet precipitation, and in the anxious strong ground bubbling of soil surface.

Comparative example 8

Premix with the technical grade material of 35 parts of embodiment 4,26.2 part succinic acid, 18.5 part sodium bicarbonate, 11.8 part sodium carbonate and 5.5 parts of sanloses (Cellogen PR) mix, the employing hammer-mill is pulverized, and adopts the roller type press dry method with the product granulation of pulverizing, and also crosses the 2mm mesh sieve and obtains homogeneous granules, with 97 parts of sized granules and 3 parts of PEG6000 powder, adopt the pelleter film-making to obtain the foaming tablet of the heavy 0.5g of every diameter 1cm.The tablet of making contains 0.5% bensulfuron-methyl, 6%Pyributicarb, and 4.5%daimuron.According to the step that is similar to embodiment 1, heavy 50g is distributed into parcel with this tablet with every bag.

Comparative example 9

Thiocyclarn premix with 25 parts of embodiment 9,30.2 part succinic acid, 22.5 part sodium bicarbonate, 13.8 part sodium carbonate and 5.5 part of 7 sanlose (Cellogen PR) mix, the employing hammer-mill is pulverized, with of the product granulation of roller type press dry method, obtain homogeneous granules again by the 2mm mesh sieve with pulverizing.With 97 parts of PEG6000 powder of sized granules and 3 parts, and to obtain every diameter with the pelleter granulation be that 1cm heavily is the foaming tablet of 0.5g.The tablet of making contains 12% thiocyclarn.According to the step that is similar to embodiment 1, heavy 50g is distributed into parcel with this tablet with every bag.

Comparative example 10-12

The 2.0g coating product that embodiment 32 is obtained is added in the various parcels, the 40 μ m water-solubility membranes (Flexinu) that parcel is made by the polyoxyethylene oxide derivative are made by water-soluble paper (Dissolvo Wap) or the thick pullulan film of 30 μ m that carboxylic acid methyl cellulose and cellulose make.

Comparative example 13-15

Adopt the step of the coating product repetition comparative example 10-12 of embodiment 42, whenever comprised the 2.0g product.

Experimental example 1: drop into back 3 minutes diffusion length on the water surface in the water

Prepare every part and contain the parcel that 2g lists in the product that obtains in embodiment in the table 1 and the comparative example.Parcel is thrown in the water, adopted following experimental procedure to measure and throw into back 3 minutes diffusion length on the water surface in the water.

Prepare a wide 90cm who is made by polystyrene foam, long 7m and dark 10cm frame flatly are placed on it in static room, and stick with the polyethylene board of black the inboard of frame.Pour water into and make it dark 5cm.From an end 50cm place, drop into the experimental preparation parcel, after 3 minutes, determine diffusion length with the distance that the preparation edge has moved.Water and polyethylene board are all changed in each experiment.Table 1 shows the result.

1 ( cm ) 1 58010 50013 52514 51515 49016 50017 49018 54019 51520 51021 49522 62023 58024 59025 50026 51027 49028 48032 50033 61034 60035 58036 51037 50038 52042 50045 51046 52047 49048 49049 49050 51051 50052 48053 58054 51055 55056 51057 52058 60059 58060 60061 5901 2202 1503 2404 1905 1706 20510 20011 13012 19013 18014 10015 150

The diffusion length of all samples that shows the embodiment of the invention is all more than 5 meters or 5 meters.In these samples, comprising the water surface diffusant, the sample of hexin surfactant especially, the about 6m of diffusion length.On the other hand, be contained in the water-soluble bag but on the water surface indiffusible sample, show that as the sample that comparative example obtained diffusion length is below 2m.

Experimental example 2: throw into back 20 minutes floating amounts on the water surface in the water

The sample that the embodiment of table 2 obtains is listed in employing, measures according to following experimental procedure and throws into back 20 minutes floating speed in water in the water.

Every part of 5g solid pharmaceutical preparation is put into the 500ml separatory funnel that 300ml water is housed, place after 10 minutes, this funnel is rotated up and down repeatedly, 1 minute is 30 times, and then places 10 minutes.Remove solid matter and most of water of bottom, floating part is forwarded on the 1G2 glass filter.With active component contained in the solid matter on the chemical analysis analysis and filter device (" A " g), the amount of active component in the known 5g sample (" B " g) is calculated floating speed by the following formula formulation.

Floating speed (%)=100/AB

The table 2 embodiment piloquinone bensulfuron-methyl pyributicarb Daim-third careless amine thiocyclarn

uron No.1 22.0 No.4 0.8 7.9 8.2 No.12 0.5 No.13 13.2 No.22 15.3 No.30 5.2 No.31 0.9 7.2 6.3 No.32 1.0 No.53 13.2 30.5 28.1 No.54 5.8 18.2 11.5 No.55 5.1 17.1 11.1 No.56 3.5 11.5 9.7 No.57 32.0 No.58 1.8 No.59 12.1 No.60 3.5 No.61 2.7

Experimental example 3: active component discharges

According to following experimental procedure, adopt embodiment 1,9,22 and 30 and the sample of comparative example 7,8 and 9 active component with suitable high-dissolvability is carried out release experiment.

800 milliliters purified waste water pour 1 liter of wide-mouth vial into, place in 20 ℃ of thermostatic chambers.Solid pharmaceutical preparation is divided into every part of 2g is added in the bottle,, measure the amount of active component in the water sample with chemical analysis getting the 5ml water sample with predetermined interval apart from 5cm depths, bottle middle part.Amount in the sample be multiply by 160, and can obtain and infer the ratio of theoretical amount, and this theoretical amount is calculated when all dissolving according to whole active components.Fig. 1-4 shows following result:

Fig. 1 shows the result of embodiment 1 and comparative example 7 preparations;

Fig. 2 shows the result of embodiment 9 and comparative example 9 preparations;

Fig. 3 shows the result of embodiment 22 and comparative example 7 preparations;

Fig. 4 shows the result of embodiment 30 and comparative example 8 preparations.

As can being clear that by these figure, compare with comparative sample, solid pharmaceutical preparation of the present invention has been controlled the release of piloquinone and thiocyclarn, still, the sustained release phase is short, it can also be seen that most of piloquinone and thiocyclarn are all by wash-out after dozens of minutes to tens hour.

Experimental example 4: the mensuration of apparent specific gravity

Measure embodiment 22, the apparent specific gravity of 30-33 and 40-42 product sample.

The about 5cm of the diameter of weighing, the 100ml garden cylindrical container of high about 5cm.2.5mm mesh sieve is installed at high 20cm place sample is put on the sieve, stir slightly with hairbrush sample is fallen in the container, when container was filled, weighing after flattening comprised the weight of container.After deducting container weight, resulting value is obtained apparent specific gravity divided by 100.

Table 3 shows the result.

Table 3

The embodiment apparent specific gravity

22 0.273

30 0.260

31 0.268

32 0.253

33 0.162

40 0.160

41 0.167

42 0.148

Experimental example 5: the mensuration of concentration ratio between landing point and the peripheral point

The preparation that is obtained by among the embodiment 53-57 is used at the center in the test rice field of area 10m * 10m respectively, and will test the rice field and be divided into every and be four squares of 5m * 5m.According to following step the active component concentration value between landing point and appointment sample point is compared.

The preparation that obtains among the embodiment 53-57 is precipitated at an A, promptly test the center, rice field, be 5cm herein deeply.After 7 days, take out the soil pattern of the thick 1cm of diameter 7cm from the A point, also from other four points, B point, C point D point and the E point earth sample that fetches earth, each point and apart 2 meters of A points, these distribute and will mix equably from the sample of B, C, D and the taking-up of E point along the line that extends from the A point and limit four square effects.Measure the amount of active ingredients that retains by in A point and the even aggregate sample by HPLC, measure the ratio of A point and B to E point place concentration.

Table 4 embodiment number 123456789 bensulfuron-methyls, 1.02 0.95 1.20 1.20 0.96 pyributicarbs, 1.20 1.11 1.20 1.15 0.89Daimuron, 1.08 0.98 1.08 1.08 1.02 piloquinones 1.08 0.97 1.03 1.06

Just as shown in table 4, adopt the present invention who swims on the water surface to contain the cork solid pharmaceutical preparation, even in peripheral point, active component is disperseed quite equably in the rice field.

Put it briefly, the present invention can provide agrochemical formulations, and the said preparation easy operating is to user and not infringement of environment.The present invention has promoted to require the development of safety and laborsaving agricultural and agrochemical industry.

Claims (10)

1. the agrochemical formulations that is used for the rice field, said preparation comprises the floating parcel of solid floatability mixture, this mixture comprises agrochemistry component and floating carrier, mixture was diffused in the water-solubility membrane on the water surface when this mixture was wrapped in the dissolving of its film, selected the parcel size and heavyly was suitable for being thrown in the rice field so that reach the parcel that agrochemical formulations is housed.

2. according to the preparation of claim 1, wherein floating carrier is the Bai Xuyan that expands.

3. according to the preparation of claim 1, wherein floating carrier is vermiculite or the expanded perlite that expands.

4. according to the preparation of claim 1, wherein floating carrier is a cork.

5. according to above arbitrary claimed formulations, the water-solubility membrane that wherein can be used for wrapping up this mixture is the derivatives membrane of polyvinyl alcohol or polyvinyl alcohol.

6. according to above arbitrary claimed formulations, wherein mixture comprises the water surface diffusant in addition.

7. according to the preparation of claim 6, wherein the water surface diffusant is an acetylene alcohol, acetylenic glycol, or its oxirane adduction product.

8. according to above arbitrary claimed formulations, wherein mixture also comprises atoleine.

9. preparation is used for the method for the agrochemical formulations in rice field, this method comprises mixes agrochemistry component and floating carrier, when mixture is wrapped in this film dissolving of water-solubility membrane inherence mixture is diffused on the water surface, selects the size of parcel and weight to be suitable for throwing in the rice field so that reach the parcel that agrochemical formulations is housed.

10. the purposes of claimed agrochemical formulations in any claim among the claim 1-8, this purposes comprises to be put into this agrochemical formulations parcel in the rice field.

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