JP3694305B2 - Sustained release pesticide and method for producing the same - Google Patents

Description

The present invention relates to a sustained-release composition containing a bioactive substance and a method for producing the same, and more specifically, a porous carrier contains a bioactive substance such as an agrochemical or a fertilizer, a coating filler, a release regulator, and the like. The present invention relates to a bioactive sustained-release composition and a method for producing the same. When the composition according to the present invention is used, it is possible to control the time when the effect of the agrochemical or fertilizer is manifested, and the agrochemical or the fertilizer with reduced harmful damage becomes possible.

Until now, agricultural chemicals used to prevent damage caused by head blight and pests of vegetables, fruits, flowers, and crops, and fertilizers used as an important nutrient source for these crops are liquid mixed with water or shaped It is usually in granular form mixed with the agent. In this case, the pesticide or fertilizer component flows out of the area where it is distributed, spreads at the time of application, or evaporates and the active ingredient concentration decreases rapidly. Therefore, since the duration of drug efficacy is usually short, it is common to distribute a large number of times at a concentration higher than actually required. The problems with the use of such transient pesticides or fertilizers are caused by the various harmful health effects of crop producers and consumers, the accumulation of salt by continuous spreading and irrigation of fertilizers, and the severity of overnutrition. Environmental pollution.

As a result, the effect of the biologically active substance of solid or liquid agricultural chemicals or fertilizers is sustained by imparting a sustained release property to the biologically active substance once at a proper concentration. Studies for controlling the onset of activity have been actively pursued.

Known methods for producing sustained-release pesticides are 1) a method in which a pesticide active substance is placed in a microcapsule, 2) a method in which the pesticide active substance is confined in cyclodextrin, and 3) a pesticide composition in granular or powder form. And a method of coating particles produced by mixing these active substances alone or with a filler or the like with a resin.

Japanese Unexamined Patent Publication No. 6-116103 discloses a method of giving sustained release by introducing an agrochemical dissolved in a solvent into a biodegradable resin injected into a plate shape. Japanese Patent Application Laid-Open No. 5-85902 discloses a method for producing a sustained-release agricultural chemical by mixing a biodegradable polymer with an agrochemical base material and dissolving it in chloroform, adsorbing and heating to granular zeolite, and evaporating the chloroform. Proposed.

U.S. Pat. No. 4,647,537 discloses a method for encapsulating phytopathogenic fungi in a carrageenan polymer matrix. U.S. Pat. No. 4,382,813 describes rapidly insolubilizing starch alkoxide containing a substance having a divalent cation selected from calcium, barium and strontium, and solidifying or precipitating the trapped insecticide. .

Korean Patent Publication No. 1989-1145 discloses a method for coating a granular pesticide, in which the granular pesticide is firstly coated with a mixture of isocyanate and liquid paraffin and secondarily coated with an organic powder or an inorganic powder.

In addition, there are several known techniques for sustained release compounds.

Korean Published Patent No. 1989-4995 discloses that an agrochemical active substance is coated with a solid water-insoluble low melting point beeswax substance and supported on a granular fertilizer.

Korean Published Patent No. 1992-7002910 discloses a method of forming a polyurea blocking film by interfacial polymerization reaction of a carrier containing an agrochemical with a polyhydroxylated compound or polyisocyanate.

Korean Published Patent No. 2000-42895 discloses mixing an agrochemical active substance with a biodegradable resin and a controlled release formulation.

In Korean Patent No. 2000-2248, a pulp containing waste paper or the like is used as an impregnating agent (matrix) and impregnated with an active substance such as fertilizer or agricultural chemical. There are fertilizers in which a secondary sulfur coating layer is formed to increase the sustained release of the active substance impregnated in the impregnating agent and sustained release agents in which the sustained release of the agricultural chemical is increased.

However, the above methods have the following problems. First, the manufacturing process is complex or limited in application. Secondly, the production cost is high and it becomes a burden to improve the agricultural chemical or fertilizer. Third, it creates a harmful environment due to the use of solvents during production. Fourthly, when actually carried out, the coating layer is rapidly biodegraded and hardly exerts a sustained release effect.

That is, some agricultural chemical compounds are not used as sustained-release preparations because they cannot be encapsulated or become inclusion compounds with cyclodextrins. In addition, since it is difficult to obtain satisfactory sustained release, a conventional method for producing a sustained release preparation may be applied. Since the sustained release effect of the agrochemical of the agrochemical formulation having sustained release is insufficient, the sustained and extended biological efficacy of the sustained release agrochemical may not be sufficiently achieved. In addition, since the method for producing sustained-release agricultural chemicals is complicated or the raw materials used are expensive, there are many problems to be solved in the technical or cost aspects in the future.

Accordingly, there is a demand for the development of a new technique relating to a sustained release agricultural chemical or fertilizer composition and / or a method for producing the same.

On the other hand, a method for coating microorganisms with polysaccharides is known, but not for the sustained release of agricultural chemical ingredients. For example, Korean Patent Application No. 2000-17801 discloses a method of coating microorganisms to have heat resistance and acid resistance using polysaccharides produced from microorganisms. Such microbial coating technology protects microorganisms that are useful to the human body (lactic acid bacteria, bacteria, etc.) from gastric acid and various intestinal digestive enzymes when the microorganisms are ingested, and the microorganisms settle on the small and large intestines. This is to make it possible. Therefore, according to the microbial coating, while maintaining acid resistance, heat resistance and resistance to digestive enzymes, the coating is rapidly disassembled when reaching a predetermined site (small intestine and large intestine), and the microorganism adheres to the small intestine and large intestine. You should be able to grow. Therefore, microbial coatings belong to a completely different field from the production of sustained-release pesticides that slowly release active substances.

In order to solve the problems of the conventional techniques as described above, an object of the present invention is to provide a sustained-release preparation of a bioactive substance that is easy to produce and a method for producing the same.

Another object of the present invention is to provide a sustained-release preparation of a bioactive substance that is inexpensive and easily available, and a method for producing the same.

An object of the present invention is to provide a bioactive substance preparation imparted with environmentally friendly and excellent sustained release properties and a method for producing the same.

In a feature of the present invention, a sustained-release preparation of a bioactive substance is provided, wherein the sustained-release preparation comprises an adsorption carrier in which 0.0005 to 50 parts by weight of the bioactive substance is adsorbed on 1000 parts by weight of a porous carrier, and 1 or 2 or more consisting of organic acid or inorganic acid 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 phosphorous acid, phosphoric acid, acetic acid, hydrochloric acid and the like 0.25 to 20 parts by weight of a release controlling agent is mixed and has a sustained release film coated on the surface of the adsorption carrier.

On the other hand, in the sustained-release preparation of the bioactive substance according to the present invention, the bioactive substance can be adsorbed on the porous carrier as described above, but can also be present in the sustained-release membrane.

The present invention also includes 1000 parts by weight of a porous carrier, 0.0005 to 50 parts by weight of a biologically active substance, 0.05 to 15 parts by weight of a polysaccharide, 0.3 to 20 parts by weight of an inorganic alkali, and phosphorous acid, Sustained release film in which 0.25 to 20 parts by weight of one or more release regulators made of organic acid or inorganic acid selected from the group consisting of phosphoric acid, acetic acid, hydrochloric acid and the like are mixed and coated on the surface of the carrier And a sustained-release preparation of the bioactive substance.

In the present invention, KOH, NaOH and the like can be applied as the inorganic alkali.

The sustained-release preparation according to the present invention is adsorbed on a porous carrier coated with a bioactive substance or is uniformly contained in a coating film, that is, a sustained-release film, to control the release of the bioactive substance. The release agent that controls the biodegradation of the substrate (polysaccharide) for a considerable period of time has the effect of slowly releasing the active substance outside the sustained-release preparation.

According to the present invention, firstly, the release is suppressed by the adsorption action between the carrier itself and the active active substance. Secondly, the release of the active substance is suppressed by the polysaccharide-coated membrane. Thirdly, a release regulator composed of organic acid and inorganic acid such as phosphorous acid, phosphoric acid, acetic acid and hydrochloric acid is first released to form micropores, through which the bioactive substance is released, Sustained release increases, and the convenience of working when distributing agricultural chemicals can be increased. Fourth, since the release regulator contained in the sustained-release membrane suppresses natural degradation of polysaccharides (by microorganisms), there is an effect that sustained release is maintained even in actual implementation.

At this time, as a carrier for adsorbing agricultural active ingredients, natural minerals that are generally used as a main component of excipients and extenders during the production of soil conditioners and agricultural chemicals, that is, zeolite, perlite, meteorite, diatomaceous earth, ceramic, sand and One or a mixture of two or more activated carbons. Any other carrier that is compatible with soil can be used. The carrier can be used as it is without being treated, and the rough is treated at a high temperature of 600 ° C. or higher in order to remove impurities inside and make the inside of the carrier the best condition, that is, calcined. You can also use a different carrier.

The porous carrier serves to adsorb the biologically active substance to absolutely reduce its diffusivity, and to spread the contact surface so that the sustained-release film coated on the surface is not detached.

On the other hand, the sustained-release preparation according to the present invention is usually distributed on the soil manually or using a distribution apparatus. Therefore, the desirable particle size range is 0.5 to 5 mm, and more preferably 2 mm or more from the viewpoint of workability and use efficiency when used in soil. Of course, the particle size may be increased or decreased depending on the use.

In the present invention, the polysaccharide is naturally degradable and includes festan, levan, xanthan gum, pullulan, polysaccharide-7, cellulose, zoglan, gellan. (Gellan), curdlan, or a suitable mixture thereof.

Examples of bioactive substances include insecticides, herbicides, plant growth regulators, anti-nematode agents, fungicides, biocides, fumigants, fumigants, animal and pest control agents, biological pest control agents, pheromones, Sex attractants, flavors, fragrances, dietary supplements, drugs and fertilizers. In the sustained-release preparation according to the present invention, the content of the bioactive substance can be appropriately selected according to the type of active substance and the prescribed activity.

Examples of agrochemical ingredients include, but are not limited to, insecticidal active ingredients, bactericidal active ingredients, herbicidal active ingredients and plant growth active ingredients.

Insecticidal active ingredients include acephate, isoxathion, imidacloprid, ethylthiodemethon, etofenprox, cartap, carbop, boss Fentezine, Cyclopyrifos-methyl, Fenbutatin-oxide, Cycloprothrin, Dimethyllinphos, Dimetholate, Dimethoate Ajinon (Diazinon), thiodicarb (Thiodicarb), thiocyclam (Thiocyclam), tebufenozide (Tebufenozide), nitenpyram (Nitenpyram), Buamidochion (Vamidothion), bifenthrin (Bifenthrin), pyridaphenthion (Pyridaphenthion), pyridaben (Pyridaben), pirimiphos-methyl (Pyrimiphos-methyl ), Fipronil, phenisobromolate, buprofezin, furathiocarb, propafos, bensultap, benf Examples include carb (Benfuracarb), formothion (Malathon), malathon (Monathofos), monocrotophos (Monocrotophos), BPMC, CVMC, DEP, EPN, MEP, MIPC, MPP, MTMC, NAC, PAP, PHC, PMP, XMC, etc. .

Bactericidal active ingredients include phosphites, acibenzolar-S-methyl, azoxystrobin, bitanol, isoprothiolane, isoprodion, and iproodion. Acetic acid salt (Iminoctadine triacetate), Oxolinic acid (Oxolinic acid), Oxone-copper, Kasugamycin (Kasugamycin), Capromid (Carpropamid), Captan (Dtan), Dithromedin (D) ), Teclophthalam, tricyclazole, valididamycin, hydroxyisoxazole, pyroquilon, phenzimol, phenimol , Polyoxin, metasulfocarb, metalaxl, metalaxl-M, methinostrobin, mepronil, ampicillin A CNA, IBP, like DF-351, NNF-9425, NNF-9850.

Examples of herbicidal active ingredients and plant growth regulating ingredients include: (Etobenzanid), Oxadiazon, Cavenstrole, Quizalofop-ethyl, Quinclorac, Cumyllon, Chlomethyoxycyclonyl uron), dithiopyr (Dithiopyr), cynosulfuron (Cinosulfuron), cyhalofop-butyl (Cimhalop-butyl), simazine (Simazine), dimethamethynyl (Dimethymethyimine) Tenylchor, Triapentenol, Naproanilide, Paclobutrazol, Bifenox, Piperophos, Pyrazopyrazol, Pyrazopyrazol n-ethyl, pyrazolate, pyributiccarb, pyriminobac-methyl, butachlor, butamifos, pretibromol, pretibromol, pretibrochlor -Methyl), benzophenap, Bentazon, Benthicarb, pentoxazone, Benfuresate, mefenanacet, Melinacet, A, BA, Molinate, BA TH, ACN, CNP, 2,4-D, MCPB, like MCPB-ethyl and the like, and plant growth regulators.

In the present invention, the biologically active substance can be used alone or in combination with a plurality of active substances.

Hereinafter, a method for producing a sustained-release preparation according to the present invention will be described. As the solvent used throughout the description, water, an organic solvent or a mixed solvent can 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 production process, the amount of use is not so important, and can be arbitrarily determined as appropriate for the workability of the production process.

(I) Production of sustained release preparation having active substance adsorbed on carrier A sustained release preparation having an active substance adsorbed on a porous carrier according to the present invention is produced as follows.

First, 0.0005 to 50 g of a predetermined biologically active substance is dissolved in a predetermined amount, for example, 100 ml of a solvent according to the specified activity and the desired activity to prepare an active substance solution (solution acquisition stage). The obtained active substance solution is mixed with 1000 g of the porous carrier and the mixture is mixed and homogeneously mixed and dried at 25 to 150 ° C. As a result, an active substance adsorbing carrier is obtained (impregnation drying step).

Next, the obtained adsorbent carrier is homogeneously mixed with the coating liquid, and the obtained mixture is dried at 25 to 150 ° C. to coat the surface of the adsorbent carrier to form a sustained-release film (coating step). The sustained-release preparation of the bioactive substance according to the invention is manufactured.

At this time, the drying temperature is appropriately determined with reference to the heat resistance of the active substance, and the degree of drying is preferably 40% or less from the viewpoint of storage and workability.

In the present invention, the polysaccharide coating can be repeated once or several times depending on the type and characteristics of the active substance and the desired degree of sustained release.

(II) Production of sustained-release preparation having active substance contained in sustained-release membrane The sustained-release preparation of another embodiment according to the present invention is produced through the following process. Unlike the above-described manufacturing method, the manufacturing method of this embodiment is simplified by simultaneously performing adsorption of an active substance and coating with a polysaccharide.

First, 0.0005 to 50 g of the bioactive substance is dissolved in a predetermined amount, for example, 50 ml of solvent to obtain an active substance solution (solution acquisition stage).

Apart from this, 0.05 to 15 g of suitable polysaccharides, 0.3 to 13 g of inorganic alkalis such as KOH, and organic acids or inorganics selected from the group consisting of phosphorous acid, phosphoric acid, acetic acid, hydrochloric acid and the like Prepare a coating liquid in which 0.25 to 10 g of one or two or more mixtures of acids are mixed and suspended (coating liquid production stage).

The obtained active substance solution and coating liquid are homogeneously mixed to obtain a coating liquid containing the active substance (active coating liquid production stage). According to the present invention, the coating liquid containing the active substance and 1000 g of the porous carrier are uniformly mixed and then dried at 25 to 150 ° C. to form a sustained-release film on the surface of the carrier (coating step). Completed the production of sustained-release preparations of bioactive substances.

At this time, the drying temperature is appropriately determined with reference to the heat resistance of the active substance. The degree of drying is preferably 40% or less from the viewpoint of storage and workability.

In the present invention, the polysaccharide coating can be repeated once or several times depending on the type and characteristics of the active substance and the desired degree of sustained release.

In the sustained-release preparation according to the present invention, the active substance is adsorbed on the porous carrier at a high concentration, and the diffusion of the adsorbed active substance is significantly reduced by the carrier than when the active substance is present at a high concentration alone. Therefore, sustained release is mainly obtained. In the sustained-release agricultural chemical according to the present invention, the surface of the adsorbent on which the active substance is adsorbed is coated with natural polysaccharide, or the polysaccharide containing the active substance is coated / adsorbed on the adsorption carrier. Therefore, since the coating component is slowly decomposed in a natural environment while maintaining the integrity of the active substance and the carrier, it is possible to achieve a double sustained release.

In addition, organic acids and inorganic acids such as phosphorous acid, phosphoric acid, acetic acid, and hydrochloric acid added as coating components prevent the polysaccharide component from being rapidly decomposed and maintain the durability of the sustained-release membrane. On the other hand, when the organic and inorganic acids are released, the bioactive substance is promoted to be released to the outside through the generated micropores.

Hereinafter, the present invention will be described in more detail through various examples. These examples are merely for explaining the present invention more specifically, and the scope of the present invention is not limited to these examples.

For convenience, phosphite was used as the active substance, zeolite was used as the carrier, curdlan was used as the coating agent made from microorganisms, and KOH was used as the inorganic alkali. However, the agrochemical components, carriers and coating agents used in the examples of the present invention are only examples selected for convenience, and the above-mentioned various analogs can be applied in the same way, and two or more It will be apparent to those skilled in the art that any combination of these agrochemical ingredients is also applicable.

Preliminary Experimental Example 1: 2.5 g of polysaccharide gelled test curdlan is added to 200 ml of water, and 8.3 g of KOH is added thereto and dissolved. Add 2.5, 5.0, 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) to the lysate The pH of each product obtained by stirring was measured. Then, each sample was gelatinized (FIG. 1). The pH and degree of gelation are shown in Table 1.

As can be seen from the table, when 2.5 g of an organic acid is added, the pH becomes about 3.4 to 5.6 when 13.1 to 13.3 and 10 g are added. When 5 g of organic acid was added, the pH was 11.7 only in the case of phosphoric acid, and when phosphorous acid or acetic acid was added, the change was slight.

It was found that the degree of gelation was more sensitive to pH change due to the addition of organic acid than the amount of organic acid added. That is, the pH of the curdlan solution is preferably 12 or less for smooth gelation.

Preliminary Experiment Example 2: Polysaccharide biodegradation prevention test 1 with organic acid
It was confirmed whether the biodegradation of polysaccharides was delayed by adding organic acid using starch.

Phosphorous acid, phosphoric acid and acetic acid were used as organic acids. The biodegradation degree was confirmed for the treatment group to which the organic acid was added and the control group to which the organic acid was not added while being left at room temperature for 18 days. Specific compositions of the experimental groups and the results are shown in Table 2.

As can be seen from the table, since only the control group was biodegraded, it was confirmed that the organic acid could significantly delay the biodegradation of the polysaccharide.

(2) After adding 2.5 g of curdlan to 200 ml of water and sufficiently stirring, it was gelled by applying heat with a microwave for 1 minute (control group). In 200 ml of water, 2.5 g of curdlan and 8.3 g of KOH were added and dissolved, and then 10 g of H ₃ PO ₃ was added and heated in a microwave for 1 minute to gel (treatment group). The degree of biodegradation was confirmed while leaving the control group and the treatment group at room temperature for 14 days.

As a result, no signs of biodegradation were found in the treated group, confirming that the control group was significantly biodegraded. This proved that organic acids (phosphorous acid) can delay the biodegradation of polysaccharides considerably (FIG. 2a).

(3) If the sustained release formulation according to the present invention is not completely biodegraded, it will have undesirable effects on the environment. Experiments were carried out to determine how much time passed and biodegradation under natural conditions, that is, conditions in which phosphite, which is the content of a sustained-release preparation, was eluted repeatedly.

An experiment was conducted in which phosphorous acid was eluted by leaving the treatment group produced in the above (2) in 400 ml of water for 1 hour every 3 days and then removing the phosphorous acid, and leaving the treatment group at room temperature. The treatment group was biodegraded after 10 elution experiments.

As a result, biodegradation of a sustained-release preparation coated with a polysaccharide to which an appropriate amount of an organic acid has been added is delayed for a considerable period in a natural state, and can be finally spontaneously degraded after maintaining sustained release. confirmed.

(4) An experiment was conducted to determine how much time passed under natural conditions to biodegrade the coating component of the subtractive preparation according to the present invention.

To 200 ml of water, 2.5 g of curdlan was added, and 8.3 g of KOH was added thereto, and after sufficient stirring, heat was applied in a microwave for 1 minute to cause gelation (control groups AC, BC, CC). After 2.5 g of curdlan and 8.3 g of KOH were added to 200 ml of water and dissolved, an amount of an organic acid as shown in Table 3 below was added and heated in a microwave for 1 minute to gel (treatment group A1). ~ C3).

5 g each of the control group and the treatment group was embedded in soil at a depth of 3 cm and stored in a greenhouse for plant cultivation at 20 to 25 ° C. It was confirmed whether it remained in soil after 3 months and 9 months.

The residual amounts of the control group and the treatment group after 3 months are shown in the photograph in FIG. 2B. As shown in FIG. 2b, in the case of the treatment group to which 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 was added, it was found that a considerable amount remained in the soil.

Although not shown, none remained in all treatment groups after 9 months.

Thus, it was found that organic acids can significantly delay the biodegradation of polysaccharides.

Preliminary Experimental Example 3: Model Test of Sustained Release Formulation A model test was conducted to visually confirm whether the sustained release formulation according to the present invention actually has sustained release properties.

As a model of a carrier on which a biologically active substance is adsorbed, a preparation containing methyl violet, which is widely used as a coloring agent for agricultural chemicals, was used. The methyl violet preparation is obtained by adsorbing 0.5 g of methyl violet on 1 kg of sand.

First, 8.3 g of KOH was dissolved in 100 ml of an aqueous solution, and curdlan 2.5, 5 and 10 g were added to the obtained solvents (treatment group 1, treatment group 2 and treatment group 3 respectively), and then phosphorous acid was added to each. 10 g was added to produce a coating agent. 1 kg of methyl violet preparation was added to each coating agent and stirred uniformly, followed by hot air drying to produce a model of sustained release preparation. An uncoated methyl violet formulation was used as a control group. A photograph of each formulation is shown in FIG.

100 mg of each treatment group formulation is placed in a test tube, 5 ml of deionized distilled water (DDW) is added, and the resulting product is allowed to stand for 1 day and collected. This process was repeated for 16 days, and the color change of the collected water was observed (FIG. 4). In the same figure, each test tube was arranged in the order of collection date. As can be seen from the figure, in the preparation in which the coating agent was not treated, a large amount of methyl violet was eluted from the first day, and the dissolution almost ended after about the ninth day. On the other hand, in the treatment group, the elution amount of methyl violet is small, and it can be seen that a small amount of elution occurs continuously over time. In particular, it was confirmed that as the curdlan content increased, the amount of methyl violet released and eluted gradually decreased.

After the lapse of 16 days, each preparation was collected and dried, and the remaining chromaticity was examined (FIG. 5). From the hue of the coated preparation, it can be seen that sustained release continues after 16 days. It was found that as the curdlan content increased, the amount of residual methyl violet increased, and in the case of the control group, methyl violet was almost eluted because of the large amount of decolorization.

Preliminary Experimental Example 4: Production of sustained-release membrane containing active substance and sustained-release test KOH 8.3 g was added to a 200 ml aqueous solution, and then 2.5 g of curdlan was added to dissolve it. For this purpose, 10 g of sodium salicylate as a signal substance was added and stirred uniformly. Next, after adding 10 g of phosphorous acid to gelate, it was dried in an 80-100 ° C. dry oven for 20 minutes to produce a sustained-release membrane containing sodium salicylate.

35 mg of a sustained-release membrane containing sodium salicylate is placed in a test tube, 5 ml of DDW is added, and the mixture is left for 1 day and collected. While repeating this process, 50 μl of each collected sample was taken and analyzed for the content of sodium salicylate in the sample solution using high performance liquid chromatography (HPLC) (FIG. 6a).

The test was performed in the same manner as described above except that 2 g of ampicillin, an antibiotic, was used as a bioactive substance instead of sodium salicylate (FIG. 6b).

Alternatively, 10 g of metalaxyl was used as the bioactive substance instead of sodium salicylate. However, except that metalaxyl was first dissolved in 50 ml of methanol, and then 10 g of phosphorous acid was added to a 150 ml aqueous solution containing 8.3 g of KOH and mixed with the stirred coating solution (FIG. 6 c).

As shown in the figure, even after 8 days, it was confirmed that the active bioactive substance of about 1/5 of the released amount on the second day was continuously eluted.

Preparation of sustained-release preparation having active substance adsorbed on carrier 10 g of metalaxyl was dissolved in 100 ml of methanol to obtain an active substance solution (solution acquisition stage).

After immobilizing 1000 g of dried zeolite in the obtained solution and mixing it uniformly, it was dried at 25 to 150 ° C. to obtain an active substance adsorbing carrier (impregnation drying stage).

In addition to the above, 2.5 g of curdlan was added to 200 ml of water, 8.3 g of KOH was added thereto, 10 g of phosphoric acid (H ₃ PO ₄ ) was added thereto, and the mixture was sufficiently stirred (coating liquid production stage).

Next, after the prepared adsorbent carrier is homogeneously mixed with the coating liquid, the resulting mixture is coated on the surface of the adsorbent carrier, and dried at 100 ° C. so that the moisture content of the active substance is 35% or less. A film is formed (coating stage) and the production of the bioactive substance sustained-release preparation according to the present invention is completed.

Production of sustained-release preparation having active substance contained in sustained-release membrane First, 10 g of metalaxyl was dissolved in 50 ml of methanol to prepare an active substance solution (solution acquisition stage).

Aside from the above, 2.5 g of curdlan is added to 200 ml of water, 8.3 g of KOH is added to it, and then 10 g of phosphoric acid (H ₃ PO ₄ ) is added, and the mixture is sufficiently stirred and suspended. A coating liquid was obtained (coating liquid production stage).

The obtained active substance solution and the coating liquid were homogeneously mixed to obtain a coating liquid containing the active substance (active coating liquid production stage). After the active substance solution and 1000 g of dry zeolite are mixed homogeneously, the surface of the dried adsorbent carrier is coated with the obtained mixture, dried at 100 ° C. so that the water content is 35% or less, and gradually released onto the surface of the adsorbent carrier. The production of the sustained-release preparation of the bioactive substance according to the present invention is completed by forming a conductive film (coating stage).

Application example: Greenhouse test of sustained-release agrochemicals In order to confirm whether the sustained-release preparation of the bioactive substance according to the present invention produced in Examples 1 and 2 described above actually has a sustained-release effect in a greenhouse, observation was performed. went.

Four sets each consisting of 24 strains of healthy chili plants that had been laid for 16 days after seeding were treated, and each set was treated with the active substance in the amount shown in Table 4 below.

After 4 weeks from the treatment, 10 ml of phytophytracapsin zoospore suspension, which is a causative agent of pepper disease, is 3.3 × 10 ³ cfu / ml, which is three times the normal concentration. Inoculated pepper plants. Seven days after the inoculation, the number of diseased strains, disease incidence and control value were examined (Table 5), and the photograph is shown in FIG. In the photograph, “A” represents the sustained release group 2, “B” represents the non-sustained release group, and “control” represents the untreated group.

In the sustained-release group 1, similar results to the sustained-release group 2 appeared, but since the photograph was damaged in the experiment, the illustration of the photograph regarding the sustained-release group 1 is omitted.

As can be seen from Table 5 and FIG. 7, even when the same initial concentration of active substance is treated, the controlled release group treated with the sustained release formulation according to the present invention has much better control than the non-sustained release group. Can be confirmed. It can also be seen that the sustained-release preparation according to Example 1 and the sustained-release preparation according to Example 2 have almost similar sustained-release effects and control values even if the production methods are somewhat different.

When the sustained-release preparation according to the present invention is used, it becomes possible to effectively control the release time and the release amount for the expression of the effect of the active substance of the agricultural chemical or fertilizer. Therefore, the same effect can be obtained even if a high concentration of agricultural chemical or fertilizer is not repeatedly added in a short cycle.

Therefore, according to the present invention, not only can the amount of agricultural chemicals or fertilizers and agricultural labor be greatly reduced, but also there is almost no risk of phytotoxicity. In addition, the sustained-release preparation of the present invention has a beneficial effect for environmental preservation.

The gelation characteristic of the polysaccharide by content of an organic acid and an inorganic acid is shown. The biodegradation delay effect of the polysaccharide by an organic acid is shown. The biodegradation delaying effect of polysaccharides by organic acids in soil is shown. Indicates a visual model of a sustained release formulation. Indicates dissolution results of a sustained-release preparation model. Indicates dissolution results of other sustained-release preparation models. It is a graph display which shows sustained release of a salicylic acid. It is a graph display which shows sustained release of ampicillin. It is a graph display which shows sustained release of a metalaxyl. Depicts the disease control effect of sustained release formulations.

Claims (12)

An adsorption carrier having 0.0005 to 50 parts by weight of a bioactive substance in 1000 parts by weight of a porous carrier;
Release of one or more of 0.05 to 15 parts by weight of polysaccharide, 0.3 to 20 parts by weight of inorganic alkali, and organic acid or inorganic acid selected from the group consisting of phosphorous acid, phosphoric acid, acetic acid and hydrochloric acid A sustained-release preparation of a biologically active substance comprising a 0.25 to 20 parts by weight of a regulator and a sustained-release film coated with the mixture on the surface of the adsorption carrier. 1000 parts by weight of a porous carrier;
It consists of 0.0005 to 50 parts by weight of biologically active substance, 0.05 to 15 parts by weight of polysaccharide, 0.3 to 20 parts by weight of inorganic alkali, and organic acids and inorganic acids of phosphorous acid, phosphoric acid, acetic acid and hydrochloric acid. Sustained release of a biologically active substance, comprising a sustained release film having a mixture of 0.25 to 20 parts by weight of one or more release regulators selected from the group and coated with the mixture on the surface of the carrier Formulation.   The bioactive substances include insecticides, herbicides, plant growth regulators, anti-nematodes, fungicides, biocides, slaughter, fumigants, animal and pest control agents, biopest control agents, pheromones, sex attractants The sustained-release preparation of a bioactive substance according to claim 1 or 2, which is one or a mixture of two or more selected from the group consisting of agents, flavoring agents, fragrances, dietary supplements, drugs and fertilizers .   The bioactive substances include phosphite, acephate, isoxathion, imidacloprid, ethylthiodemethon, etofenprox, bitanol, and bitanol. ), Carbosulfan, Clofentezine, Cyclopyrifos-methyl, Fenbutatin-oxide, Cycloprothrin, Dimethyphos, Dimethoyl (Dimethoate), Shirafu Offen (Silaflufen), Diazinon (Diazonin), Thiodicarb (Thiodiclam), Thiobylid (Teifenide), Nitenpyram (Nitepyram) Pyrimiphos-methyl, fipronil, phenisobromolate, buprofezin, furathiocarb, propofos, propofos Sultap, Benfuracarb, Formothion, Marathon, Monocrotophos, BPMC, CVMC, DEP, EPN, MEP, MIPC, MPP, MTMC, NAC, PAP XMC, acibenzolar-S-methyl, azoxystrobin, bitanol, isoprothiolane, isoprodione, acetic acid triodium salt (Oxolinic acid), Oxone (Oxone-copper), Kasugamycin, Capromid, Captan, Diclomezine, Thiabendazole, Thifludazole, Thifluzamide, Thifludazole Hydroxyisoxazole, Pyroquilon, Fenarimol, Ferimzone, Fthalide, Blasticidin, Polyoxin (P) lyoxin), metasulfocarb (Metalasulfocarb), metalaxyl (Metalaxl), metalaxyl (Metalaxyl), metminostrobin (Meminostrobin), mepronil (Mepronil), N-51, FNA, N -9850, azisulfuron, atrazine, ametrine, inabenfide, imazosulfuron, uniconazole, esprocarb, Eprocrub diazon, caffentrol, quizalofop-ethyl, quinchlorac, cumylron, thiomethoxyl, thiometholyl, cyclosulfuron (Cyclosulfuron) Cyhalof-butyl, simazine, dimetamethrin, dimethylpiperate, cinmethylylin, dimmron, tenylcorol, trinylchor iapentenol), naproanilide, paclobutrazol, bifenox, piperophos, pyrazoxyphen, pyrazosulfylethyl , Pyriminobac-methyl, Butachlor, Butamifos, Pretilachlor, Bromobutide, Bensulfuron-benzoyl, Bensulfuron-methyl Benzofenap, Bentazone, Bentocarb, Bentocarb, Pentoxazone, Benfuresate, Mefenacet, Molinate, JA, SA, AC, B, B, TH The sustained-release preparation of a bioactive substance according to claim 3, which is a mixture of 1 or 2 or more selected from the group consisting of 1, 4-D, MCPB, and MCPB ethyl.   The organism according to claim 1 or 2, wherein the porous carrier is one or more release regulators selected from the group consisting of zeolite, perlite, aragonite, diatomaceous earth, ceramic, sand and activated carbon. Sustained release formulation of active substance.   The polysaccharide comprises a group consisting of festan, levan, xanthan gum, pullulan, polysaccharide-7, cellulose, zoglan, gellan, and curdlan. The sustained-release preparation of a bioactive substance according to claim 1 or 2, which is a mixture of one or more selected. A method for producing a sustained release formulation of a bioactive substance according to claim 1,
Dissolving 0.0005 to 50 parts by weight of the bioactive substance in a predetermined amount of solvent to obtain an active substance solution;
Obtaining an active substance adsorbing carrier by uniformly mixing the active substance solution and 1000 parts by weight of the porous carrier and then drying;
Release of one or more of 0.05 to 15 parts by weight of polysaccharide, 0.3 to 20 parts by weight of inorganic alkali, and organic acid or inorganic acid selected from the group consisting of phosphorous acid, phosphoric acid, acetic acid and hydrochloric acid Mixing 0.25 to 20 parts by weight of a regulator, the mixture covering the surface of the adsorption carrier with a predetermined amount of solution, obtaining a suspended coating solution;
After the active substance adsorbing carrier and the coating liquid are homogeneously mixed, the surface of the adsorbing carrier is coated with a coating solution, and the resulting product is dried to form a sustained-release film. A method for producing a sustained-release preparation of a biologically active substance. A method for producing a sustained release formulation of a bioactive substance according to claim 2,
Dissolving 0.0005 to 50 parts by weight of the bioactive substance in a predetermined amount of solvent to obtain an active substance solution;
Release of one or more of 0.05 to 15 parts by weight of polysaccharide, 0.3 to 20 parts by weight of inorganic alkali and organic acid selected from the group consisting of phosphorous acid, phosphoric acid and acetic acid in a predetermined amount of solvent Obtaining 0.25 to 20 parts by weight of a modifier to obtain a suspended coating solution;
Homogeneously mixing the coating liquid into the active substance solution to obtain a coating liquid containing the active substance;
And after uniformly mixing the coating liquid containing the active substance and 1000 parts by weight of the porous carrier, drying the obtained product to form a sustained-release film on the surface of the porous carrier. A method for producing a sustained release formulation of a bioactive substance characterized.   The bioactive substances include insecticides, herbicides, plant growth regulators, anti-nematodes, fungicides, biocides, slaughter, fumigants, animal and pest control agents, biopest control agents, pheromones, sex attractants The sustained-release preparation of a bioactive substance according to claim 7 or 8, which is one or a mixture of two or more selected from the group consisting of an agent, a flavoring agent, a fragrance, a dietary supplement, a drug and a fertilizer How to manufacture.   The bioactive substances include phosphite, acephate, isoxathion, imidacloprid, ethylthiodemethon, etofenprox, bitanol, and bitanol. ), Carbosulfan, Clofentezine, Cyclopyrifos-methyl, Fenbutatin-oxide, Cycloprothrin, Dimethyphos, Dimethoyl (Dimethoate), Shirafu Offen (Silaflufen), Diazinon (Diazonin), Thiodicarb (Thiodiclam), Thiobylid (Teifenide), Nitenpyram (Nitepyram) Pyrimiphos-methyl, fipronil, phenisobromolate, buprofezin, furathiocarb, propofos, propofos Sultap, Benfuracarb, Formothion, Marathon, Monocrotophos, BPMC, CVMC, DEP, EPN, MEP, MIPC, MPP, MTMC, NAC, PAP XMC, acibenzolar-S-methyl, azoxystrobin, bitanol, isoprothiolane, isoprodione, acetic acid triodium salt (Oxolinic acid), Oxone (Oxone-copper), Kasugamycin, Capromid, Captan, Diclomezine, Thiabendazole, Thifludazole, Thifluzamide, Thifludazole Hydroxyisoxazole, Pyroquilon, Fenarimol, Ferimzone, Fthalide, Blasticidin, Polyoxin (P) lyoxin), metasulfocarb (Metalasulfocarb), metalaxyl (Metalaxl), metalaxyl (Metalaxyl), metminostrobin (Meminostrobin), mepronil (Mepronil), N-51, FNA, N -9850, azisulfuron, atrazine, ametrine, inabenfide, imazosulfuron, uniconazole, esprocarb, Eprocrub diazon, caffentrol, quizalofop-ethyl, quinchlorac, cumylron, thiomethoxyl, thiometholyl, cyclosulfuron (Cyclosulfuron) Cyhalof-butyl, simazine, dimetamethrin, dimethylpiperate, cinmethylylin, dimmron, tenylcorol, trinylchor iapentenol), naproanilide, paclobutrazol, bifenox, piperophos, pyrazoxyphen, pyrazosulfylethyl , Pyriminobac-methyl, Butachlor, Butamifos, Pretilachlor, Bromobutide, Bensulfuron-benzoyl, Bensulfuron-methyl Benzofenap, Bentazone, Bentocarb, Bentocarb, Pentoxazone, Benfuresate, Mefenacet, Molinate, JA, SA, AC, B, B, TH The method for producing a sustained-release preparation of a bioactive substance according to claim 9, which is a mixture of one or more selected from the group consisting of 1, 4-D, MCPB, and MCPB ethyl.   The organism according to claim 7 or 8, wherein the porous carrier is one or more release regulators selected from the group consisting of zeolite, pearlite, aragonite, diatomaceous earth, ceramic, sand and activated carbon. A method for producing a sustained release formulation of an active substance. The polysaccharide comprises a group consisting of festan, levan, xanthan gum, pullulan, polysaccharide-7, cellulose, zoglan, gellan, and curdlan. The method for producing a sustained-release preparation of a bioactive substance according to claim 7 or 8, which is a mixture of one or more selected.

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