MXPA06005248A

MXPA06005248A - Soil-fumigant-containing solid material

Info

Publication number: MXPA06005248A
Application number: MXPA/A/2006/005248A
Authority: MX
Inventors: Ozawa Shuji; Wakaki Noriyuki
Original assignee: Mitsui Chemicals Inc
Priority date: 2003-11-11
Filing date: 2006-05-10
Publication date: 2006-10-17

Abstract

Preparations of high soil fumigant content that at the use of soil fumigant, exhibit highly limited release of the soil fumigant and that after the application to soil, accomplish fumigation of soil within a short period of time;and a method of soil fumigation therewith. There is provided a soil-fumigant-containing solid material characterized by containing 60 to 85 wt.%of soil fumigant, 0.5 to 15 wt.%of gelatin, 0 to 10 wt.%of inorganic mineral, 1 to 15 wt.%of polysaccharide that reacts a divalent or higher-valency metal salt to thereby cause gelation and 0.5 to 20 wt.%of water.

Description

SOLID MATERIAL THAT CONTAINS FUMIGATOR FOR THE EARTH Field of the Invention The present invention relates to a solid material that contains a fumigator for the earth and a process for producing the same. More specifically, the present invention relates to a solid material in which the release of the fumigator on the ground is suppressed in an extreme manner, so that the farmer may not feel an irritating odor at the time of use and that the fumigator is easily released. on earth when it is treated in a field and a process to produce it. Background of the Invention The soil sprayer represented by chloropicrin and DD has a high vapor pressure and is easily subjected to gasification under normal conditions of use. In particular, it is necessary to use protective lenses, a protective mask and gloves when using chloropicrin because chloropicrin has an irritating odor. In order to fumigate the earth with chloropicrin, chloropicrin is infused into the earth using a special infuser and the surface of the earth is covered with a gas barrier film after it is infused. It has been developing as an odorless chloropicrin formulation, a formulation which seals chloropicrin absorbed with dextrin in a polyvinyl alcohol film bag or which is sealed with only chloropicrin in a bag made of polyvinyl alcohol. (US Patent No. 5846904 and JP1995-324002A). The ground day fumigator, such as chloropicrins or the like, has been widely used to avoid the continuous hazard of crops in a complex area for growing crops and a specialized area of production and is treated throughout the years until the next. plantation after harvest. In order to increase the frequency of plant harvests during a year, the period of fumigation of the land is preferably as short as possible. In general, the time required for fumigation of the earth is 1 0 to 1 5 days when the average temperature of the earth is 1 5 ° C to 25 ° C. A specific gelatinized material in which the active material containing the gelatinized material having a porous structure has been known (J P 980-25456A). The gelatinized material is obtained by dispersing the active materials such as spices, agricultural chemicals or the like in an aqueous solution of sodium alginate or in an aqueous solution of low methoxyl pectin and then reacting the sodium alginate or the pectin. of low methoxyl with a highly valent or divalent metal salt. The active materials are used in an amount not greater than 20% by weight based on the sol ution. In addition, the gelatinized material obtained by drying in which the release of the active material can be suppressed is also described in the above document. Preferably, the soil sprayer represented by the chloropicrin in which the release of the same is suppressed in an extreme manner, so that a farmer may not feel the irritating smell at the time of use. On the other hand, it is necessary to complete the fumigation of the soil within a short period of time after the fumigator has been applied to the soil. With respect to this contradictory claimed property in the above document, a method for suppressing the release of the active material is described, but a method for releasing an active material within a short period of time is not described. In addition chloropicrin is very heavy, having a specific gravity of 1 .67. Therefore, even if the chloropicrin was stirred with an aqueous solution of sodium alginate or an aqueous solution of low methoxyl pectin in the presence of a surfactant, no emulsion of the oil-in-oil type containing chloropicrin in a high concentration. When the amount of the surfactant used to obtain an oil-in-water emulsion containing chloropicrin at a high concentration has been increased., a homogeneous emulsion has not been obtained. Because the solid material is deposited from the aqueous solution of sodium alginate or the aqueous solution of low methoxyl pectin. For this reason, it was necessary to reduce extremely the amount of chloropicrin used in order to obtain a dispersion of chloropicrin by stirring chloropicrin with an aqueous solution of sodium alginate or an aqueous solution of low methoxyl pectin in the presence of a chloropicrin. surfactant, so that only the dispersion with the concentration of chloropicrin not greater than 5% by weight has been obtained. The gelatinized material obtained from the dispersion with a low concentration of chloropicrin had a low content of chloropicrin. Consequently, a large amount of water must be removed from the gelatinized material in a drying step in order to release the fumigator from the ground in an extreme manner. Therefore, there has been a problem that the load in the dryer was also heavy. Patent Document 1: North American Patent No. 5846904 Patent Document 2: JP 1 995-324002A Patent Document 3: JP 1 980-25456A Document that is not Patent 1: Website of the Internet address http: // village .infoweb.ne.ip / ~ chlopic / siryou / ekizai / ekizai.htm SUMMARY OF THE INVENTION It is an object of the present invention to provide a solid material containing a soil fumigator with a high content of soil sprayer and a process to produce the formulation. Another object of the present invention is to provide a solid material containing the fumigator for the soil in which the release of the solid fumigator is suppressed in an extreme manner, so that a farmer may not feel the irritating odor at the time of use and a process to produce the formulation. In addition, a further object of the present invention is to provide a solid material that contains a soil sprayer that quickly releases the sprayer into the soil when it is treated on the ground and completes the spraying of the soil within a short period of time and a process to produce the formulation. The present inventors have made a careful study of the emulsification with an aqueous solution of sodium alginate or an aqueous solution of low methoxyl pectin using chloropicrin. The present inventors have discovered that an oil-in-water type emulsion was fairly easily obtained by allowing the coexistence of gelatin in the chloropicrin, while not obtaining an oil-in-water type emulsion with a high chloropicrin content. according to the conventional method using a surfactant. As a result, a gelatinized material with a high content of chloropicrin was obtained by reacting the emulsion with a higher or divalent valent metal salt and then when the gelatinized material was dried, a solid material with the soil fumigator content in it. which a farmer did not feel the irritating odor, that is, that the chloropicrin release was suppressed in an extreme way, and in which the content of chloropicrin was high. It has been discovered that although the solid material contained in the soil fumigator suppresses the release of chloropicrin in an extreme manner, it has the ability to rapidly release chloropicrin and complete the fumigation of the earth within a short period of time when It is applied to the earth. Therefore, the present invention has been completed. That is, the present invention is specified by the following matters: [1] A solid material containing a fumigator for the earth in an amount not less than 60% and not greater than 85% by weight of a fumigator for the land, not less than 0.5% and not more than 1 5% by weight of gelatin, not less than 0% and not more than 10% by weight of an inorganic mineral, not less than 1% and not more than 15% by weight of a polysaccharide which reacts with a higher or divalent valent metal salt to thereby cause gelatinization and not less than 0.5% and not more than 20% by weight of water; [2] The solid material that contains a fumigator for the earth as described in point [1], where the fumigator for the earth is a fumigator for the earth that has a boiling point of not less than 40 ° C and a vapor pressure not less than 70 Pa / 20 ° C; [3] The solid material that contains a soil sprayer as described in point [2], where the soil sprayer is one or more types of soil sprays selected from chloropicrin, DD, and isothiocyanate at i lo; [4] The solid material that contains a fumigator for the soil as described in any of points [1] to [3], where the polysaccharide reacts with the highest or divalent valent metal salt to cause thus gelatinization is one or more types thereof selected from a water-soluble alginate salt, low methoxyl pectin and kapa-carragean; [5] A process to produce the solid material that contains the fumigator for the land as described in point [1], which comprises the following steps from (a) to (c): (a) the step of producing an oil-in-water type emulsion with a soil fumigator content of not less than 10% and not more than 85% by weight by stirring an aqueous solution of the polysaccharide that reacts with the highest or divalent valent metal salt to cause in this way the gelatinization, a fumigator for the earth, a gelatin and an inorganic mineral; (b) the step of producing the gelatinized material by reacting the emulsion obtained in step (a) with a higher or divalent valent metal salt; and (c) the step of producing a solid material containing a fumigator for the soil by drying the gelatinized material obtained in step (b); [6] The process to produce the solid material that contains the soil fumigator as described in item [5], where the soil fumigator is one or more types of soil sprayers selected from chloropicrin , DD and isothiocyanate at i; [7] The process to produce the solid material that contains the soil fumigator as described in point [5] or [6], where the polysaccharide reacts with the highest or divalent valent metal salt to thus causing the gelatinization is used in an amount not less than 1% and not more than 15% by weight based on the fumigator of the earth; [8] The process to produce the solid material containing the soil fumigator as described in any of points [5] to [7], where the polysaccharide reacts with the highest valent metal salt or divalent to thereby cause gelatinization is one or more types thereof selected from a water soluble alginate salt, low methoxyl pectin, kapa-carragean; [9] The process to produce the solid material that contains the fumigator of the earth as described in any of the points of [5] to [8], where the gelatin is used in an amount not less than 0.5% and not more than 15% by weight based on the soil fumigator; [10] The process to produce the solid material that contains the soil fumigator as described in any of points [5] to [9], where the inorganic mineral is used in an amount not less than 0 % and not more than 10% by weight based on the soil fumigator; [11] The process to produce the solid material that contains the fumigator of the earth as described in any of points [5] to [10], where the water is contained in an amount not less than 0.5% and not greater than 20% by weight based on the solid material that contains the soil fumigator when the gelatinized material obtained in step (b) is dried; [12] A solid material containing an earth fumigator produced in accordance with the method of step (c) as described in any of [5] to [11]; [13] A gelatinized material produced according to the method of step (b) as described in any of points [5] to [10]; and [14] An oil-in-water type emulsion produced according to the method of step (a) as described in any of [5] to [10]. Because the soil fumigator material of the present invention is produced from an oil-in-water type emulsion with a soil fumigator at a high concentration, a solid material containing a soil fumigator is obtained that has less load at the time of drying and that contains the fumigator of the earth in a high content. Because the release of the fumigator from the soil is suppressed in an extreme way, so that a person does not smell, a farmer can handle it easily. In addition, when this solid material is applied to the soil, the solid fumigator is released quickly and the fumigation of the soil can be completed within a short period of time. Therefore, said solid material is useful for the production of crops without reducing the frequency of planting in one year. Detailed Description of the Invention The solid material containing the soil fumigator of the present invention is produced by means of the following steps, ie (a) a step to produce an oil-in-water type emulsion by stirring an aqueous solution of the polysaccharide which reacts with a higher or divalent valent metal salt to thereby cause gelatinization, a soil fumigator, a gelatin and an inorganic material, (b) the step of producing the gelatinized material containing the fumigator of the earth by reacting the emulsion obtained in step (a) with the highest or divalent valent metal salt and (c) the step of producing a solid material containing the soil fumigator by drying the gelatinized material obtained in step ( b) The gelatinized material mentioned in the present invention refers to the solid material obtained in step (b) and the solid material containing the soil fumigator refers to a solid material obtained in step (c). First, step (a) will be explained. In step (a), an oil-in-water type emulsion with an earth fumigant content of not less than 10% and not more than 85% by weight is produced by stirring an aqueous solution of the polysaccharide which reacts with a salt of higher or divalent valent metal to thereby cause gelatinization, a soil fumigator composition, a gelatin and an inorganic mineral. The soil fumigator used in the present invention is a chemical that is used by fumigation for the purpose of soil pest control. It is preferred that the soil fumigator have a boiling point of not less than 40 ° C and a vapor pressure of not less than 70 Pa / 20 ° C. Suitable examples thereof include chloropicrin, D-D (1,3-dichloropropene) and allyl isothiocyanate. The soil fumigator of the present invention can be used as a single formulation of chloropicrin, D-D or allyl isothiocyanate, or as a mixture of two types thereof. In addition, chloropicrin, D-D or allyl isothiocyanate can also be mixed with other agricultural chemicals to produce a functional solid material with a soil-containing content. Specifically, an agricultural chemical mixed with other agricultural chemicals, such as fostiazate, pyraclofos, dichlorodiisopropyl ether, methylisothiocyanate and the like, may also be used. A mixed agricultural chemical obtained by mixing chloropicrin and / or DD with other agricultural chemicals is also included in the solid material containing the soil fumigator of the present invention. The polysaccharide used in the present invention is a polysaccharide that reacts with a higher or divalent valent metal salt to thereby cause gelatinization. (The polysaccharide that reacts with a higher or divalent valent metal salt to thereby cause gelatinization according to the present invention, it is simply described in some cases as polysaccharide throughout the description). As the polysaccharide having said property, for example, the alginate salt, the low methoxyl pectin or the kapa-carragean (K-carragean) can be exemplified. As the alginate salt, for example, sodium alginate, potassium alginate, ammonium alginate, and a water soluble salt obtained using alginic acid can be used as the starting raw material. In general, sodium alginate, which is cheap and widely used in the field of food, is preferably used. Low methoxyl pectin refers to pectin with an esterification degree of not more than 50%. The kapa-carrágena is classified within the carrágena of the kapa type. And it may not necessarily be purified or it may be a crude extract. These polysaccharides can be used alone or in combination of two or more types. In the present invention, the amount of polysaccharide used affects the removal of the odor from the soil fumigator, or impacts the strength of the solid material that the soil fumigator contains. That is, when the amount of polysaccharide used is lower in relation to the soil fumigator, the odor suppression of the solid material contained in the soil fumigator becomes insufficient or has an impact on the strength of the solid material it contains. the fumigator of the earth, which becomes smaller. For this reason, the polysaccharide is used in an amount not less than 1% by weight based on the soil fumigator. The upper limit of the amount of the polysaccharide used is determined correctly from the economic point of view. However, it may not be more than 1 5% by weight based on the soil sprayer. These polysaccharides are used in the form of an aqueous solution with a concentration of not less than 0.5% and not more than 15% by weight. The soil fumigator-containing solid material of the present invention needs the gelatin in order to produce an oil-in-water type emulsion by stirring the solid fumigator and an aqueous solution of the polysaccharide. Although the gelatin is dissolved in an aqueous solution containing the polysaccharide and then the solution is stirred with the soil fumigator, an oil-in-water type emulsion is not obtained. Only when gelatin is added to the solid fumigator and then the solid fumigator with the added gelatin is stirred with an aqueous solution containing the polysaccharide, an oil-in-water type emulsion is obtained with the solid fumigator contained in a high concentration . The gelatin used in the present invention is preferably in the powder form. When the particle diameter of the gelatin powder becomes large, a homogeneous emulsion is not obtained. Therefore, it is preferred to use gelatin in the form of a fine powder. The gelatin powder having a particle diameter of not more than 3 mm and preferably not greater than 1 mm is desirable. Correct examples thereof include, a Fine Powder R (a product of Nitta Gelatin Inc.) or the like. The amount of gelatin used is not less than 0.5% and not more than 15% by weight and preferably not less than 1.0% and not more than 15% by weight based on the soil fumigator. Thus, in the event that the soil fumigator, the gelatin and an aqueous solution of polysaccharide are stirred, an oil-in-water type emulsion can easily be produced. The oil-in-water type emulsion mentioned in the present invention refers to one that is in a condition that separation of the two phases does not occur even after the emulsion is allowed to settle for 10 minutes after Agitation stops. That is, no liquid droplets of the earth fumigator are observed. The oil-in-water type emulsification of the present invention can be produced only by the agitation of the soil fumigator., the gelatin and the aqueous solution of the polysaccharide. However, when an inorganic mineral is added to the fumigator of the earth, the generation of oil in water is much more accelerated. As the inorganic mineral used in the present invention, one can have, for example, zeolite, white carbon, talc, clay and the like. A fine particle having a particle diameter no greater than 200 μ is desirable. Examples of such inorganic material in the form of a fine particle which is readily available include white carbon and clay powder. The inorganic mineral may be used in an amount not less than 0% and not more than 10% by weight based on the soil fumigator. The oil-in-water type emulsion of the present invention comprises a soil fumigator, a gelatin, a polysaccharide which reacts with a higher or divalent valent metal salt to thereby cause gelatinization, and water as needed , an inorganic mineral, while an ultraviolet absorbent, a preservative, a colorant and the like may be added, further to a degree where the generation of the oil-in-water type emulsion is not impeded. As described above, in step (a), it is possible to produce an oil-in-water type emulsion containing the soil fumigator at a concentration of not less than 10% and not more than 85% by weight. Among said emulsions, an emulsion containing the soil fumigator in a concentration of not less than 30% and not greater than 80% by weight preferably from the viewpoint of the operating capacity of an emulsion or the reduction of the charge at the time of drying in step (c). Next, step (b) will be explained. In step (b), the oil-in-oil emulsion is reacted with a higher or divalent valent metal salt to produce a gelatinized material containing the soil migrator. The highest or divalent valent metal salt used in the present invention is a cation such as calcium, magnesium, barium, zinc, nickel, copper, lead and the like as its cation. As an aqueous solution containing the aforementioned cation, there may be for example, aqueous solutions of calcium salt such as calcium chloride, Galium nitrite, calcium lactate, calcium citrate or the like.; magnesium salt, such as magnesium chloride and similar; barium salt, such as barium chloride and the like; zinc salt, such as zinc chloride, zinc nitrate, zinc sulfate and the like; nickel salt, such as nickel chloride or the like; copper salt, such as copper sulfate or the like; lead salt, such as lead acetate or the like and silver salt, such as silver nitrate or the like. Among these, the one that is economically preferred is calcium chloride, since it is cheaper. The metal salt thereof can be used in an amount not less than 1 time by weight based on the amount of the polysaccharide used. In addition, the metal salt can be used in the form of an aqueous solution of 0.1% or a higher percentage by weight for a saturated concentration. The reaction of the oil-in-oil emulsion with a higher or divalent metal salt can be carried out according to the method of dropping emulsion droplets in an aqueous solution containing a higher valent metal salt. or divalent or by the method of spraying the aqueous solution with a higher or divalent valent metal salt content in the emulsion droplets or the like. When the oil-in-water type emulsion of the present invention is contacted with the aqueous solution containing the highest or divalent valent metal salt, the gelatinized material is obtained in an instant, and the contents of the soil fumigator are obtained. in the obtained gelatinized material it is almost of the same value as the concentration of the soil fumigator in the oil-in-water type emulsion. Because the concentration of the soil fumigator in the emulsion is high in the present invention, the content of the soil fumigator in the gelatinized material is also increased. In this way, the gelatinized material containing the soil fumigator is not less than 10% and not more than 85% by weight and preferably not less than 30% and not more than 80% by weight produced in accordance with the step ( b) Although the gelatinized material obtained in step (b) suppresses the release of the fumigator from the soil, a smell of the soil fumigator is felt. In order not to feel the irritating odor of the soil fumigator when a farmer uses such material, the gelatinized material is dried in step (c). That is, the solid material containing the soil fumigator of the present invention is produced by drying the gelatinized material obtained in step (b). Finally, step (c) will be described. In step (c), drying can be carried out according to any of the general drying methods at a temperature no higher than the boiling point of the soil fumigator, such as hot air drying, vacuum drying and dried by air. However, drying under atmospheric pressure is preferred. The drying is carried out until the amount of moisture of the solid material containing the fumigator of the soil is not less than 0.5% and not more than 20% by weight, preferably not less than 1.0% and not more than 20% by weight. % in weigh . The solid material that contains the soil fumigator obtained in this manner contains not less than 60% and not more than 85% by weight of the soil fumigator, not less than 0.5% and not more than 1 5% by weight of gelatine, not less than 0% and not more than 10% by weight of an inorganic mineral, not less than 1% and not more than 15% by weight of the polysaccharide which reacts with a higher or divalent metal salt to cause in this way the gelatinization, and not less than 0.5% and not more than 20% by weight of water. The content of the soil fumigator in relation to the solid material containing soil fumigator mentioned in the present invention, refers to a value obtained by analyzing the amount of the soil fumigator by means of an analyzer such as gas chromatography, high performance liquid chromatography or similar, and the content of gelatin, an inorganic mineral and a polysaccharide that reacts with a higher or divalent metal salt to cause gelatinization in relation to the solid material that contains the soil fumigator is a value obtained by dividing the amount of each of the raw materials between the weight of the solid material that contains the migrant fu of the earth. In addition, the water content is a value obtained by subtracting the content of the soil fumigator, gelatin, an inorganic material and a polysaccharide that reacts with a higher or divalent metal salt to thereby cause the gelatinization of the solid material containing the fumigator of the earth. The solid material that contains the soil fuming obtained in step (c) in which the release of the soil fumigator is suppressed in an extreme manner, so that the agriculturalist may not feel the irritating odor. . In order to promote the liberation of the earth's fumigant from the solid material that contains the earth's fuming material, the solid material that contains the fumigator of the earth can simply be mixed in the earth or buried in the earth. A further feature of the present invention is that the soil sprayer is released rapidly into the soil when the release of the solid material containing the soil migrator which is treated on the ground is suppressed extremely. If the soil can be treated with the existing chloropicrin formulation, the solid material that contains the soil sprayer also releases the soil sprayer into the soil, such as the chloropicrin formulation and the soil spraying period. It is also almost the same. In the case of a solid material containing the soil fumigator of the present invention, the period of soil fmigation is different depending on the particle diameter and the temperature of the soil. However, in general, the fumigation of the earth is completed over a period of 10 to 15 days when the particle diameter of the solid material contained in the earth migrator is from 2 to 30 mm, and the Earth temperature is from 1 5 ° C to 25 ° C. At the time of application of the solid material containing the soil sprayer, the solid material can be treated by a method such as a method comprising spraying the solid material which the soil sprayer contains manually or using a fertilizer sprinkler on the surface of the earth and then mixing it in the soil, or a method that involves plowing a place to transplant the crops and spraying the solid material that contains the soil fumigator into the fields and then covering the soil , or similar. In the past, because the earth migrator had an irritating odor, it was not possible to even think of treating a solid fertilizer, a solid form, such as an insecticide, a fungicide and / or a herbicide and a pesticide sprayer. the earth at the same time. The solid material containing the soil fumigator of the present invention is a solid material in which the release of the soil fumigator is suppressed in an extreme manner. Therefore, the solid material containing the soil sprayer can be treated together with the aforementioned solid formulations at the same time. The solid material that contains the soil sprayer can be sprayed on the surface of the soil and then can be sprayed on the aforementioned solid formulations, the solid formulations mentioned above can be sprayed and then the solid material that contains the sprayer of the soil. soil can be sprayed, or the solid material containing the soil sprayer can be mixed with the solid formulations mentioned above in advance and the resulting mixed granules can be sprayed. As in the case of the existing chloropicrin formulation, in order to increase the effect of fumigation of the earth, the solid material that contains the fumigator of the earth is treated in the earth and then the surface of the earth is covered with a gas barrier film. EXAMPLES The present invention will now be illustrated more specifically with reference to the examples. Example 1 Production of an oil-in-water type emulsion (Emulsion No. A) containing the Earth Sprayer. To a 300-ml 4-necked flask were introduced 49 g of chloropicrin (a product with a purity of 99.5%) and 0.9 g of gelatin powder (a product of Nitta Gelatin Inc., Fine Powder R). Four grams of a sodium alginate in 1.5% aqueous solution (a product of Kimica Corporation) was added to the 4-necked flask and the resulting mixture was stirred under a condition of 66 m / min peripheral speed of a mixing blade. . An oil-in-water type emulsion was obtained at 5 minutes after stirring started. EXAMPLE 2 Production of Oil-in-Water Type Emulsion (Emulsion No. B) with an Fumigant Content of the Earth 49 g chloropicrin (a product with a purity of 99.5%) was introduced into a 300-ml 4-necked flask. ), 0.9 g of gelatin powder, (a product of Nitta Gelatin Inc., Fine Powder R) and 0.9 g of white carbon. Four grams of an aqueous solution of 1.5% sodium alginate (a product of Kimica Corporation) was added to the 4-necked flask, and the resulting mixture was stirred under a condition of 66 m / min of peripheral velocity in a blade. mixed. An oil-in-water type emulsion was obtained at 2 minutes after the stirring was started. EXAMPLE 3 Production of oil-in-water type emulsions (Emulsions Nos. C to K) with content of soil sprayer According to the method of example 1 or 2, the mixture was stirred for the time required to generate an emulsion of oil type in water with a soil fumigator content under the conditions described in table 1 and the stirring was stopped after the emulsion was obtained and then the existence of phase separation was examined, resting for 10 minutes. The results of these are shown in table 1. In addition, the following are the abbreviations and symbols of the table. CP: Chloropicrin (a product of Mitsui Chemicals, Inc.). SO: Soilean (a product of Mitsui Chemicals, Inc., a mixture of 40% by weight of chloropicrin and 52% by weight of DD) DD: 1,3-dichloropropene (a product of Agro-Kanesho Co., Ltd., 92% by weight) Inorganic mineral: white carbon was used. ARG: Sodium Alginate (a product of Kimica Corporation) PEC: Low Methyl Pectin (a product of Nitta Gelatin Inc.,) No: No phase separation occurred even when the emulsion was allowed to stand for 10 minutes after it was stopped the agitation. Yes: A phase separation occurred when the emulsion was allowed to stand for 10 minutes after the stirring was stopped or an oil-in-water type emulsion was not obtained. < -" OR\ Table 1 Test Results with an Oil / Water Type Emulsion From the results described above, it was discovered that using gelatine, an oil-in-water emulsion could be produced with a soil fogger contained in a high concentration. In addition, it was discovered that when an inorganic mineral was also added, the generation of the oil-in-water type emulsion was accelerated. Example 4 Production of the Gelatine Material (Gelatin Material No. (a)) with the content of the soil sprayer 200 g of a 1.5% aqueous solution of calcium chloride were introduced in the form of drops 97 g of emulsification A of the oil in water type produced in example 1 to obtain 98 g of a gelatinized material (a) with chloropicrin content (chloropicrin content: 49% by weight). In the same way, the gelatinized materials from (b) to (k) of the emulsion (B) to (K) were obtained, as described in examples 2 and 3. The results are shown in table 2.

Table 2 Material Production Results Gelatinized From the results described above, it was discovered that a gelatinized material with a high content of soil fumigator could be produced. Example 5 Production of a Solid Material with a soil fumigator content (Solid material with soil fumigator content No. (A-a)). Ninety g of the gelatinized material (a) produced in Example 4 were dried in the air at room temperature for 48 hours to obtain 39 g of the solid material containing earth fumigator (Aa) (chloropicrin content: 80%). . The gelatinized materials from (b) to (k) obtained in Example 4 above were dried under the conditions described in Table 3 to obtain the solid materials containing soil fumigator (Bb) at (Kk) , respectively.

Ui Table 3 Results of Solid Material Production with content of Earth fumigator u or O From the results described above, it was discovered that solid material could be produced with the fumigator content of the earth with a high content of soil fumigant. In addition, the smell of the soil migrator was not observed in the solid material with the contents of the soil fumigator. Reference Example 1 Analysis of the Quantity of the Fumigator of the Earth in the Solid material with the content of the Earth Fumigator. Twenty ml of a methanol solution and water (9: 1, volume: volume) were fed into a 50-ml test tube with a silicone plug which was weighed exactly in advance, and weighed in a manner Exact A tablet of the solid material containing earth migrant fu (A-a) was placed in this solution to obtain the exact weight. The resulting solution was maintained at room temperature for 6 days and then the amount of the soil fumigator in the solution was measured by high performance liquid chromatography. The amount of the soil sprayer contained in the material containing the soil sprayer was calculated from the amount of soil sprayer in the solution. Example 6 Measurement of the Odor of the Solid Material Containing the Earth Sprayer Five g of the gelatinized material or the solid material with the soil sprayer content obtained in Example 4 and 5 were fed in terms of the amount of chloropicrin in the soil. a 500-ml poly-container, which was hermetically sealed and kept at room temperature for 24 hours. Two hundred ml of air were collected in the gas phase and the collected air was absorbed in 10 ml of methanol. The amount of chloropicrin in the methanol solution was measured by high performance liquid chromatography. Table 4 Amount of Chloropicrin in the Gas Phase From the results described above, the solid material with the fumigator content of the earth in which the release of the fumigator from the earth in relation to the fumigator of the earth and the gelatinized material is suppressed in an extreme way. Example 7 In a 300-ml 4-necked flask, 37 g of chloropicrin (a product with a purity of 99.5%) and 12 g of fostiazate (product name: Nemathrin) were fed and mixed. 0.9 g of gelatin powder (a product of Nitta Gelatin I nc., Fine Powder R) and 0.9 g of white carbon were fed into the resulting mixture. Within the resulting mixture, 48 g of 1.5% sodium alginate was added. (a product of Kimica Corporation) in aqueous solution and the resulting mixture was stirred under conditions of 66 m / m in. peripheral speed of a mixing blade to produce an oil-in-water type emulsion. Drops were incorporated in the form of 97 g of the emulsion in 200 g of a 1.5% aqueous solution of calcium chloride to obtain 98 g of the gelatinized material with the content of chloropicrin and fostiazate (content of chloropicrin: 37% by weight and content of fosthiazate: 1.2% by weight). Ninety g of the above gelatinized material were air-dried for 48 hours to obtain 45 g of a solid material with a content of chloropicrin and fosthiazate (chloropicrin content: 55% by weight and content of fosthiazate: 26% by weight). The smell of chloropicrin was not felt. From the results, it was discovered that a solid material with soil fumigant content was obtained even from an agricultural chemical mixed with chloropicrin and another agricultural chemical. Example 8 Test of the Treatment of the Earth with the Solid Material with the Container of the Earth Sprayer A container with a volume of 62.2 L was filled with 41 L of earth (soil moisture: 15% by weight) in the suburbs of Mobara -shi. Three g of the solid materials with soil fumigant content A-a, B-b, F-f, G-g and J-j obtained in Example 5 were buried in terms of the amount of chloropicrin at a depth of 10 cm in the center of the container. In a similar manner, the following comparative formulations X and Y were buried. After burying, the surface was covered with a 0.5-mm vinyl sheet for agricultural use. After 30 minutes, 1 hour, 3 hours, 7 hours, 24 hours, 48 hours, 72 hours, 96 hours, 168 hours and 240 hours, 200 ml of air was collected in the gas phase and the collected air was absorbed into the gas phase. of 10 ml of methanol. The methanol solution was analyzed by HPLC to examine the amount of chloropicrin. Comparative Formulation X: A formulation that is 3 g of chloropicrin placed inside a 4 cm x 9 cm bag made of a polyvinyl alcohol film (a product of Nippon Synthetic Chemical Industry Co., Ltd., Hi-Selon S400C) and sealed hermetically. Comparative Formulation Y: A formulation that is 3 g of Soilean (a product of Mitsui Chemicals, I nc.) Placed in a 4 cm x 9 cm bag made of a polyvinyl alcohol film (a product of Nippon Synthetic Chemical I nd ustry Co., Ltd., H i-Selon S400C) and hermetically sealed. Table 5 Test results in the treatment of soil of solid material with soil fumigator content From the results described above, it was discovered that when the solid material containing the earth's fumigant was treated in the earth, the fumigation of the earth could be carried out in a manner equal to that of the earth fumigator that is the comtiva formulation.

Example 9 Effect of Cucumber Fusarium Wilt A field contaminated with Fusarium oxysporum f. sp. cucumerinum was drawn and plowed with a tractor. An area of 1 20 cm wide and 600 cm long was used as an experimental trace. In the total surface, 55 g of the solid material containing the fumigator of the earth I-i obtained in Example 5 were sprayed and then mixed in the soil. After being mixed in the earth, the surface of the earth was covered with a polyethylene film that has a thickness of 0.05 mm. As a comparative formulation, chloropicrin (a product of M itsui Chemicals, I nc.) Was introduced at a depth of 1 5 cm at intervals of 30 cm by 3 ml per hole and the holes were covered with soil and surface the earth was covered with a polyethylene film. After 20 days of treatment, the polyethylene film cover was cleaned and 40 plants of cucumbers were scribbled for each stroke. After 40 days of the transplant, the incidence of Fusarium wilt disease of the cucumber was examined from the degrees of darkening in the basal part.

Table 6 Effect of Fusarium oxysporum f. sp. cucumerinum For table 6, it was found that the solid material with the soil fumigator content I-i exhibited the same effect as the chloropicrin formulation which was the comparative formulation. That is, it was discovered that the solid material with soil fumigator content had the same effect as the solid fumigator that was the comparative formulation. The solid material containing soil fumigator according to the present invention is produced from the emulsion with a soil fumigator contained in a high concentration. Therefore, it is a solid material with soil fumigator content with less load at the time of drying and with a high content of soil fumigator. Because the solid material in which the soil fumigant is extremely prime, so that a person may not feel the irritating odor, a farmer can handle it easily. In addition, when the above solid material is applied to the ground, the soil can be fumigated quickly and within a short period of time. This solid material is useful for the production of crops without reducing the frequency of planting in a year.

Claims

REVIVAL DICTION IS 1. A solid material with soil fumigator content containing not less than 60% and not more than 85% by weight of a soil fumigator, not less than 0.5% and not more than 1 5% by weight of gelatin, not less than 0% and not more than 10% by weight of a mineral and norwegian, not less than 1% and not more than 15% by weight of a polysaccharide that reacts with a higher or divalent valent metal salt to cause This mode is gelatinization and not less than 0.5% and not more than 20% by weight of water. 2 . The solid material with fuming content of the earth according to claim 1, characterized in that the soil fumigator is a soil fumigator that has a boiling point of not less than 40 ° C and a vapor pressure not lower of 70 Pa / 20 ° C. 3. The solid material with soil fume content as described in claim 2, characterized in that the soil fumigator is one or more types of soil fumigators selected from chloropicrin, D-D and allyl isothiocyanate. 4. The solid material containing earth-migrating fu as described in any of the claims 1 to 3, characterized in that the polysaccharide which reacts with the higher or divalent valent metal salt to cause thus gelatinization is one or more types selected from water soluble alginate salt, low methoxyl pectin and kapa-carragean. 5. A process for producing the solid material with soil fumigator content as described in claim 1, which comprises the following steps from (a) to (c): (a) the step of producing an emulsion of oil type in water with a soil fumigator content of not less than 10% and not more than 85% by weight by stirring an aqueous solution of the polysaccharide that reacts with the higher or divalent valent metal salt to thereby cause gelatinization, a fumigator of the earth, a gelatin and inorganic mineral; (b) the step of producing the gelatinized material by reacting the emulsion obtained in step (a) with the highest or divalent valent metal salt; and (c) the step of producing a solid material containing soil fumigator by drying the gelatinized material obtained in step (b). 6. The process for the production of solid material with soil fumigator content according to claim 5, characterized in that the soil fumigator is one or more types of soil fumigators selected from chloropicrin, D-D and allyl isothiocyanate. 7. The process for producing the solid material with soil fumigator content as described in claim 5 or 6, wherein the polysaccharide which reacts with the higher or divalent valent metal salt to thereby cause The gelatinization is used in an amount not less than 1% and not more than 1 5% by weight based on the soil fumigator. 8. The process for the production of the solid material containing earth migrant fu as described in any of claims 5 to 7, characterized in that the polysaccharide which reacts with the highest valent metal salt or divalent to thereby cause gelatinization is one or more types selected from water-soluble alginate salt, low methoxyl pectin and carrageenan layer. 9. The process for the production of the solid material with soil fumigator content as described in any of claims 5 to 8, characterized in that the gelatin is used in an amount not less than 0.5% and not more than 1 5% by weight based on the soil sprayer. 10. The process for producing the solid material with the content of the soil migrator as described in any of claims 5 to 9, characterized in that the inorganic mineral is used in an amount not less than 0. % and not more than 10% by weight based on the migrant of the earth. eleven . The process for producing the solid material with the soil fumigator content as described in any of claims 5 to 10, characterized in that the water is contained in an amount not less than 0.5% and not more than 20% by weight based on the solid material with soil fumigator content when the gelatinized material obtained in step (b) is dried . 12. A solid material with soil fumigator content produced according to step (c) of the method as described in any of claims 5 to 11. 3. The gelatinized material produced according to step (b) of the method as described in any of the claims from 5 to 1 0. 14. An oil-in-oil emulsion produced in accordance with step (a) of the method as described in any one of claims 5 to

1.