• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    PURPOSE: A process of preparing a sustained release formulation containing a biologically active substance, a coating agent and a release-controlling agent in a porous carrier is provided. Therefore, the use of the formulation effectively controls the release time and quantity of an active material of agricultural chemicals or a fertilizer, reduces the amount of the agricultural chemicals or fertilizer to be used and minimizes crop injury caused by the agricultural chemicals or fertilizer. CONSTITUTION: A sustained release composition comprises an absorbing carrier and a sustained release layer. In the composition, 0.0005 to 50 parts by weight of a biologically active substance is absorbed into 100 parts by weight of a porous carrier, a mixture of 0.05 to 15 parts by weight of polysaccharides, 0.3 to 20 parts by weight of inorganic alkali and 0.25 to 20 parts by weight of one or two or more release-controlling agents selected from the group consisting of phosphorous acid, phosphoric acid, acetic acid, hydrochloric acid or the like is coated on the surface of the absorbing carrier.
    公开号:KR20030064310A
    申请号:KR1020030004457
    申请日:2003-01-23
    公开日:2003-07-31
    发明作者:박해준
    申请人:(주)바이오드림스；
    IPC主号:
    专利说明:

    Sustained-Releasing Agricaltural Chemical and the Method for Producing Thereof}
    [11] The present invention relates to a sustained-release biologically active composition containing a biologically active substance and a method for preparing the same, and more particularly, to a sustained-release substance containing a biologically active substance such as pesticides or fertilizers, a coating agent and a release controlling agent in a porous carrier. A biologically active composition and a method for producing the same. By using the composition according to the present invention, the time of effect expression of the pesticide or fertilizer active substance can be controlled, and the sustained-release pesticide or fertilizer which is less likely to cause weakening or the like becomes possible.
    [12] Until now, vegetables such as lettuce, cucumbers, tomatoes and pesticides used to control pests such as fruit trees, flowers and grains, or fertilizers used to supply nutrients to them, have been mixed with water or granulated with excipients. It is common to be In this case, the active ingredient concentration is rapidly reduced by spilling, acidifying or evaporating outside the area where the pesticide or fertilizer component is applied. Therefore, since the duration of drug efficacy is usually short, it is a general reality to apply the spray several times in an amount exceeding the usage amount or concentration. Excessive use of pesticides or fertilizers causes various health problems for farmers and crop consumers, and causes serious environmental pollution due to salt accumulation and overnutrition due to continuous spreading and irrigation of soil.
    [13] Accordingly, by providing sustained release to biologically active substances such as various pesticides and fertilizers in solid or liquid form, spraying an appropriate concentration of pesticides or fertilizers at a time to control the timing of activity of biologically active substances so that the effect is maintained for a long time. Research is being actively conducted.
    [14] Methods for preparing sustained-release pesticides include: 1) Method of incorporating pesticide active material into microcapsules: 2) Method of enclosing pesticide active material into cyclotextrin: 3) Pesticide preparation active materials such as Japanese patent granules and powder Background of the Invention Methods for producing particles by mixing alone or with an extender and the like and coating the produced particles with a resin are known.
    [15] Japanese Patent No. Hei 6-116103 discloses a method of introducing sustained release by introducing a pesticide dissolved in a solvent into a biodegradable resin injected into a plate, and Japanese Patent No. Hei 5-85902 mixes a biodegradable polymer with a pesticide raw material. After dissolving in chloroform, and adsorbed on granular zeolite and heated, chloroform was evaporated to prepare a sustained-release pesticide.
    [16] U.S. Pat.No.4647537 discloses an attempt to bioencapsulate a plant disease inhibiting microorganism in a carrageenan polymer matrix, and U.S. Pat.No.4382813 discloses starch alkoxide containing a substance having a divalent cation selected from calcium, barium and strontium. Rapid insolubilization describes the coagulation or precipitation of the entrapped pesticide.
    [17] Korean Patent Publication No. 1989-1145 discloses a method of first coating a granular pesticide with a mixture of isocyanate and liquid paraffin, and second coating with an organic powder or an inorganic powder.
    [18] A technique for coating other pesticide active materials with solid water-insoluble low-melting beeswax and supporting them on granular fertilizers (Korean Patent No. 1989-4995), a polyhydroxylated compound or a polyisocyanate carrier containing a pesticide Interfacial polymerization reaction to form a polyurea barrier film (Korean Patent No. 1992-7002910), a method of mixing the pesticide active material with a biodegradable resin and a release control aid, injection molding (Korea Patent Publication No. 2000-42895 No.), impregnating active materials such as fertilizers or pesticides by using pulp including waste paper as an impregnant, and then forming the primary resin coating layer and the secondary sulfur coating layer to impregnate the active material with the impregnating agent. Sustained release (Korea Patent Publication No. 2000-2248) and the like are known to increase the sustained release of fertilizers and pesticides to increase the sustained release of.
    [19] However, these methods are 1) complicated in manufacturing process or limited in application, 2) expensive to manufacture pesticides or fertilizers due to high production cost, and 3) cause harmful manufacturing environment due to use of solvents in manufacturing. In particular, 4) it has a problem that the coating layer is rapidly biodegraded when applied to the actual field, so that the sustained release effect is hardly exerted.
    [20] In other words, depending on the type of pesticide compound, there are some pesticide compounds that cannot be sustained-release preparations due to the encapsulation of microcapsules or the inclusion of a cyclodextrin and a clathrate compound. In addition, a conventional method for producing a sustained-release preparation may be applied, and satisfactory sustained release is not obtained, and the sustained-release effect of the obtained pesticide preparation is insufficient, and thus sustaining and extending biological effects, which is one of the objectives of sustained-release pesticides, may be applied. In many cases, reduction or the like cannot be sufficiently achieved. In addition, because the manufacturing technology of the sustained-release pesticide is complicated or the raw materials used are expensive, there are still many problems to be solved in technical or economic aspects.
    [21] Therefore, there is a demand for the development of new techniques for sustained-release pesticides or fertilizer compositions or methods for their preparation.
    [22] On the other hand, a method for coating microorganisms with polysaccharides is known, although not for sustained release of the pesticide component. For example, the invention described in Korean Patent Application No. 2000-17801 relates to a method of coating a microorganism to have heat resistance and acid resistance using a microsaccharide derived from a microorganism. This microbial coating is to protect the microorganisms from gastric acid and various intestinal digestive enzymes when ingesting microorganisms (such as lactic acid bacteria) useful for the human body so that the microorganisms can be seated in the small and large intestine. Therefore, the microbial coating must be disassembled immediately upon reaching the necessary site (small intestine and large intestine) while maintaining resistance to acid, heat and digestive enzymes, so that the microorganism can adhere to and grow in the small intestine and large intestine.
    [23] Thus, microbial coatings belong to a completely different field from the manufacture of sustained-release pesticides that allow the active material to be released slowly.
    [24] The present invention to solve the problems of the prior art as described above, an object of the present invention is to provide a sustained-release preparation of a biologically active substance is simple to manufacture and a method for producing the same.
    [25] It is another object of the present invention to provide a sustained release preparation of a biologically active substance which is inexpensive and readily available.
    [26] It is another object of the present invention to provide a biologically active substance formulation which is environmentally friendly and has excellent sustained release.
    [1] 1 is a photograph showing the gelling properties of polysaccharides according to the content of organic and inorganic acids.
    [2] Figure 2a is a photograph showing the biodegradation delay effect of the polysaccharides by the organic acid.
    [3] Figure 2b is a photograph showing the biodegradation delay effect of the polysaccharides by organic acids in the soil.
    [4] 3 is a photograph of a visual model of a sustained release formulation.
    [5] Figure 4 is a photograph showing the dissolution test results of the sustained release formulation model.
    [6] Figure 5 is another picture showing the dissolution test results of the sustained release formulation model.
    [7] 6A is a graph showing the sustained release of salicylic acid.
    [8] 6B is a graph showing sustained release of ampicillin.
    [9] 6C is a graph showing the sustained release of metalaccil.
    [10] Figure 7 is a photograph showing the effect of the combination of the sustained release formulation.
    [27] The present invention for achieving the above object, (I) an adsorbent carrier adsorbed 0.0005-50 parts by weight of the biologically active material to 1000 parts by weight of the porous carrier; 0.05 to 15 parts by weight of polysaccharide, 0.3 to 20 parts by weight of inorganic alkali, and 0.25 to 20 parts by weight of one or two or more release regulators selected from the group consisting of organic acids and inorganic acids such as phosphorous acid, phosphoric acid, acetic acid, hydrochloric acid, and the like The sustained-release formulation of a biologically active substance consisting of a sustained release membrane coated on the surface of (sustained release formulation in which the active substance is adsorbed on a carrier).
    [28] On the other hand, in the sustained release preparation of the biologically active substance according to the present invention, the biologically active substance may be adsorbed to the porous carrier as described above, but may also be present in the sustained release membrane.
    [29] The present invention also provides (II) 1000 parts by weight of the porous carrier; One or two or more release regulators selected from the group consisting of 0.0005-50 parts by weight of biologically active substance, 0.05-15 parts by weight of polysaccharide, 0.3-20 parts by weight of inorganic alkali, and organic and inorganic acids such as phosphorous acid, phosphoric acid, acetic acid and hydrochloric acid 0.25 The sustained-release preparation of the biologically active substance (the sustained-release preparation in which the active substance is contained in the sustained release membrane) which consists of -20 weight part mixed the sustained-release film coated on the surface of the said carrier.
    [30] In the present invention, the inorganic alkali may be applied to KOH, NaOH and the like.
    [31] The sustained-release preparation according to the present invention is adsorbed on a porous carrier coated with a biologically active substance or is evenly contained in a coating membrane, that is, a sustained release membrane, controls the release of the biologically active substance and controls biodegradation of the matrix (polysaccharide) for a long time. By the release controlling agent to exhibit an effect that the active material is slowly released to the outside of the sustained release formulation.
    [32] According to the present invention, (1) suppression of release by the adsorption of the carrier itself and the active substance, (2) inhibition of release of the active substance by the membrane of the coated polysaccharide, (3) release control agents (phosphoric acid, phosphoric acid, acetic acid, Organic acids and inorganic acids such as hydrochloric acid) are released first, and then the release of the active substances is controlled in two to three stages, such as biologically active substances are released through the microcavities formed by the release of them, so that the sustained release is good, Not only can the convenience be increased, but the release control agent contained in the sustained release film suppresses the natural decomposition (by microorganisms) of the coated polysaccharide, so that the sustained release property is maintained in the field.
    [33] At this time, as a carrier for adsorption of agricultural active ingredients, natural minerals such as zeolite, pearlite, vermiculite, diatomaceous earth, ceramic, activated carbon and sand are commonly used as main components of excipients and extenders in soil improving agents and pesticides. One or two or more mixtures selected from the group consisting of these may be used, and any other carrier may be used as long as it is a soil-compatible carrier. The carrier may be used as it is, or may be one obtained by treating the raw material at a high temperature of 600 ° C. or higher, that is, a calcined carrier, in order to remove impurities in the interior and to make the conditions inside the carrier at the best condition.
    [34] The porous carrier adsorbs a biologically active material to absolutely reduce its diffusion property, and serves to widen the contact surface so that the sustained release film coated on the surface does not detach.
    [35] On the other hand, the sustained-release preparation according to the present invention is generally sprayed on the soil by using a hand or a spreading device, the preferred particle size range is 0.5 to 5mm, usually diameter of 2mm or more workability when applied Not only is it good, it doesn't disperse into the air and it falls to the ground, increasing its effectiveness. Of course, for other applications, the particles may be smaller or larger.
    [36] In the present invention, as the polysaccharide is degradable in nature, festan, levane, xantham gum, pullulan, polysaccharide-7, cellulose, juglan, gellan, curdlan or an appropriate mixture thereof may be used.
    [37] Biologically active substances to which the present invention can be applied include insecticides, herbicides, plant growth regulators, nematicides, fungicides, fungicides, rodenticides, fumigants, animal and pest control agents, biopesticides, pheromones, sex attractants, flavorants, fragrances, Dietary supplements, drugs, and fertilizers.
    [38] In the sustained-release preparation according to the present invention, the content of the biologically active substance can be appropriately selected depending on the kind and specific activity of the active substance.
    [39] Examples of the pesticide ingredient include insecticidal active ingredients, bactericidal active ingredients, herbicidal active ingredients and plant growth active ingredients. However, the active ingredient is not limited to those exemplified.
    [40] Pesticide active ingredients include Acephate, Isoxathion, Imidacloprid, Ethylthiodemeton, Ethofenprox, Cartap, Carbosulphan ( Carbosulfan, Clofentezine, Cyclopyrifas-methyl, Fenbutatin-oxide, Cycloloprothrin, Dimetylrinphos, Dimethoate , Silafluofen, Diazinon, Thiodicarb, Thiocyclam, Tebufenozide, Nitenpyram, Vamidothion, Vamidothion Bifenthrin, Pyridaphenthion, Pyridaben, Pyrimiphos-methyl, Fipronil, Phenisobromolate, Bupropezin Buprofezin, Furathiocarb, Propafos, Bensu ltap), benfuracarb, formothion, marathon, monocrotophos, BPMC, CVMC, DEP, EPN, MEP, MIPC, MPP, MTMC, NAC, PAP, PHC, PMP , XMC, and the like.
    [41] Examples of bactericidal active ingredients include phosphite, acibenzolar-S-methyl, azoxystrobin, bitanol, isoprothiolane, isopurodione and isoprodionate. (Iminoctadine triacetate), Oxolinic acid, Oxone-copper, Kasugamycin, Carpropamid, Captan, Diclomezine, Thiabenda Thiabendazole, Thifluzamide, Tecloftalam, Tricyclazole, Varidamycin, Hydroxyisoxazole, Pyroquilon, Phenariquina Fenarimol, Ferrimzone, Fthalide, Blasticidin, Polyoxin, Metasulfocarb, Metalaxyl, Metalaxyl-M, Meme Tominostrobin, Mepronil, Ampicillin, CNA, IBP, DF -351, NNF-9425, NNF-9850, etc. are mentioned.
    [42] Herbicidal active ingredients and plant growth regulators include Azimsulfuron, Atrazine, Amethin, Inabenfide, Imazosulfuron, Uniconazole and Espro Esprocarb, Etobenzanid, Oxadiazon, Carfenstrole, Quizarofop-ethyl, Quinclorac, Cumylron, Chlomethoxynil, Cyclosulfamuron, Dithiopyr, Cinosulfuron, Cyhalofop-butyl, Simazine, Dimethamerin (Dimetametryn) ), Dimepiperate, Cinmethylin, Dymron, Thenylchor, Triaphentenol, Naproanilide, Paclobutrazol , Bifenox, Piperophos, Pyrazoxyfen, Pyrazulfuronethyl osulfuron-ethyl, Pyrazolate, Pyributicarb, Pyriminobac-methyl, Butachlor, Butamifos, Pretilachlor, Bro Bromobutide, Bensulfuron-methyl, Benzofenap, Bentazon, Benticarb, Pentoxazone, Benfuresate, Mefenase Mefenacet, molinate, jasmonic acid (JA), salicylic acid (SA), BABA, BTH, ACN, CNP, 2,4-D, MCPB, MCPBethyl, and the like and plant growth regulators. have.
    [43] In the present invention, the various biologically active substances may be applied alone, or a plurality of active substances may be applied to one sustained-release preparation by appropriate combination and combination.
    [44] Hereinafter, a method for producing a sustained release formulation according to the present invention will be described. As the solvent used in the description below, water or an organic solvent or a mixed solution of a solvent may be appropriately selected according to the polarity and stability of the active ingredient. In addition, since the solvent and water are components that are evaporated and removed during the manufacturing process, the amount of use thereof is not critical, and thus, the solvent and water may be arbitrarily determined at a level suitable for the workability of the manufacturing process.
    [45] (I) Preparation of Sustained Release Formulations in which Active Material is Adsorbed on Carrier
    [46] According to the present invention, a sustained release preparation in which an active substance is adsorbed on a carrier is prepared as follows.
    [47] First, an active material solution is prepared by dissolving a predetermined biological active material in a predetermined volume, for example, 0.0005-50 g in 100 ml of a solvent depending on its inactivation and desired activity (solution acquisition step). The active material solution is mixed homogeneously with 1000 g of the porous carrier, and the mixture is dried at 25 to 150 ° C. to obtain an active material adsorption carrier (impregnation drying step).
    [48] Apart from the above, a predetermined volume of solvent, for example, 0.05-15 g of a polysaccharide suitable for 200 ml of water, 0.3-13 g of an inorganic alkali such as KOH, and organic acids and inorganic acids such as phosphorous acid, phosphoric acid, acetic acid and hydrochloric acid, or 0.25-10 g of the mixture is added and mixed evenly to prepare a suspended coating solution (coating solution preparation step).
    [49] Subsequently, the prepared dry adsorption carrier is mixed homogeneously with the prepared coating solution and dried at 25 to 150 ° C. to form a sustained release film on the surface of the adsorption carrier (coating step), thereby preparing a sustained release preparation of a biologically active substance according to the present invention. .
    [50] At this time, the drying temperature can be appropriately determined with reference to the heat resistance of the active material, the drying degree is good for storage and workability so that the moisture is 40% or less.
    [51] In the present invention, the polysaccharide coating may be repeated once or several times depending on the type and nature of the active substance and the degree of sustained release desired.
    [52] (II) Preparation of Sustained-Release Formula Containing Active Material in Sustained-Release Membrane
    [53] Sustained release preparation of another biologically active substance according to the present invention is prepared through the following process. Unlike the above method, the manufacturing process is simplified by simultaneously adsorbing the active material and coating the polysaccharide.
    [54] First, prepare an active material solution by dissolving 0.0005-50 g of the biologically active substance in a predetermined volume, for example, 50 ml of solvent (solution acquisition step), and separately from a predetermined volume of solvent, for example, polysaccharide in 150 ml of water. 0.05-15 g, 0.3-13 g of inorganic alkalis, such as KOH, and 0.25-10 g of 1 or 2 or more release control agents chosen from the group which consists of organic acids, such as phosphorous acid, phosphoric acid, acetic acid, hydrochloric acid, and an inorganic acid, are suspended. Prepare (coating solution preparation step).
    [55] The prepared active material solution and the coating solution are homogeneously mixed to obtain a coating solution containing the active material (active coating solution preparation step). After homogeneously mixing the coating solution containing the active material and 100 g of the porous carrier, and then homogeneously mixed the prepared dry adsorption carrier with the prepared coating solution and dried at 25 ~ 150 ℃ to form a sustained release film on the surface of the adsorption carrier ( Coating step) to prepare a sustained release formulation of the biologically active substance according to the present invention.
    [56] At this time, the drying temperature can be appropriately determined with reference to the heat resistance of the active material, the drying degree is good for storage and workability so that the moisture is 40% or less.
    [57] In the present invention, the polysaccharide coating may be repeated once or several times depending on the type and nature of the active substance and the degree of sustained release desired.
    [58] In the sustained-release preparation according to the present invention prepared through the above process, the active material is adsorbed to the porous carrier at a high concentration, and once the active material is adsorbed to the outside by the carrier structure (the active material alone at a high concentration) Rather than present), the sustained release is obtained primarily. In addition, the sustained-release pesticide prepared according to the present invention has a natural polysaccharide coated on the surface of the adsorbent to which the active substance is adsorbed, or a polysaccharide containing an active active substance is coated-adsorbed onto the adsorption carrier, thereby providing a mixture of the active substance and the carrier mixture. While maintaining the integrity, the coating component is gradually decomposed in the natural environment, thereby enabling dual sustained release.
    [59] In addition, organic acids and inorganic acids such as phosphorous acid, phosphoric acid, acetic acid, and hydrochloric acid added as coating ingredients prevent the polysaccharides from being rapidly decomposed by bacteria and the like to maintain the sustained release film, and when they are slowly released to the outside, The micro holes generated as they are released promote the release of biologically active substances to the outside.
    [60] Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention in more detail, it will be apparent to those skilled in the art that the scope of the present invention is not limited to these examples. For convenience, a phosphite is used as an active material, zeolite as a carrier, curdlan as a coating agent derived from microorganisms, and KOH as an inorganic alkali. However, pesticides, carriers, and coatings used in the examples are just examples selected for convenience, and various similar substances mentioned above may be applied in the same manner, and combinations of two or more pesticides may be applied to those skilled in the art. something to do.
    [61] Preliminary Experimental Example 1: Gelation Test of Polysaccharides
    [62] 2.5 g of curdlan was added to 200 ml of water, and dissolved in 8.3 g of KOH. Then, 2.5, 5.0, and 10.0 g of phosphorous acid (H 3 PO 3 ), phosphoric acid (H 3 PO 4 ), acetic acid (CH 3 COOH) and Hydrochloric acid (HCl) was added and thoroughly stirred to determine the respective pH. Each sample was then gelled (FIG. 1). The pH and degree of gelation are shown in Table 1.
    [63] As can be seen from the table, when 2.5 g of organic acid was added, the pH reached 13.1 to 13.3, and when 10 g was added, the pH reached 3.4 to 5.6. When 5 g was added, the pH was 11.7 only for phosphoric acid and phosphorous or acetic acid was added. When added, the change was minimal.
    [64] The degree of gelation was found to be more sensitive to pH change by the addition of organic acid than the amount of organic acid added. That is, for smooth gelation, it is preferable that the pH of the curdlan solution is 12 or less.
    [65] Organic acid Addition amount (g) pH Gelation degree Phosphorous acid2.513.2- 513.0- 105.61Good Phosphoric Acid2.513.1- 511.7Good 103.45Good Acetic acid2.513.3- 513.2- 105.53Good Inorganic hydrochloric acid2.512.5- 52.0Good 101.0Good
    [66] Preliminary Experimental Example 2: Test for preventing biodegradation of polysaccharides by organic acids 1
    [67] (1) It was confirmed whether biodegradation of polysaccharides was delayed by addition of organic acid to starch.
    [68] The degree of biodegradation was confirmed for 18 days at room temperature with respect to the control group to which the phosphoric acid, phosphoric acid and acetic acid was added as an organic acid and the control group not added. Specific compositions of the experimental zones and the results are shown in Table 2.
    [69] As can be seen from the table, only the control was biodegraded, confirming that organic acids can significantly delay the biodegradation of polysaccharides.
    [70] Starch Other additions Biodegradation degree Control2.5 g of starch in 100 ml of water Biodegradation Treatment tool 12.5 g of starch in 100 ml of waterKOH 8.3g, H 3 PO 3 10gNot observed Treatment 22.5 g of starch in 100 ml of waterH 3 PO 3 10gNot observed Processing Unit 32.5 g of starch in 100 ml of waterKOH 8.3g, H 3 PO 4 10gNot observed Treatment tool 42.5 g of starch in 100 ml of waterKOH 8.3g, CH 3 COOH 10gNot observed
    [71] (2) 2.5 g of curdlan was added to 200 ml of water, and the mixture was sufficiently stirred. After heating for 1 min in microwave, gelled control and 2.5 g of curdlan and 8.3 g of KOH were dissolved in 200 ml of water, followed by dissolving 10 g of H 3 PO 3. The gel was added to the gel and heated for 1 min in the microwave, and the biodegradation rate was checked while standing at room temperature for 14 days.
    [72] As a result, no signs of biodegradation were found in the treatment, and the control was significantly biodegradable. As a result, it was found that organic acids (phosphoric acid) can significantly delay the biodegradation of polysaccharides (FIG. 2A).
    [73] (3) Since it is a problem that the sustained release preparation according to the present invention is completely resistant to biodegradation, a certain amount of time is maintained under natural conditions, that is, a condition in which the phosphite, which is the content of the sustained release preparation, is repeatedly eluted. It was tested to see if biodegradation occurred.
    [74] Phosphorous acid was eluted by leaving the treated tool prepared in (2) in 400 ml of water for 1 hour at intervals of 3 days, and the experiment was carried out at room temperature. After 10 elution experiments, signs of biodegradation were found.
    [75] As a result, it was confirmed that the sustained-release preparation coated with the appropriate amount of the organic acid-added polysaccharide could be naturally decomposed while maintaining the sustained release while delaying biodegradation for a long time in the natural state.
    [76] (4) It was tested whether the coating component of the preparation according to the present invention biodegraded to what time in natural conditions.
    [77] 2.5 g of curdlan was added to 200 ml of water, and 8.3 g of KOH was added to the mixture, followed by stirring. After heating for 1 minute in a microwave, gelled control (AC, BC, CC) and 2.5 g of curdlan were added to 200 ml of water and KOH. After dissolving by adding 8.3g, the organic acid in the amount shown in Table 3 was added, and then heated to 1 minute in Microwave to prepare a gelled treatment (A1 ~ C3).
    [78] H 3 PO 3 (g) H 3 PO 4 (g) CH 3 COOH (g) A11.0A20.84A30.78 B10.5B20.42B30.39 C10.33C20.28C30.26
    [79] 5g each of the prepared control and treatment were buried 3 cm deep into the soil collected from the package and stored in a plant cultivation greenhouse at 20-25 ° C. to check whether it remained after 3 months and 9 months.
    [80] After 3 months, the remaining amount of the control and treatment was shown in the photograph in Figure 2b. As can be seen from the photograph, it was found that a significant amount remained in the treated groups added with 0.5 g or more of phosphorous acid, 0.42 g or more of phosphoric acid, or 0.39 g or more of acetic acid.
    [81] Although not shown, after 9 months, none of the treatments remained.
    [82] This suggests that organic acids can significantly delay the biodegradation of polysaccharides.
    [83] Preliminary Experimental Example 4: Model Test of Sustained Release Formulations
    [84] Model tests were performed to visually confirm that the sustained release formulations according to the invention are indeed sustained release.
    [85] As a model of "carrier to which biologically active substance is adsorbed," a preparation containing methyl violet, which is widely used as a dye for agrochemicals, was used. The methyl violet preparation is obtained by adsorbing 0.5 g of methyl violet to 1 Kg of sand.
    [86] First, 2.5, 5, and 10 g of Curdlan were added and dissolved in 100 ml of an aqueous solution of 8.3 g of KOH dissolved therein, respectively, and 10 g of phosphorous acid was added thereto to prepare a coating agent. 1 Kg of methyl violet preparation was added to each of the coating agents, stirred evenly, and hot-air dried to prepare a model of a sustained release preparation. The uncoated methyl violet formulation was used as a control. The photograph of each formulation is shown in FIG.
    [87] 100 mg of each treatment formulation was placed in a test tube, and 5 ml of DDW was added thereto for 1 day, and the recovery was repeated for 16 days, and the color change of the recovered water was observed (FIG. 4). In the figure, each test tube is listed in the order of date of recovery. As can be seen in the figure, the untreated coating agent showed a phenomenon in which a large amount of methyl violet was eluted from day 1 and then almost eluted after about 9 days. On the other hand, in the treatment groups, the amount of methyl violet is little and the time elapses. In particular, the more the content of the curdlan was confirmed that the amount of methyl violet was eluted by the sustained release.
    [88] After 16 days, each formulation was recovered and dried to examine the degree of residual color (FIG. 5). In the case of the coated formulation, it can be seen that sustained release may be continued even after 16 days. The more the content of the curdlan, the greater the amount of methyl violet remaining, and the control group was found to be much discolored, it can be seen that most of the methyl violet is eluted.
    [89] Preliminary Experimental Example 5: Preparation and Sustained Release Test of Sustained Release Film Containing Active Material
    [90] 2.5 g of curdlan was dissolved in a 200 ml aqueous solution containing 8.3 g of KOH, and 10 g of salicylate, a signal substance that induces resistance of plants, was added and stirred evenly. Subsequently, 10 g of phosphorous acid was added thereto, followed by gelation, followed by drying for 20 minutes in a 80 to 100 ° C. dry oven to prepare a sustained-release film containing salicylate.
    [91] 35 mg of the sustained-release film containing salicylate was placed in a test tube, and 5 ml of DDW was added to it for 1 day, and then the procedure was repeated. 50 μl of the recovered sample was taken, and the content of salicylate in the solution was analyzed by HPLC. (FIG. 6A).
    [92] Instead of salicylate, the antibiotic ampicillin (2 g) was tested as a biologically active material in the same manner as above (FIG. 6b).
    [93] Metalaccil (10 g) was used as a biologically active substance instead of salicylate. Metalacyl was first dissolved in 50 ml of methanol, and then phosphorous acid (10 g) was added to a 150 ml aqueous solution containing 8.3 g of KOH, and then mixed with the stirred coating solution.
    [94] As can be seen from the accompanying drawings, it was confirmed that even after 8 days, the active biologically active substance was continuously eluted around 1/5 of the release amount on the second day.
    [95] Example 1 Preparation of a Sustained-Release Formulation Containing an Active Substance in a Carrier
    [96] 10 g of Metalaxyl was dissolved in 100 ml of methanol to prepare an active material solution (solution acquisition step). The solution was homogeneously mixed with 1000 g of dry zeolite, and the mixture was dried at 25 to 150 ° C. to obtain an active substance adsorbent carrier (impregnation drying step).
    [97] Apart from the above, 2.5 g of curdlan was added to 200 ml of water and dissolved by adding 8.3 g of KOH, followed by addition of 10 g of phosphoric acid (H 3 PO 4 ), followed by sufficient stirring (coating solution preparation step).
    [98] Subsequently, the prepared dry adsorption carrier was mixed homogeneously with the prepared coating solution, and dried at 100 ° C. so that the moisture was about 35% or less to form a sustained release film on the surface of the adsorption carrier (coating step). Sex formulations were prepared.
    [99] Example 2 Preparation of Sustained-Release Formulation Containing Active Material in Sustained-Release Membrane
    [100] First, 10 g of Metalaxyl was dissolved in 50 ml of methanol to prepare an active material solution (solution acquisition step). Apart from the above, 2.5 g of curdlan was added to 200 ml of water, and dissolved by adding 8.3 g of KOH. Then, 10 g of phosphoric acid (H 3 PO 4 ) was added thereto, followed by sufficient stirring to prepare a suspended coating solution (coating solution preparation step).
    [101] The prepared active material solution and the coating solution were homogeneously mixed to obtain a coating solution containing the active material (active coating solution preparation step). After homogeneously mixing the coating solution containing the active material and 1000 g of dry zeolite, and dried to 100% or less moisture at 100 ℃ to form a sustained-release film on the surface of the adsorbent carrier (coating step) biological activity according to the present invention Sustained release formulations of materials were prepared.
    [102] Application example: Greenhouse test of sustained-release pesticides
    [103] It was confirmed whether the sustained release formulation of the biologically active substance of the present invention prepared in Examples 1 and 2 exhibits sustained release effect in the actual greenhouse.
    [104] Four sets of 24 healthy pepper plants each 16 days after sowing were prepared, and each set was treated with the relevant substances in the amounts shown in Table 4 below.
    [105] Throughput Per PlantActive substance content (mg) per plant MetalaxylOrganic acid Western Province 11 g of preparation according to Example 1 (dry basis)10mg10mg Western Province 21 g of preparation according to Example 2 (dry basis)10mg10mg Non-Western150 ml each of Metalaxyl and 66 ml of phosphoric acid10mg10mg No treatmentNo treatment00
    [106] Treatment were inoculated four weeks elapsed after which a pepper blight pathogen Phytophthora capsici zoospore 3X concentration of 3.3 × 103cfu / ㎖ zoospore suspension of 10㎖ than normal concentration of each pepper plant. The number of onset days, the incidence rate, and the control value were examined 7 days after the inoculation (Table 5), and a photograph thereof is shown in FIG. 7. In the figure, A denotes sustained-release sphere 2, B denotes non-sustained sphere, and control denotes untreated sphere. The results were similar to those in the Western District 2, but the photographs were damaged, and thus the illustration of the Photo of the Western District 1 is omitted.
    [107] Disease developmentIncidence (%)Control price (%) Western Province 1312.585.7 Western Province 2416.780.9 Non-Western1666.623.9 No treatment2187.5-
    [108] As can be seen from the table and figure, even when the active material of the same initial concentration is treated, it can be seen that the sustained-release spheres treated with the sustained-release preparation according to the present invention have superior control value than the non-sustained release sphere. In addition, even if the manufacturing method is slightly different, it can be seen that the sustained release formulation according to Example 1 and the sustained release formulation according to Example 2 have almost similar sustained release effect and control value.
    [109] By using the sustained-release preparation according to the present invention, it is possible to effectively control the release time and the release amount for expressing the effect of the pesticide or fertilizer active material. Therefore, the same effect can be obtained even if a high concentration of pesticides or fertilizers are not repeatedly added in a short cycle.
    [110] As a result, farmers can not only significantly reduce the amount of used pesticides and fertilizers, but also reduce risks such as weakness, and can also have a positive effect on environmental preservation.
    权利要求:
    Claims (12)
    [1" claim-type="Currently amended] An adsorption carrier having 0.0005 to 50 parts by weight of a biologically active substance adsorbed on 1000 parts by weight of a porous carrier;
    0.05 to 15 parts by weight of polysaccharide, 0.3 to 20 parts by weight of inorganic alkali, and 0.25 to 20 parts by weight of one or two or more release regulators selected from the group consisting of organic acids and inorganic acids such as phosphorous acid, phosphoric acid, acetic acid, hydrochloric acid, and the like Sustained release film coated on the surface of the;
    Sustained release preparation of biologically active substance.
    [2" claim-type="Currently amended] 1000 parts by weight of the porous carrier;
    One or two or more release regulators selected from the group consisting of 0.0005-50 parts by weight of biologically active substance, 0.05-15 parts by weight of polysaccharide, 0.3-20 parts by weight of inorganic alkali, and organic and inorganic acids such as phosphorous acid, phosphoric acid, acetic acid and hydrochloric acid 0.25 A sustained release film mixed with 20 parts by weight of the carrier and coated on the surface of the carrier;
    Sustained release preparation of biologically active substance.
    [3" claim-type="Currently amended] The method according to claim 1 or 2,
    The biologically active substances include insecticides, herbicides, plant growth regulators, nematicides, fungicides, fungicides, rat drugs, fumigants, animal and pest control agents, biopesticides, pheromones, sex attractants, flavoring agents, fragrances, dietary supplements, drugs ( drug) and a sustained release preparation of a biologically active substance, characterized in that one or two or more mixtures selected from the group consisting of fertilizers.
    [4" claim-type="Currently amended] The method of claim 3, wherein
    The biologically active substance may be phosphite, acephate, isoxathion, imidacloprid, ethylthiodemeton, ethofenprox, or bitanol. Cartap, Carbosulfan, Copenpentezine, Cyclopyrifas-methyl, Fenbutatin-oxide, Cycloloprin, Dimethylbin Dimetylrinphos, Dimethoate, Silafluofen, Diazinon, Thiodicarb, Thiocyclam, Tebufenozide, Nitenpyram Nitenpyram, Vamidothion, Bifenthrin, Pyridaphenthion, Pyridaben, Pyrimiphos-methyl, Fipronil, Pheniso Phenisobromolate, Buprofezin, Furathiocarb, Papafos, Bensultap, Benfuracarb, Formothion, Marathon, Monocrotophos, BPMC, CVMC, DEP, EPN, MEP, MIPC, MPP, MTMC, NAC, PAP, PHC, PMP, XMC, Acibenzolar-S-methyl, Azoxystrobin, Isoprothiolane, Isoprothiolane, Isoprodion, Iminooctadine Acetate triacetate, Oxolinic acid, Oxone-copper, Kasugamycin, Carpropamid, Captan, Diclomezine, Thiabendazole ( Thiabendazole, Thifluzamide, Tecloftalam, Tricyclazole, Varidamycin, Hydroxyisoxazole, Pyroquilon, Phenarimol Fenarimol, Ferrimzone, Fthalide, Blasticidin, Polyoxin, Metasulfocarb (M ethasulfocarb), metalaxyl, metalaxyl, metominostrobin, methominostrobin, mepronil, ampicillin, CNA, IBP, DF-351, NNF-9425, NNF-9850 Azimsulfuron, Atrazine, Amethrin, Ametryn, Inabenfide, Imazosulfuron, Uniconazole, Esprocarb, Etobenzanid ), Oxadiazon, Carfenstrole, Quizalopethyl (Quizalofop-ethyl), Quinclorac, Cumylron, Chlomethoxynil, Cyclosulfamuron (Cyclosulfamuron), Dithiopyr, Cinosulfuron, Cyhalofop-butyl, Simazine, Dimetametryn, Dimepiperate, Synmethes Cinmethylin, Dymron, Tenylchor, Triaphentenol, Naproanilide, Paprobutrazole (Paclob) utrazol, Bifenox, Piperophos, Pyrazoxyfen, Pyrazosulfuron-ethyl, Pyrazolate, Pyributicarb, Pyributicarb Pyriminobac-methyl, Butachlor, Butamifos, Butamifos, Pretilachlor, Bromobutide, Bensulfuron-methyl, Benzofenap, Bentazon, Benthiocarb, Pentoxazone, Benfuresate, Mefenacet, Molinate, Jasmonic Acid (JA), Salicylic Acid (SA) , BABA, BTHACN, CNP, 2,4-D, MCPB and MCPB ethyl is a sustained-release preparation of a biologically active substance, characterized in that one or more mixtures selected from the group consisting of.
    [5" claim-type="Currently amended] The method according to claim 1 or 2,
    The porous carrier is a sustained-release preparation of a biologically active substance, characterized in that one or more release controlling agents selected from the group consisting of zeolite, pearlite, vermiculite, diatomaceous earth, ceramic, sand and activated carbon.
    [6" claim-type="Currently amended] The method according to claim 1 or 2,
    The polysaccharide is a sustained release of a biologically active substance, characterized in that one or more mixtures selected from the group consisting of festan, levane, xantham, pullulan, polysaccharide-7, cellulose, juglan, gellan and curdlan. Sex preparations.
    [7" claim-type="Currently amended] In the method for preparing a sustained release preparation of the biologically active substance according to claim 1,
    (A) a solution obtaining step of dissolving 0.0005 to 50 parts by weight of the biologically active substance in a predetermined volume of solvent to obtain an active substance solution;
    (B) an impregnation drying step of homogeneously mixing 1000 parts by weight of the active material solution and the porous carrier and drying to obtain an active material adsorption carrier;
    (C) 0.05 to 15 parts by weight of a polysaccharide, 0.3 to 20 parts by weight of an inorganic alkali, and one or two or more release regulators selected from the group consisting of organic acids and inorganic acids such as phosphorous acid, phosphoric acid, acetic acid and hydrochloric acid in a predetermined volume of solvent Preparing a coating solution by mixing 20 parts by weight to obtain a suspended coating solution;
    (D) a coating step of homogeneously mixing the dried active material adsorption carrier and the coating solution and then drying to form a sustained release film on the surface of the adsorption carrier;
    Method for producing a sustained release formulation of the biologically active substance comprising a.
    [8" claim-type="Currently amended] A method for preparing a sustained release preparation of a biologically active substance according to claim 2,
    (A) a solution obtaining step of dissolving 0.0005 to 50 parts by weight of the biologically active substance in a predetermined volume of solvent to obtain an active substance solution;
    (B) 0.25 to 20 parts by weight of one or two or more release regulators selected from the group consisting of 0.05 to 15 parts by weight of polysaccharide, 0.3 to 20 parts by weight of inorganic alkali, and organic acids such as phosphorous acid, phosphoric acid and acetic acid in a predetermined volume of solvent Preparing a coating solution to obtain a suspended coating solution;
    (C) an active coating solution preparation step of homogeneously mixing the active material solution in the coating solution to obtain a coating solution containing the active material;
    (D) a coating step of homogeneously mixing 1000 parts by weight of the coating liquid and the porous carrier containing the active material and drying to form a sustained release film containing the active material on the surface of the carrier;
    Method for producing a sustained release formulation of the biologically active substance comprising a.
    [9" claim-type="Currently amended] The method according to claim 7 or 8,
    The biologically active substances include insecticides, herbicides, plant growth regulators, nematicides, fungicides, fungicides, rat drugs, fumigants, animal and pest control agents, biopesticides, pheromones, sex attractants, flavoring agents, fragrances, dietary supplements, drugs ( drug) and a mixture of one or two or more selected from the group consisting of fertilizers.
    [10" claim-type="Currently amended] The method of claim 9,
    The biologically active substance may be phosphite, acephate, isoxathion, imidacloprid, ethylthiodemeton, ethofenprox, or bitanol. Cartap, Carbosulfan, Copenpentezine, Cyclopyrifas-methyl, Fenbutatin-oxide, Cycloloprin, Dimethylbin Dimetylrinphos, Dimethoate, Silafluofen, Diazinon, Thiodicarb, Thiocyclam, Tebufenozide, Nitenpyram Nitenpyram, Vamidothion, Bifenthrin, Pyridaphenthion, Pyridaben, Pyrimiphos-methyl, Fipronil, Pheniso Phenisobromolate, Buprofezin, Furathiocarb, Papafos, Bensultap, Benfuracarb, Formothion, Marathon, Monocrotophos, BPMC, CVMC, DEP, EPN, MEP, MIPC, MPP, MTMC, NAC, PAP, PHC, PMP, XMC, Acibenzolar-S-methyl, Azoxystrobin, Isoprothiolane, Isoprothiolane, Isoprodion, Iminooctadine Acetate triacetate, Oxolinic acid, Oxone-copper, Kasugamycin, Carpropamid, Captan, Diclomezine, Thiabendazole ( Thiabendazole, Thifluzamide, Tecloftalam, Tricyclazole, Varidamycin, Hydroxyisoxazole, Pyroquilon, Phenarimol Fenarimol, Ferrimzone, Fthalide, Blasticidin, Polyoxin, Metasulfocarb (Me thasulfocarb, Metalaxil, Metalaxyl, Metominostrobin, Mepronil, Ampicillin, CNA, IBP, DF-351, NNF-9425, NNF-9850, Azimsul Azimsulfuron, Atrazine, Amethrin, Ametryn, Inabenfide, Imazosulfuron, Uniconazole, Esprocarb, Etobenzanid ), Oxadiazon, Carfenstrole, Quizalopethyl (Quizalofop-ethyl), Quinclorac, Cumylron, Chlomethoxynil, Cyclosulfamuron (Cyclosulfamuron), Dithiopyr, Cinosulfuron, Cyhalofop-butyl, Simazine, Dimetametryn, Dimepiperate, Synmethes Cinmethylin, Dymron, Thenylchor, Triaphentenol, Naproanilide, Paprobutrazole (Paclob) utrazol, Bifenox, Piperophos, Pyrazoxyfen, Pyrazosulfuron-ethyl, Pyrazolate, Pyributicarb, Pyributicarb Pyriminobac-methyl, Butachlor, Butamifos, Butamifos, Pretilachlor, Bromobutide, Bensulfuron-methyl, Benzofenap, Bentazon, Benthiocarb, Pentoxazone, Benfuresate, Mefenacet, Molinate, Jasmonic Acid (JA), Salicylic Acid (SA) , BABA, BTHACN, CNP, 2,4-D, MCPB and MCPB ethyl, a method for producing a sustained-release preparation of a biologically active substance, characterized in that at least one mixture selected from the group consisting of.
    [11" claim-type="Currently amended] The method according to claim 7 or 8,
    The porous carrier is a method for producing a sustained-release preparation of a biologically active substance, characterized in that one or two or more mixtures selected from the group consisting of zeolite, pearlite, vermiculite, diatomaceous earth, ceramic, sand and activated carbon.
    [12" claim-type="Currently amended] The method according to claim 7 or 8,
    The polysaccharide is a sustained release of a biologically active substance, characterized in that one or more mixtures selected from the group consisting of festan, levane, xantham, pullulan, polysaccharide-7, cellulose, juglan, gellan and curdlan. Method for preparing sex preparations.
    类似技术:
    公开号 | 公开日 | 专利标题
    Kashyap et al.2015|Chitosan nanoparticle based delivery systems for sustainable agriculture
    EP2680685B1|2019-08-28|Seed coating compositions and methods for their production
    Tsuji2001|Microencapsulation of pesticides and their improved handling safety
    US10021824B2|2018-07-17|Superabsorbent polymer seed coatings and associated methods
    ES2298274T3|2008-05-16|Pesticide distribution system.
    AU626561B2|1992-08-06|Terrestrial delivery compositions
    US5567430A|1996-10-22|Insecticidal delivery compositions and method for controlling a population of insects in an aquatic environment
    EP2330890B1|2017-01-18|Solid core microcapsular compositions and uses thereof
    ES2588182T3|2016-10-31|Protection of germinating seeds and pills containing pesticides
    US9061950B2|2015-06-23|Water-dispersible pellets
    Roy et al.2014|Controlled pesticide release from biodegradable polymers
    US5183690A|1993-02-02|Starch encapsulation of biologically active agents by a continuous process
    CN102696587B|2014-03-26|Compound controlled-release granular pesticide preparation and preparation method thereof
    Campos et al.2014|Applications of controlled release systems for fungicides, herbicides, acaricides, nutrients, and plant growth hormones: a review
    JP4625811B2|2011-02-02|Elution controlled pesticide formulation
    US4344857A|1982-08-17|Encapsulation by entrapment
    DE4309756B4|2006-09-07|Controlled release microcapsules and controlled release method of a chemical agent
    US20110319341A1|2011-12-29|Method of controlling pests with biosurfactant penetrants as carriers for active agents
    JP5173848B2|2013-04-03|Stabilized granular pesticide
    CN104387157B|2018-01-12|Granular controlled release agrochemical compositions and preparation method thereof
    EP1982590B1|2017-08-16|Pesticide-containing resin compositions controlled in dissolution, process for production thereof, and pesticide preparations
    AU2002352873B2|2006-11-09|A product for use in agriculture or horticulture
    US7867507B2|2011-01-11|Pesticide delivery granule
    CA1313154C|1993-01-26|Starch encapsulation of biocontrol agents
    US7789932B2|2010-09-07|Dispersible potash pellets
    同族专利:
    公开号 | 公开日
    KR100408157B1|2003-12-01|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2002-01-23|Priority to KR1020020003833
    2002-01-23|Priority to KR20020003833
    2003-01-23|Application filed by (주)바이오드림스
    2003-01-23|Priority claimed from JP2003561339A
    2003-07-31|Publication of KR20030064310A
    2003-12-01|Application granted
    2003-12-01|Publication of KR100408157B1
    优先权:
    申请号 | 申请日 | 专利标题
    KR1020020003833|2002-01-23|
    KR20020003833|2002-01-23|
    [返回顶部]