JUMBO FORMULATION COMPRISING PESTICIDES AND THE PROCESS THEREOF

Abstract: The present invention discloses the jumbo formulations for hand-throw application into paddy water or on irrigation gates, comprising liquid pesticide mixture absorbed into lump-shaped porous carrier in water-soluble bag. The jumbo formulations of the invention are prepared by either packing the granular materials such as sea sand into the porous bag which is enveloped with water-soluble bag, absorbing liquid pesticide mixture of active ingredient of the pesticide, surfactants, solvents, and auxiliary agents into the bag, and heat-sealing the above; or preparing the block-shaped porous carrier by binding granular materials with adhesives, inserting the carrier into the water-soluble bag, absorbing the said liquid pesticide mixture into the bag, and heat-sealing the above. The present jumbo formulations are not disintegrated in water and thus maintain their original shapes. In addition, the present jumbo formulations have excellent spreadability and dispersability of active ingredients. The active ingredients from the present jumbo formulations are evenly dispersed throughout all the applied area of paddy field only by hand-throw application of several to several tens of the pack-like pieces of the formulations per 10a. The present jumbo formulations greatly reduce the danger of being poisoned by pesticides and save the labor and the time required for manual application of the pesticides. The present jumbo formulations are prepared by simple formulation processes with cheap materials. Furthermore, the present jumbo formulations provide excellent controlling effects on weeds, insect pests, and plant diseases without causing severe phytotoxicity to rice plants, since their dispersion in paddy water is not much influenced by any impediments on the paddy water and wind.

Description: DESCRIPTION JUMBO FORMULATION COMPRISING PESTICIDES AND THE PROCESS THEREOF TECHNICAL FIELD The present invention relates to the jumbo formulation comprising pesticides for hand-throw application, which effectively controls various weeds, insect pests, and plant diseases in a broad wetland such as paddy fields, ponds, and lakes. More particularly, the present invention relates to the jumbo formulation of which containing pesticides are evenly distributed to a broad area, when being treated in paddy water. The present invention also relates to the formulation process for the jumbo formulation. Concisely, the formulation process comprises inserting the water- or organic solvent-insoluble lump-shaped porous carrier into the water- soluble film bag, absorbing liquid pesticide mixture of active ingredient of pesticide, surfactants, solvents, and auxiliary agents into the bag, and heat-sealing the bag. The present jumbo formulation is characterized by slow release and even distribution of the active ingredients of pesticides to a broad area when the formulation is applied into flooded paddy fields or on irrigation gates by hand- throw without using special pesticide applicators. BACKGROUND ARTS Increased urbanization and industrialization have rapidly changed modern agriculture to a labor-saving one. Although most farm practices in rice cultivation have become increasingly mechanized, pesticides are still often applied by farmer's hands. Such work in a wet paddy field is very laborious because of the difficulty of walking around the muddy field and often endangers the farmers being poisoned by pesticides . In the Far East countries including Korea, furthermore, an aerial application of pesticides can be used to only a few immense areas, since farming in such countries is labor-intensively managed. Therefore, pesticides have to be applied manually to paddy fields until completely mechanized farm practices in paddy fields are in common. Like the smoke generators which have conveniently been used in greenhouses, labor-saving pesticide formulations and their application methods have long been desired to be developed for effectively controlling weeds, insect pests, and plant diseases in a broad area such as paddy fields, ponds, and lakes. Several types of liquid formulations including suspension concentrates, emulsion concentrates, and emulsifiable concentrates have been developed for reducing the labor and the danger during the manual application of pesticides in paddy field. However, such formulations have not been used successfully in a broad area due to their defects, such as contact damage to the rice plant by applied liquid pesticides and inconvenient application methods in the field. Therefore, they have been used m restricted areas of narrow paddy fields. For these reasons, the "jumbo formulations have intensively been developing in Japan and Korea. The jumbo formulations have different physico-chemical properties from those of the conventional formulations, since the active ingredients from -jumbo formulations should evenly be dispersed throughout all the applied area of paddy field even with hand-throw application of several to several tens of the pack-like pieces of the formulations per 10 a. The jumbo formulations are much bigger than the conventional granular or tabletted formulations and thus generally called as "jumbo formulations". Various jumbo formulations with different shapes, sizes, and action mechanisms are currently being investigated and developed. Good jumbo formulations should be prepared economically and have properties allowing their active ingredients to disperse evenly over the broad area when the formulations are applied into paddy water. Furthermore, such properties should not be reduced or lost during the prolonged storage. Several types of jumbo formulations have been developed so far. One is the gas-generating type. This type of formulations is tablet-shaped and has usually several to several tens of weight in gram. When it is contacted with water, it is rapidly disintegrated into fine particles by vigorously generating gas of carbon dioxide and concurrently the particles are dispersed to far distance. However, this type of formulations has sometimes caused severe phytotoxicity to the rice plant by the excessive residual activity of the active ingredient at the treated sites. Since this type of formulations contains some acids or bases, pesticides readily decomposed by chemical reactions (e.g. hydrolysis) cannot be prepared as the above formulation and thus chemically stable pesticides can only be prepared as jumbo formulations. Furthermore, the formulations tend to lose their gas generating power by the reaction with water being permeated during the storage. Their costs for the preparations are much higher than those of the conventional formulations. Another process for preparing jumbo formulation is known as one which comprises putting an emulsifiable concentrate or an oily suspension of desired pesticide directly or after absorbing it to water-soluble or practically water-insoluble carrier into water-soluble capsule or water-soluble bag and subsequently sealing it. When the water-soluble bag of the formulation containing water-insoluble carrier is solved in water, however, the active ingredient of pesticide is not completely released into water and often accumulated on the surface of the paddy soil. Therefore, this formulation does not provide even distribution of the active ingredient of pesticide, causing phytotoxicity to the rice plant around the treated sites as well as being reduced the pesticidal efficacy far from treated sites. In the case of the formulation containing water-soluble carrier, when the liquid pesticide mixture of the formulation is emulsified, the aqueous carrier solution is readily incorporated into the emulsion particles and thus the specific gravity of the emulsion particles becomes greater than 1. Consequently, most of the emulsion particles containing active ingredients are settled down onto the soil surface, resulting in uneven dispersion over the broad areas and thereby causing phytotoxicity to the rice plant at or close to the formulation-treated sites as well as being reduced the pesticidal efficacy far from the treated sites. Although various jumbo formulations other than the above formulations have also been known, they cannot widely be applied to a number of pesticides and have little practical importance because of their own defects. Accordingly, the jumbo formulations which are highly dispersible in water and easily prepared with low cost have eagerly been needed to be developed DISCLOSURE OF THE INVENTION In order to overcome the problems of aforementioned jumbo formulations, the present inventors have conducted an extensive studies on the formulations. As a result, the jumbo formulations with excellent physico-chemical properties enabling them to exert maximum pesticidal efficacy have successfully been made. These formulations were prepared by absorbing the self-emulsiflable or easily dispersible liquid pesticide mixture to a lump-shaped water-undismtegrable porous carrier enveloped in water-soluble film bag. Accordingly, an object of the present invention is to provide the jumbo formulations comprising liquid pesticide mixture, water-undismtegrable porous carrier, and water- soluble film bag. Another object of the present invention is to provide the formulation processes of jumbo formulations. These processes include packing the water-insoluble granular materials into the porous bag whose outer surface is laminated with water-soluble film, absorbing liquid pesticide mixture into the bag, and sealing the above; or packing the water-insoluble granular materials into the porous bag, sealing the bag, inserting the above sealed bag into the water-soluble bag, absorbing liquid pesticide mixture, and sealing the above; or preparing the block-shaped porous carrier by binding the water-insoluble granular materials with adhesives, inserting the porous carrier into the water- soluble bag, absorbing liquid pesticide mixture, sealing the bag, inserting the bag again into the aluminum envelope, and sealing the above. BEST MODE FOR CARRYING OUT THE INVENTION The carrier 1 used as absorbing materials for liquid pesticide mixture in the present invention is the porous pack densely packed into the porous bag with powdery or granular materials which are practically insoluble in water or in organic solvents. These powdery or granular materials have few fine pores inside and have the diameter of larger than 0.1 mm. The included materials are organic or inorganic. Examples are inorganic minerals of sea sand, hollow microsphere, calcium carbonate, dolomite, baked granular bentonite, zeolite, kaolin, talc, pyrophyllite, etc.; powdery or granular polymers of polyethylene, polypropylene, polyvinyl chloride, etc.; and organic materials of sawdust, rice husk, granular charcoal, cereal, etc. Any of the above illustrated materials could be used depending on the pesticides. Generally, sea sand, calcium carbonate, dolomite, pyrophyllite, talc, hollow microsphere (e.g., Microcells SL made in Australia, Scotchlite made in USA, Shirasu baloon made in Japan), and polyvinyl chloride are suitable to use. The most suitable carrier materials are sea sand, hollow microsphere, calcium carbonate, dolomite, pyrophyllite, and talc, since they have smooth outer surface, low absorption capacity to organic liquids, high affinity to water and organic solvents, excellent degradability in nature, and high environmental safety. After the porous bag is packed with one of the above carrier materials as densely as possible and then sealed, the pack is inserted into a water-soluble bag. The water-soluble bag containing the porous pack can be used as an absorbent for liquid pesticide mixture. The carrier materials can also be directly packed into the water-soluble bag whose inner surface is laminated with the porous bag. Pore size distribution and total pore volume of the porous pack can be maintained by packing carrier materials densely. More than two different kinds of carrier materials can also be packed into the bag to adjust the bulk density. The carrier 2 used as absorbing materials in the present invention are the porous blocks with an average pore size of 20-100μm m diameter. The block-like carrier 2 has a pressure strength of more than 4 kg/cm 2 which allows the porous blocks not to be damaged during their preparation and formulation processes. Bound inorganic minerals, which are insoluble in water and organic solvents, and porous natural materials can be used as porous blocks. Generally, calcium carbonate, talc, baked granular bentonite, pyrophyllite, dolomite, hollow microsphere, and sea sand, which are all bound by using urea, vinyl, or phenol resin adhesive, are suitable to use. The most suitable ones are sea sand, calcium carbonate, talc, dolomite, and pyrophyllite each mixed with hollow microsphere, when considering the affinity to water and organic solvents, degradability in nature, and environmental safety. The carrier 2 can be prepared by binding sea sands, calcium carbonate, hollow microsphere individually or in combination with hollow microsphere with an aid of urea, vinyl, or phenol resin adhesive, and subsequently by hardening them. In the case of sea sand- or calcium carbonate -hollow microsphere blocks, the bulk densities of the carrier blocks can be controlled by adjusting the proportion of sea sand or calcium carbonate mixed ranging from 30 to 70%. Therefore, it is possible to make the jumbo formulation be floated or sedimented in water. Urea, vinyl, or phenol resin adhesive at a proportion of 3 to 20% is added during the preparation of the porous blocks of the carrier 2. Weights of the carriers are in the range of 2.5 to 99% of the total weight of the jumbo formulations. If the porous pack (carrier Dor the porous block (carrier 2) used for the present invention is too light, it is difficult to throw it far. On the contrary, if it is too heavy, it gets stuck into paddy soil, resulting in incomplete release of containing liquid pesticide. Accordingly, it is necessary to adjust the bulk density and size of the jumbo formulation depending on the use and the field condition to be applied. When the paddy soil is soft as in the period right before and after rice transplantation, the bulk density of the formulation should be lowered so as not to get stuck into the soil by using the mixture of sea sand and hollow microsphere as a porous carrier in the formulation. Reversely, when rice plants are actively growing in the field, higher bulk density of the formulation is needed to pass through the canopy of the rice plants. In addition, the jumbo formulations having highly water-soluble active ingredient should have low bulk density, thereby enabling the formulation to be floated in water and ensuring the active ingredient to be dispersed satisfactorily. The porous bags used in the carrier 1 have innumerable pores with an average pore size of more than 50μm in diameter and their air permeability are more than 10m 3 /m 2 /min. Their tensile, bursting, and tear strength, and cut proof degree are properly regulated not to be torn or bursted during the formulation process or application of the formulation. Anything made with natural or synthetic fibers, such as nonwoven cloth, woven gauze, heat-sealable filter paper, and adhesive-sealable filter paper can be used as material for preparing the porous bag. Actually, there is no limitation for the porous bag materials, unless the materials are soluble in water and in organic solvents. However, heat- sealable teabag filter papers are the most suitable material for this purpose, since they are very cheap, easy to get, and highly degradable in nature. Heatseal Teabag Paper (Grade Reference 474601, Crompton, UK) is a good example of such material. After liquid pesticide mixture is absorbed into the porous carrier, the carrier is inserted into a water-soluble film bag (hereinafter called to "water-soluble bag") . The water-soluble bag is then sealed for preventing the liquid pesticide mixture from leaking and migrating to the adjacent formulations. The water-soluble films of polyvinyl alcohol, water-soluble cellulose, or water-soluble dextrin and of 25- 75μm thick can be used for the water-soluble bag. More than 50% of the film should be dissolved in water within 10 minutes at a temperature ranging from 10 to 40 °C and the film should be heat-sealable. The examples of such material include Monosol ® of Model 7030, Model 8533, and Model 8534 (Chris-Craft Industrial Products, Inc., USA), and HI-SELON of Model S-400 and Model C-200 AX (Japan) . The dissolution velocity of the water-soluble bag in water does not considerably affect the efficacy of jumbo formulation. Therefore, any water-soluble bag can be used for this purpose, even if it is relatively slowly dissolved in water. When the water-soluble bag is inner-laminated with the heat-sealable porous bag, it is preferable to use. It is more preferable to use, when the sealed part of the porous bag is covered with the water-soluble bag and the edge of porous bag is adhered only to the sealed part in a manner that any parts of the porous bag are not exposed to outside, but parts of the bag other than the sealed part are actually separated from the water-soluble bag. Any pesticides, such as herbicides, insecticides, and fungicides, can be used in the present invention, if they are in a liquid state at room temperature or highly soluble in organic solvents. Herbicides applicable to the present invention include N-butoxymethyl-2-chloro-2 ' , 6' -diethyl- acetanilide (butachlor) , 2-chloro-2' , 6' -diethyl-N- (2- propoxyethyl) acetanilide (pretilachlor) , 2-chloro-N- (3- methoxy-2-thienyl)methyl-2' , 6' -diethylacetanilde (NSK-850) , S- (ot, α-dimethylbenzyl) piperidine-1-carbothioate (dimepiperate) , S- (4-chlorobenzyl) N,N-diethylthiocarbamate (benthiocarb) , S-ethyl azepane-1-carbothioate (molinate) , S- benzyl N-ethyl-N- (1, 2-dimethylpropyl) thiocarbamate (esprocarb) , 2, 3-dihydro-3, 3-dimethyl-5-benzofuranyl- ethanesulfonate (benfuresate) , 5- (4, 6-dimethoxypyrimidin-2- yl-carbamoylsulfamoyl) -l-methylpyrazol-4-=carboxylic acid (pyrazosulfuron ethyl), 4-nitrophenyl-2, 4, 6-trichlorophenyl ether (chlornitrofen), 5- (2, 4-dichlorophenoxy) -2-nitroanisole (chlomethoxyfen) , methyl 5- (2, 4-dichlorophenoxy) -2- nitrobenzoate (Bifenox) , 1, 1, l-=trifluoro-2' -methyl-4' - (phenylsulfonyl)methanesulfonanilide (perfluidone) , 2-[4- (2, 4-dichlorobenzoyl) -1, 3-dimethylpyrazol-5-yloxy] - acetophenone (pyrazoxyfen) , S-2-methylpiperidinocarbonyl- methyl 0,0-dipropyl phosphorodithioate (piperophos) , 4,6- dichloro-2-phenylpyrimidine (fenclorim), N ~' - (1, 2-dimethyl- propyl) N'-ethy1-6-methy1thio-1, 3, 5-triazine-2, 4-diamine (dimethametryn) , 4- (4-chloro-O-tolyloxy) butyric acid (MCPB) , 5-tert-butyl-3- (2, 4-dichloro-5-isopropoxyphenyl) -1,3,5- oxadiazol-=2 ( 3H) -one (oxadiazon) , etc. Insecticides applicable to the present invention include 0,0-diethyl-0-2- isopropyl-6-methylpyrimidin-4-ylphosphorothioate (diazinon) , 0,0-diethyl 0-3, 5, 6-trichloro-2-pyridyl phosphorothioate (chloropyrifos) , 2-sec-butylphenyl methylcarbamate (BPMC) , dimethyl (E) -l-methyl-2- (methylcarbamoyl)vinyl phosphate (monocrotophos), 0,0-diethyl 0-4-nitrophenyl phosphorothioate (parathion) , 0-ethyl-0-2-isopropoxycarbonyl phenyl isopropylphosporamidothioate (isofenphos) , 2, 3-dihydro-2, 2- dimethylbenzofuran-7-yl (dibutylaminothio) =methylcarbamate (carbosulfan) , (RS) -ct-cyano-3-phenoxybenzyl ( RS) -2 , 2- dichloro-1- (4-ethoxyphenyl)=cyclopropanecarboxylate (cycloprothrin) , 2- (4-ethoxyphenyl) -2-methylpropyl 3- phenoxybenzyl ether (ethofenprox) , ethyl N- [2, 3-dihydro-2, 2- dimethylbenzofuran-7-yloxycarbonyl (methyl)=amino-thio] -N- isopropyl- β-alaninate (benfuracarb) , 0,0-dimethyl 0-3,5,6- trichloro-2-pyridyl phosphorothioate (chlorpyrifos-methyl) , etc. Fungicides applicable to the present invention include S-benzyl 0,0-di-isopropyl phosphorothioate (IBP), 1,2,5,6- tetrahydropyrrolo [3, 2, 1-ij ] quinolin-4-one (pyroquilon) , 3- allyloxy-1, 2-benz [d] isothiazole-1, 1-dioxide (probenazole) , di-isopropyl 1, 3-dithiolan-2-ylidenemalonate (isoprothiolane) , etc. In addition to the above illustrated pesticides, any pesticides which are in a liquid state at room temperature or highly soluble in organic solvents can be used in the present invention. One active ingredient of pesticide alone or in combination with other active ingredients can be incorporated into the present jumbo formulation. The active ingredients in the formulations are in the range of 0.01 to 98% of the total weight. Organic solvents having a boiling point of more than 60 °C and specific gravity of less than 1 can preferably be used in the present jumbo formulation. In addition, the specific gravities of liquid pesticide mixtures vary with the organic solvents used. Considering that the specific gravities of active ingredients are usually more than 1, the organic solvents having lower specific gravity can preferably be used for preparing highly concentrated liquid pesticides. The examples of the solvents are xylene, liquid paraffins, cyclohexanone, cyclohexane, cyclohexanol, methyl naphthalene, Solvesso 100, Solvesso 150 Solvesso 200, N-methyl pyrrolidone, N-butyl pyrrolidone, diethyl benzene, triethyl benzene, ketones (e.g., methylethyl ketone), polyalkyl glycols, and alcohols (e.g., methanol) . Although the nonpolar organic solvents are used as a major solvent, water-soluble solvents can also be used as co- solvents for the active ingredients of pesticides. For providing better emulsiflability and dispersability to pesticides, various surfactants can be added to liquid pesticide mixture as emulsifiers, solubilizers, or dispersants. Both non-ionic and anionic surfactants can be used for this purpose. The examples of non-ionic surfactants are polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene styryl aryl ethers, polyoxyethylene polyoxypropylene block polymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, glyceric fatty acid esters, polyoxyethylene glyceric fatty acid esters, acetylene glycols, and acetylene alcohols. The examples of anionic surfactants are calcium alkylbenzene sulfonates, sodium alkyl sulfosuccinates, and sodium polyoxyethylene alkyl aryl ether sulfate esters. In addition to the above illustrated surfactants, no particular limitation is imposed on the surfactants being used in the present jumbo formulation, if they can be used for either emulsifiable concentrates or spreadable oil formulations. The surfactants added in the liquid pesticide mixtures are in the range of 5 to 15% of the total weight, but more preferably 10%. Viscosity builder such as ethyl cellulose can be added for controlling the viscosity of the liquid pesticide mixture. Anti-decomposition agents or stabilizers such as epichlorohydrin, soybean oil, phosphoric acid, etc. can also be added to the liquid pesticide mixture for stabilizing the physico-chemical properties of the jumbo formulations during the prolonged storage, but they should have no effects on the dispersability of the mixture in water. When the jumbo formulations are applied to the paddy water, almost all of active ingredients from the jumbo formulations should be released within a day. Specifically, more than 90% of liquid insecticides and fungicides, and more than 95% of herbicides are required to be released within approximately 24 hours, respectively. Therefore, it is necessary to adjust the specific gravity of pesticide mixture to a range of 0.80 to 0.995 and to adjust its viscosity, depending on the pore size of the carriers used. The present jumbo formulations are prepared to have their weight of 5 to 200 grams per piece, depending on their hand-throw distance and subsequent settling status on the paddy field. The number of the jumbo formulations to be applied varies with the water dispersability of the active ingredients included in the formulations. The formulations of 5 to 200 pieces can be applied to the paddy field of 10 a, but it is preferable to apply 5 to 50 pieces. For preventing the possibilities that the liquid pesticide mixtures are leaked from the formulations during the storage and that human bodies are contaminated with the leaked pesticides, the liquid pesticide mixtures are absorbed to the porous carriers up to 80 to 90% of the total pore volume. Although the processing steps for the present jumbo formulations are not particularly limited, the formulations are generally processed as the following three examples. First, 1) Two pieces of heatseal teabag filter paper are inserted mbetween two pieces of water-soluble film and their three edges thereof are heat-sealed to make a bag by using an impulse sealer. 2) Sea sand is packed into the resulting bag. 3) Liquid pesticide mixture is added to the bag packed with sea sand, and then the open part of the bag is heat-sealed. 4) The resulting jumbo formulation is put into an aluminum envelope, and then sealed for storage. Second, 1) Carrier 1 is prepared by packing granular materials into a bag of heatseal teabag filter paper followed by subsequent sealing. 2) Carrier 1 is put into a water- soluble bag. 3) Liquid pesticide mixture is added to the carrier 1 and then the open part of the water-soluble bag is heat-sealed by using an impulse sealer. 4) The resulting jumbo formulation is put into an aluminum envelope, and then sealed for storage. Third, 1) Block-shaped porous carrier 2 is prepared by mixing granular materials with phenol resin adhesive followed by subsequent shaping and hardening. 2) Carrier 2 is put into a water-soluble bag. 3) Liquid pesticides mixture is added to the carrier 2 and then the open part of the bag is heat-sealed by using an impulse sealer. 4) The resulting jumbo formulation is put into an aluminum envelope, and then sealed for storage. When the jumbo formulations prepared as above are applied to paddy fields, they are floated on the paddy water or sedimented on the paddy soil depending on the bulk density of the formulations, although they contain liquid pesticide mixture whose specific gravity is less than 1. As soon as the water-soluble bag is dissolved in water, liquid pesticide mixture from the porous carrier is gradually released to or near the water surface. Concurrently, the liquid pesticide mixture is emulsified, spread, and dispersed to a broad area, resulting in the even distribution of active ingredients within 24 hours in the treated area. In case that the pesticides are highly water-soluble, their dispersability can be enhanced by floating the jumbo formulations being exposed to the air. Reversely, in case that the pesticides are barely soluble in water and their emulsion stability is high enough, accumulation of the pesticides in a certain area can be avoided by sedimenting the jumbo formulations and thereby not influenced by wind. In addition, when the jumbo formulations contain spreadable oil of highly volatile non- viscous petroleum solvents in the oily mixture, spreadable oil from the formulation are rapidly released and spread along the water surface in the form of thin membrane. The active ingredients of the present jumbo formulations are easily dispersed and evenly distributed in water, and thus their efficacy is seldom reduced, unless the surface of the treated paddy water is completely covered with rice straw, moss, or aquatic weeds such as duckweed. When the present jumbo formulations of 5 to 50 pieces are applied to a paddy field of 10 a, they can exert their maximum efficacy. The number of the present formulations to be applied can of course be adjusted. When the present jumbo formulations are applied to paddy field, they are floated on the paddy water or sedimented on the paddy soil. When the water-soluble bags are dissolved in water, liquid pesticide mixture from the porous carrier is gradually released to or near the water surface. Since the present jumbo formulations contain nonpolar solvents and surfactants having high self- emulsifiability and dispersabililty, the active ingredients are dispersed to a broad area within 24 hours, resulting in the even distribution of its concentration. Even under condition of strong gust, the active ingredients are evenly dispersed and exert their effect sufficiently without causing any phytotoxicity to rice plants. In addition, since the present jumbo formulations comprise only liquid pesticide mixture, porous carrier, and water-soluble bag, they are prepared by simple formulation processes with cheap materials The invention will be further be described by reference to the following detailed examples. These examples are provided for the purposes of illustration only, and are not intended to be limiting unless otherwise specified. In the examples, "parts" and "%" refer to parts by weight and % by weight, respectively. Example 1 Two pieces of filter paper used for teabag (Heatseal teabag, Grade Reference 474601, Crompton, UK; air permeability, 100 mVmVmin) were inserted inbetween two pieces of water-soluble film (Monosol ® of Model 7030 or Model 8534; Chris-Craft Industrial Products, Inc.) and their three edges thereof were heat-sealed to make a bag (hereinafter called as "water-soluble film-filter paper bag") by using an impulse sealer in a manner that the edges of the filter paper were centered in the sealed parts and thus any parts of the filter paper were not exposed to outside. In addition, filter paper used for teabag and water-soluble film were heat-sealed separately to make the respective bags (hereinafter called as "filter paper bag" and "water-soluble bag", respectively) . The said bags were used for the following preparation of the jumbo formulations. Example 2 The filter paper bags were packed with sea sand of 14.4g and Microcells SL 350 ® of 9.6g and then sealed. The resulting porous packs were used for the following preparation of the jumbo formulations. Example 3 After mixing sea sand and Microcells SL 350 in a ratio of 47:47, phenol resin (Resol type) was added to the resulting mixture in a ratio of 9:94. The resulting carrier mixture was shaped into rods with a diameter of 2.7 cm' by extrusion, hardened by drying at 150 °C for 2 hours, and then cut into pieces with an appropriate size. The resulting carriers (hereinafter called as "porous blocks") were used for the following preparations of the jumbo formulations. Example 4 Six point six parts of pyrazosulfuron ethyl (purity, 99.0%) were dissolved in 472.8 parts of molinate (purity, 98.0%) . To this mixture, 400.6 parts of xylene (industrial grade) and 120 parts of emulsifiers (the mixture of polyoxyethylene alkylphenyl ether, polyoxyethylene special alkyl phosphonate, calcium dodecylbenzene sulfonate and antidecomposition agent) were added while mixing to make the emulsifiable concentrate of molinate-pyrazosulfuron ethyl having active ingredient of 47.0% and specific gravity of 0.970. The said liquid pesticide mixture was used for in Examples 5,6,7,8, and 15. Example 5 Sea sand having particle size of 0.3 to 0.5 mm was prepared by being ground in a mortar and pestle, sieved, washed with water, and then dried. The said sea sand of 57g was densely packed into the water-soluble film-filter paper bag. The molinate-pyrazosulfuron ethyl emulsifiable concentrate of 11.3g was added to the said bag and the bag was heat-sealed to make the jumbo formulation having the active ingredient of 7.78%. The jumbo formulation was put into an aluminum envelope and then the resulting envelope was heat-sealed. Example 6 Sea sand having particle size of 0.3 to 0.5 mm was prepared by being ground in a mortar and pestle, sieved, washed with water, and then dried. The said sea sand of 57 g was densely packed into the filter paper bag and the bag was heat-sealed to make a porous pack. The resulting porous pack was put into the water-soluble bag of Monosol ® of Model 7030. The molinate-pyrazosulfuron ethyl emulsifiable concentrate of 11.3g was added to the said bag and the bag was heat-sealed to make the jumbo formulation having the active ingredient of 7.78%. The jumbo formulation was put into an aluminum envelope and then the resulting envelope was heat-sealed. Example 7 The porous pack as in Example 2 was put into the water- soluble bag of Monosol ® of Model 7030. The molinate- pyrazosulfuron ethyl emulsifiable concentrate of 11.3g was added to the said bag and the bag was heat-sealed to make the jumbo formulation having the active ingredient of 7.78%. The jumbo formulation was put into an aluminum envelope and then the resulting envelope was heat-sealed. Example 8 Calcium carbonate of 57g having particle size of 0.3 to 0.5 mm was densely packed into the water-soluble film-filter paper bag. The molinate-pyrazosulfuron ethyl emulsifiable concentrate of 11.3g was added to the said bag and the bag was heat-sealed to make the jumbo formulation having the active ingredient of 7.78%. The jumbo formulation was put into an aluminum envelope and then the resulting envelope was heat-sealed. Example 9 Sea sand of 15.2g having particle size of 0.3 to 0.5 mm and Microcells SL 350 of 10.Ig were densely packed into the water-soluble film-filter paper bag. The Ronstar ® emulsifiable concentrate (active ingredient, 12%; specific gravity 0.92; Han-Nong Agrochemical Co., Korea) of 12.3g was added to the said bag and the bag was heat-sealed to make the jumbo formulation having the active ingredient of 3.9%. The jumbo formulation was put into an aluminum envelope and then the resulting envelope was heat-sealed. Example 10 Five hundred and fifty six parts of butachlor (purity, 87%), 100 parts of emulsifiers (the mixture of polyoxyethylene nonylphenyl ether and calcium dodecylbenzene sulfonate) , and 344 parts of xylene (industrial grade) were added while mixing to make the emulsifiable concentrate of butachlor. Sea sand of 91g having particle size of 0.3 to 0.5 mm was densely packed into the water-soluble film-filter paper bag. The butachlor emulsifiable concentrate of 18.6g was added to the said bag and the bag was heat-sealed to make the jumbo formulation having the active ingredient of 8.21%. The jumbo formulation was put into an aluminum envelope and then the resulting envelope was heat-sealed. Example 11 Three hundred and ninety five point four parts of diazinon (purity, 96.1%), 100 parts of emulsifiers (the mixture of polyoxyethylene nonylphenyl ether, polyoxyethylene caster oil ether, and calcium dodecylbenzene sulfonate) , 20 parts of epichlorohydrin, and 484.6 parts of xylene (industrial grade) were added while mixing to make the emulsifiable concentrate of diazinon having specific activity of 0.970. Sea sand of 68g having particle size of 0.3 to 0.5 mm was densely packed into the water-soluble film-filter paper bag. The diazinon emulsifiable concentrate of 13.5g was added to the said bag and the bag was heat-sealed to make the jumbo formulation having the active ingredient of 6.3%. The jumbo formulation was put into an aluminum envelope and then the resulting envelope was heat-sealed. Exampl e 12 Two hundred and thirty one point two parts of diazinon (purity, 96.4%), 228.6 parts of BPMC (purity, 97.5), 100 parts of emulsifiers (the mixture of polyoxyethylene nonylphenyl ether, polyoxyethylene caster oil ether, and calcium dodecylbenzene sulfonate), and 440.2 parts of xylene (industrial grade) were added while mixing to make the emulsifiable concentrate of diazmon-BPMC having the specific activity of 0.970. Sea sand of 68g having particle size of 0.3 to 0.5 mm was densely packed into the water-soluble film- filter paper bag. The diazmon-BPMC emulsifiable concentrate of 13.5g was added to the said bag and the bag was heat- sealed to make the jumbo formulation having the active ingredient of 7.38%. The jumbo formulation was put into an aluminum envelope and then the resulting envelope was heat- sealed. Example 13 Forty two parts of ethofenprox (purity, 96.9%), 40 parts of emulsifiers (the mixture of polyoxyethylene nonylphenyl ether, polyoxyethylene caster oil ether, and calcium dodecylbenzene sulfonate), 460 parts of di-isopropyl phthalate, and 458 parts of xylene (industrial grade) were added while mixing to make the ethofenprox spreadable oil. Sea sand of 50g having particle size of 0.3 to 0.5 mm was densely packed into the water-soluble film-filter paper bag. The ethofenprox spreadable oil of lOg was added to the said bag and the bag was heat-sealed to make the jumbo formulation having the active ingredient of 6.67%. The jumbo formulation was put into an aluminum envelope and then the resulting envelope was heat-sealed. Example 14 One hundred and twelve point six parts of hexaconazole (purity, 88.8%) were dissolved in 500 parts of cyclohexanone (industrial grade) . To this mixture, 100 parts of emulsifiers (the mixture of polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl phosphonate, and calcium dodecylbenzene sulfonate) and 287.4 parts of xylene (industrial grade) were added while mixing to make the emulsifiable concentrate of hexaconazole. Sea sand of 68g having particle size of 0.3 to 0.5 mm was densely packed into the water-soluble film-filter paper bag. The hexaconazole emulsifiable concentrate of 20g was added to the said bag and the bag was heat-sealed to make the jumbo formulation having the active ingredient of 1.67%. The jumbo formulation was put into an aluminum envelope and then the resulting envelope was heat-sealed. Example 15 The porous block of 22. Ig was put into the water- soluble bag of Monosol ® of Model 7030. The molinate- pyrazosulfuron ethyl emulsifiable concentrate of 11.3g was added to the said bag and the bag was heat-sealed to make the jumbo formulation having the active ingredient of 7.78%. The jumbo formulation was put into an aluminum envelope and then the resulting envelope was heat-sealed. The distribution of the active ingredients and their efficacy following the application of the present jumbo formulations to paddy fields will further be described by references to the following detailed experimental examples. Experimental example 1 : The evaluation of the distribution of the active ingredients and their controlling effects on weeds following the application of the jumbo formulation of herbicide molinate-pyrazosulfuron ethyl to paddy field Rice seedlings were transplanted in the paddy field of 13 m x 15.3 m. The field was sectioned into 2 m x 2 m by piling PVC pipes having diameter of 1 cm and length of 1.2 m. Immediately after the rice transplantation, seeds of barnyard grass (Echinochloa crus-galli Beauv.), water chestnut [ Eleocharis Kuroguwai Ohwi), flatsedge { Cyperus serotinus Rottb.), and arrowhead { Sagi ttaria trifolia L.) were planted in the center of each section. At 10 days after the rice transplantation, the water level of the experimental field was adjusted to about 6 cm. Six pieces of the jumbo formulations of molinate-pyrazosulfuron ethyl as in Example 7 were thrown to the field as evenly as possible. At 24 hours after the application, 5 ml of the water were sampled from the center of the each section. The concentrations of Molinate in the samples were determined by using high performance liquid chromatography. Phytotoxic effects on the rice plants and controlling effects on the weeds of the treated jumbo formulation were visually evaluated at 30 days after the treatment. The distribution of the active ingredients in the paddy water at 24 hours after the treatment is presented in Figure 1. Figure 1. Distribution of molinate in the paddy water at 24 hours after the treatment of the molinate- pyrazosulfuron ethyl jumbo formulation. The treated paddy field had a size of 13 m x 15.3 m. The numbers represent the concentration of molinate in ppm. The active ingredients were relatively evenly distributed, even though the water in the paddy field was dwindled naturally with a maximum rate of 2-3 cm per day and wind was continuously blowing to the upper direction shown in Figure 1. The average concentration of molinate in the paddy field at 24 hours after the treatment was 1.23 ppm with the variation coefficient of 23.4%. Molinate from the jumbo formulation was more evenly distributed in water compared to that from the conventional granular formulations having the variation coefficient of 25-30%. The jumbo formulation did not cause any phytotoxicity to the rice plants, except in the sites of Φ, ©, and (D where only one hill of rice plants exhibited the growth inhibition by 50, 60, and 30%, respectively. The jumbo formulation completely controlled the four different weed species planted in the paddy field. Experimental example 2: The distribution of the active ingredient following the treatment of the Diazinon jumbo formulation to paddy field When rice plants were at the stage of earning, the paddy field of 13 m x 15.3 m was sectioned into 2 m x 2 m by piling PVC pipes having diameter of 1 cm and length of 1.2 m. After the water level of the experimental field was adjusted to about 6 cm, six pieces of the diazinon jumbo formulation as in Example 11 were thrown to the field as evenly as possible. At 24 hours after the treatment, 5 ml of the water were sampled from the center of the each section. The diazinon concentrations in the samples were determined by using high performance liquid chromatography. The distribution of the active ingredients in the paddy water at 24 hours after the treatment is presented in Figure 2. Figure 2. Distribution of diazinon m the paddy water at 24 hours after the treatment of the diazinon jumbo formulation. The treated paddy field had a size of 13 m x 15.3 m. The numbers represent the concentration of diazinon in ppm. The active ingredient, diazinon, was relatively evenly distributed. The average concentration of diazinon in the paddy water at 24 hours after the treatment was 0.61 ppm with the variation coefficient of 28.5%. The variation coefficient was similar to that of the conventional granular formulations. From these results, excellent controlling effects on insect pests would be expected. As shown in the above, the jumbo formulations of the present invention can be applied to paddy fields only by throwing 5 to 50 pieces per 10 a without using special pesticide applicators. The jumbo formulations can greatly save the labor and reduce the danger of being poisoned by pesticides during manual application of pesticides. Therefore, the jumbo formulations comprising pesticides for hand-throw application can successfully substitute for the conventional formulations with excellent controlling effects on weeds, insect pests, and plant diseases.

Claims: CLAIMS 1. The jumbo formulation for hand-throw application into paddy water or on irrigation gates, comprising liquid pesticide mixture absorbed in water- and organic solvent- insoluble undisintegrable lump-shaped porous carrier into the sealed bag which is enveloped with organic solvent-insoluble, but water-soluble film. 2. The jumbo formulation according to claim 1, wherein the said porous carrier is the sealed porous bag densely packed with organic or inorganic powdery or granular materials. 3. The jumbo formulation according to claim 1, wherein the said porous carrier is the water- and organic solvent- insoluble undisintegrable block-shaped porous carrier of bound granular materials with adhesives. 4. The porous carrier according to claim 2, wherein the said organic or inorganic powdery or granular materials consist of 1 or more than 1 of inorganic materials of sea sand, hollow microsphere, calcium carbonate, dolomite, pyrophyllite, talc, kaolin, baked granular bentonite, and zeolite; or powdery or granular polymers of polyethylene, polypropylene, and polyvinyl chloride; or organic materials of sawdust, rice husk, granular charcoal, and cereal. 5. The porous carrier according to claim 2 or 4, wherein the said organic or inorganic powdery or granular materials have average diameters of more than 100 μm. 6. The porous carrier according to claim 2 or 4, wherein the said organic or inorganic powdery or granular materials are inorganic materials sea sand, hollow microsphere, calcium carbonate, dolomite, pyrophyllite, or talc. 7. The porous carrier according to claim 3, wherein the said granular materials consist of 1 or more than 1 of sea sand, calcium carbonate, talc, pyrophyllite, dolomite, and hollow microsphere. 8. The porous carrier according to claim 3, wherein the said water- and organic solvent-insoluble undisintegrable block- shaped porous carrier is bound sea sand-hollow microsphere mixture, calcium carbonate-hollow microsphere mixture, talc- hollow microsphere mixture, pyrophyllite-hollow microsphere mixture, or dolomite-hollow microsphere mixture. 9. The porous carrier according to claim 2, wherein the said porous bag is nonwoven cloth, woven gauze, or heat-sealable teabag filter paper, made with natural or synthetic fibers. 10. The porous carrier according to claim 2 or 9, wherein the said porous bag has innumerable pores with an average pore size of more than 50μm in diameter. 11. The porous carrier according to claim 2 or 9, wherein the said porous bag is made with heat-sealable teabag filter paper. 12. The jumbo formulation according to claim 1, wherein the said organic solvent-insoluble, but water-soluble film bag is made largely with polyvinyl alcohol, water-soluble cellulose, or water-soluble dextrin. 13. The jumbo formulation according to claim 1 or 12, wherein the said organic solvent-insoluble, but water-soluble film bag has a thickness of 25-75μm. 14. The jumbo formulation according to claim 1, wherein the said liquid pesticide mixture comprises the active ingredient of the pesticide, organic solvents, surfactants, and auxiliary agents. 15. The jumbo formulation according to claim 1 or 14, wherein the said active ingredient of pesticides is either in a liquid state at room temperature or highly soluble m organic solvent. 16. The jumbo formulation according to claim 1 or 14, wherein the said liquid pesticide mixture has a specific gravity of 0.800 to 0.995. 17. The liquid pesticide mixture according to claim 14, wherein the said active ingredients in the jumbo formulation are in the range of 0.01 to 98% of the total weight. 18. The formulation process for jumbo formulation for hand- throw application into paddy water or on irrigation gates, comprising the absorbing the liquid pesticide mixture into the water- and organic solvent-insoluble undisintegrable porous carrier enveloped in a water-soluble film bag and heat-sealing the said bag. 19. The formulation process according to claim 18, wherein the sai porous carrier in water-soluble bag is prepared by packing the pow or granular materials into the porous bag and inserting the bag in water-soluble bag. 20. The formulation process according to claim 18 or 19, wherein the said porous carrier in water-soluble bag is prepared by packing the powdery or granular materials into the porous bag, sealing the bag, and inserting the bag into water-soluble bag. 21. The formulation process according to claim 18 or 19, wherein the said porous carrier in water-soluble bag is prepared by packing the powdery or granular materials into the porous bag whose outer surface is laminated with water- soluble film. 22. The formulation process according to claim 18, wherein the said carrier in water - soluble bag is prepared by mixing granular materials with adhesives and shaping and followed by hardening it and inserting the resulting water- and organic solvent - insoluble undisintegrable block - shaped carrier into the water - soluble film bag.

Inventors: CHO KWANG YUN, LIM HE KYUNG, YU JU HYUN, CHO, KWANG, YUN, LIM, HE, KYUNG, YU, JU, HYUN
Applicants: KOREA RES INST CHEM TECH, KOREA RESEARCH INSTITUTE OF CHEMICAL TECHNOLOGY
Application year: 1997
Main classification: A01N25
IPC codes: A01N25, A01N47