WO2017104384A1 - Algae inhibitor, method for producing algae inhibitor and algae inhibition method - Google Patents

Algae inhibitor, method for producing algae inhibitor and algae inhibition method Download PDF

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Publication number
WO2017104384A1
WO2017104384A1 PCT/JP2016/085033 JP2016085033W WO2017104384A1 WO 2017104384 A1 WO2017104384 A1 WO 2017104384A1 JP 2016085033 W JP2016085033 W JP 2016085033W WO 2017104384 A1 WO2017104384 A1 WO 2017104384A1
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WIPO (PCT)
Prior art keywords
algae
inhibitor
water
lysine
malonic acid
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PCT/JP2016/085033
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French (fr)
Japanese (ja)
Inventor
正爾 坂本
勝 中條
洋 岩崎
邦光 彼谷
友潔 竹山
高橋 宏彰
光紘 岩船
Original Assignee
日本リファイン株式会社
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Application filed by 日本リファイン株式会社 filed Critical 日本リファイン株式会社
Priority to CN201680070945.8A priority Critical patent/CN108366553A/en
Priority to JP2017555953A priority patent/JPWO2017104384A1/en
Priority to AU2016370997A priority patent/AU2016370997A1/en
Publication of WO2017104384A1 publication Critical patent/WO2017104384A1/en

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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/26Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/02Saturated carboxylic acids or thio analogues thereof; Derivatives thereof
    • A01N37/04Saturated carboxylic acids or thio analogues thereof; Derivatives thereof polybasic
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/50Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment

Definitions

  • the present invention relates to an algal inhibitor containing at least a core agent containing a specific medicinal component and a coating agent, a method for producing the algal inhibitor, and a method for suppressing algae.
  • the main means of algae removal is, for example, draining all the water in the pond and replacing the water, continuing filtration for a long time, carrying out the weir, forcing convection by physical energy
  • Patent Document 1 discloses an algae control method using a liquid in which lysine and malonic acid are mixed. Moreover, it is disclosed that the cyanobacteria can be efficiently suppressed by using lysine and malonic acid in combination. However, in order to suppress cyanobacteria by spraying a liquid such as an aqueous solution in which lysine and malonic acid are mixed, the large amount of aqueous solution may be sprayed or algae may be dispersed in consideration of the dilution effect due to diffusion into water. It was necessary to spray the liquid directly.
  • cyanobacteria such as algal bloom float on the surface of the water during sunshine hours and sink when they exceed sunshine hours, and it is necessary to consider that point in the case of suppression, but in the method of Patent Document 1, Characteristics could not be considered. Furthermore, since cyanobacteria move by being blown by the wind when floating, when a liquid inhibitor is sprayed, it has to be sprayed directly to the cyanobacteria breeding site during the day. Therefore, for example, if cyanobacteria were moved by wind, there was a problem that they had to be scattered again at the moving place.
  • Patent Document 2 discloses a floating water repellant granule material for ponds and mars, in which a mixture of an organic material, a water bloom inhibitor, a specific gravity adjusting material, and a binder is granulated into porous particles.
  • the water-repellant-suppressing granular material is a solid water-repellant water-floating agent which is not considered for sustained release, and there is no description or suggestion about means for continuing elution of the medicinal ingredient.
  • the active ingredient of the water-bloom-suppressing granular material of Patent Document 2 is an inorganic compound such as a hydroxide of zinc or a hydroxide of copper and has a large environmental load, and the technology is an organic substance “ It was not applicable to active ingredients consisting of lysine or lysine salt "and" malonic acid or malonic acid salt ".
  • Patent Document 3 discloses a floating package which floats in water and suppresses the growth of phytoplankton by releasing hydrogen peroxide at a constant concentration.
  • hydrogen peroxide is not only specifically suppressed to blue-green algae such as blue-green algae, but it may have adverse effects on lake organisms.
  • the release of hydrogen peroxide to a constant concentration is disclosed, the control of the rate (method) is not specifically described or suggested.
  • the technology for slow release of hydrogen peroxide was not applicable to the active ingredients consisting of the organic substance "lysine or lysine salt” and "malonic acid or malonic acid salt”.
  • any of the above-mentioned patent documents does not specifically disclose a drug floating on the surface of the water and having a controlled elution time of the active ingredient and a method of suppressing algae using the drug, There is almost no description of problems, purpose of solution, awareness of problems, etc. regarding the composition, physical properties, etc. of the algae inhibitor corresponding thereto.
  • the present invention has been made in view of the above background art, and its problems are solved by solving the above-mentioned problems, developing a drug which floats in water and in which the elution time of the medicinal active ingredient is controlled, and is simple and efficient It is to provide an inhibitor of algae such as green algae which has a low environmental load.
  • the present inventors made the inhibitor contain a specific medicinal component and a specific component as a core agent, and further, the surface of the core agent was coated with a coating agent.
  • a coating agent By coating the drug active ingredient contained in the core agent in a sustained release manner, it becomes possible to exert an effect along with the ecology of the blue-green algae, and further, the inhibitor is suspended on the water surface, It has been found that it is possible to effectively suppress the floating blue-green algae).
  • an algae inhibitor having a desired sustained release (elution rate) further corresponding to the characteristics of algae can be obtained by the composition of the core agent, the coating amount of the coating agent, etc.
  • the present invention is an algae inhibitor which floats on the water surface and suppresses algae floating on the water surface,
  • a pharmaceutically active ingredient comprising at least a lysine or lysine salt and malonic acid or malonate, and a core agent containing a binder for retaining the pharmaceutically active ingredient,
  • a coating agent which is present on the surface of the core agent and controls the sustained release of the pharmacologically active ingredient; It is an algal inhibitor characterized by having.
  • the present invention is a method for producing the above-mentioned algae inhibitor, A step of adding a polymer derived from the above-mentioned natural product and water to a mixed powder of lysine or lysine salt and a medicinal component consisting of malonic acid or malonate to form a slurry, drying the slurry, and granulation And a process of producing an algal inhibitor.
  • the present invention is a method for producing the above-mentioned algae inhibitor,
  • the above non-environmental pollutants and water are added to a mixed powder of lysine or lysine salt and a medicinal component consisting of malonic acid or malonate to form a solution, and then a gelling agent is added to the solution to form a gel.
  • a process for producing an algal inhibitor comprising the steps of: drying the gel; and granulating.
  • the present invention is a method of suppressing algae using the above-mentioned algae inhibitor, Add 1 g or more and 100 g or less of the algae inhibitor per 1 m 2 of water,
  • the method for controlling algae is characterized in that the coating agent controls the sustained release rate of the medicinal ingredient, and the medicinal ingredient is continuously eluted from the algae inhibitor on the water surface for 30 minutes or more after the application.
  • the present invention it is possible to solve the above-mentioned problems and the above-mentioned problems, and to control algae such as water bloom generated in a pond, a lake or the like.
  • the algae inhibitor of the present invention floats on the water surface, algae floating on the water surface can be efficiently suppressed.
  • the algae inhibitor of the present invention contains a binder that holds a medicinal ingredient, and further, since the "core agent containing a medicinal ingredient and a binder" is coated with a coating agent, the controlled release rate of the medicinal ingredient is controlled. Can. By controlling the sustained release rate, algae can be efficiently suppressed.
  • the sustained release rate is defined by the release amount per unit time of the pharmacologically active ingredient released from the algal inhibitor into water when the algal inhibitor is introduced into the water surface.
  • the sustained release rate can be controlled to a desired rate by the composition of the core agent of the algal inhibitor, the composition and coating amount of the coating agent, the shape and size of the algal inhibitor, and the like.
  • Algae inhibitors can be provided according to
  • “Lysine or lysine salt and malonic acid or malonate” which is a medicinal component of the algal inhibitor of the present invention, dissolves in water and diffuses in water, or independently spreads on water surface where algae do not exist In some cases, it can be made to stay on the water surface by blending it with the algae inhibitor of the embodiment of the present invention, and it becomes possible to move together with the algae floating on the water surface by wind, waves, water flow etc. Can be efficiently suppressed.
  • “lysine or lysine salt and malonic acid or malonic acid salt” have high solubility in water, they dissolve and diffuse immediately in water, but they can be dissolved by mixing them with the algae inhibitor having the aspect of the present invention. The release rate can be controlled, and the suppression suitable for the characteristics of algae such as algal bloom is possible.
  • the algae inhibitor of the present invention since the algae inhibitor of the present invention has a coating agent on the surface, it can maintain medicinal effects for a long time after being dropped in a pond, a lake, etc. where the algae inhibitor is to be inhibited. Can move the water surface together with the algae, and the medicinal effect can be used efficiently. Therefore, reproduction of algae can be efficiently suppressed with a small amount of algae inhibitor.
  • the medicinal component can be brought into contact with the algae only when it floats to the water surface in summer, algae can be suppressed extremely efficiently.
  • the algae inhibitor of this invention moves the water surface by a wind etc., it can suppress the algae of the place where direct spraying is difficult.
  • the medicinal component of the algal inhibitor of the present invention is effective only on specific cyanobacteria in algae, it does not adversely affect other ecology.
  • the pharmaceutically active ingredient is highly soluble and the other substance constituting the algal inhibitor is a biodegradable or low environmental load substance, the algal inhibitor of the present invention has less environmental load.
  • the algal inhibitor of the present invention is an algal inhibitor which is suspended on water and suppresses algae floating on the water, and is at least a lysine or lysine salt and a medicinal component comprising malonic acid or malonate, and It is characterized in that it comprises a core agent containing a binder which holds a medicinal component, and a coating agent which is present on the surface of the core agent and controls the sustained release of the medicinal component.
  • the algae inhibitor of the present invention is used for control of growth of algae, control of buoyancy and the like.
  • “suppression” means decrease in number or density.
  • the algae inhibitor of the present invention is to reduce and inhibit algae by suppressing reproduction.
  • algae it is preferably used for suppression of cyanobacteria, more preferably for suppression of cyanobacteria of the genus Microcystis, and particularly preferably used for suppression of algae.
  • Microcystis viridis Microcystis viridis
  • Microcystis aeruginosa Microcystis wesenbergii etc.
  • any of them is highly selective. Especially preferred.
  • the algae inhibitor of the present invention floats on the water surface, it is characterized by suppressing algae floating on the water surface as well, but it does not exclude the suppression of algae in the water, but suppresses algae in the water or in the water bottom. Can also be used.
  • the algal inhibitor can suppress algae and the like attached to moss existing on the bottom of the bottom of the bottom of the bottom of the bottom of the bottom by a medicinal ingredient.
  • the algae inhibitor of the present invention has a core.
  • the core agent contains a medicinal ingredient and a binder holding the medicinal ingredient.
  • the active ingredient consists of lysine or lysine salt, and malonic acid or malonate.
  • lysine or lysine salt examples include, but are not limited to, specifically, lysine, lysine hydrochloride, lysine acetate, lysine glutamate, lysine aspartate and the like. It is particularly preferable to use lysine hydrochloride as the above-mentioned "lysine or lysine salt”.
  • malonic acid or malonic acid salt include, but are not limited to, malonic acid, sodium malonate, potassium malonate, magnesium malonate, calcium malonate and the like. It is particularly preferable to use malonic acid as the above-mentioned "malonic acid or malonic acid salt”.
  • lysine or lysine salt only one of lysine and lysine salt may be used, or both may be used as a mixture.
  • malonic acid or malonic acid salt only one of malonic acid and malonic acid salt may be used, or both may be mixed and used.
  • the binder is preferably a component selected from the group consisting of "naturally-derived polymers” and “non-environmental pollutants” Use of “naturally-derived polymers” or “non-environmental pollutants” alone The “naturally-derived macromolecule” and the “non-environmental pollutant” may be used in combination.
  • carrageenan, gelatin, pectin, agarose, starch, collagen, pullulan, mannan, dextrin, cellulose, etc., as the above-mentioned polymers derived from natural products, have no toxicity, relatively low environmental impact, absorb water It is preferable from the point of being excellent in the gelation performance which turns into a gel, and easy to be decomposed naturally.
  • One selected from these can be used alone or in combination of two or more.
  • non-environmental pollutants substances having low environmental impact, such as substances approved for use as feed additives and food additives, and substances consisting of clay minerals present in large amounts in the natural world, etc. can be mentioned.
  • silicates such as sodium silicate, carboxymethylcellulose, sodium carboxymethylcellulose, sodium alginate and the like can be mentioned.
  • One selected from these can be used alone or in combination of two or more.
  • the non-environmental pollutants preferably contain a gelling agent.
  • the above-mentioned silicates and the like preferably contain an inorganic acid or an organic acid as a gelling agent. The inorganic acid or organic acid can gelate the silicate by neutralization.
  • the above-mentioned carboxymethylcellulose, carboxymethylcellulose sodium, sodium alginate and the like preferably contain polyvalent cation-containing compounds such as calcium chloride, magnesium chloride and aluminum chloride as gelling agents. Therefore, as the gelling agent contained in the above non-environmental pollutants, inorganic acids or organic acids, and compounds containing polyvalent cations are particularly preferable.
  • the gelling agent may be combined with the above-mentioned medicinal component.
  • Preferred binders are, for the aforementioned reasons, in particular compounds or salts thereof selected from the group consisting of silicic acid, polysaccharides, carboxymethylcellulose and collagen.
  • polysaccharide also includes complex polysaccharides.
  • salt of silicic acid includes sodium salts of metasilicic acid represented by the composition formula (Na 2 O) (SiO 2 ) or Na 2 SiO 3 .
  • binders are, for the above reasons, specifically the following.
  • silicic acid or salt thereof include silicic acid, sodium silicate, and those obtained by reacting sodium silicate with an acid (aqueous solution is water glass No. 1 to 4 etc.).
  • polysaccharides or salts thereof amylose (starch), cellulose, agarose, carrageenan, pectin, sodium alginate, "a product obtained by reacting sodium alginate, pectin and the like with a cation-containing substance having a valence of 2 or more" Etc.
  • carboxymethylcellulose or a salt thereof examples include carboxymethylcellulose, "a product obtained by reacting carboxymethylcellulose with a cation-containing substance having a valency of 2 or more", and the like. Gelatin etc. are mentioned as said "collagen or its salt”.
  • binders include sodium silicate, amylose (starch), agarose, carrageenan, pectin, sodium alginate, "obtained by reacting carboxymethyl cellulose with a cation-containing substance having a valency of 2 or more", collagen, gelatin, etc. It can be mentioned.
  • a highly biodegradable material and / or a substance having a low environmental load from the viewpoint of controlling the sustained release rate of the pharmaceutically active ingredient and reducing the environmental load.
  • pectin, gelatin, starch, "carboxymethylcellulose sodium and calcium chloride”, “silicate and acid”, sodium alginate and calcium chloride and the like are mentioned as more preferable binders.
  • the binder With regard to the preparation of the binder, it is preferable to carry out "naturally-derived polymers” and “non-environmental pollutants” by dispersing or dissolving them in water in water.
  • the gelling agent is also preferably made into an aqueous solution (or a fine dispersion) and then mixed with each other. Both are then dried, and if dry they are not granulated or flaked (if necessary) and crushed (if necessary) to granulate or flaked, and the obtained one with a core agent (or a component of the core agent) It is preferable to do.
  • the algae inhibitor of the present invention has "a coating agent which is present on the surface of the above-mentioned core and controls the sustained release of the medicinal ingredient” as an essential member.
  • coating includes the meaning of “coating, application, external addition, application”.
  • the coating agent it is preferable to use a highly biodegradable and / or low environmental load material from the viewpoint of floating on the water surface, adjustment of the sustained release rate of the medicinal ingredient, reduction of environmental load and the like.
  • the algae which are present in the bottom of a water can also be suppressed by releasing a medicinal ingredient in the bottom of a water.
  • the coating agent controls the sustained release rate of the pharmaceutically active ingredient and continuously elutes the pharmaceutically active ingredient over 30 minutes after the application of the algal inhibitor, and one hour after the application of the algal inhibitor It is more preferable that the pharmaceutically active ingredient be continuously eluted over the above, and it is particularly preferable that the pharmaceutically active ingredient be continuously eluted for 2 hours or more after the application of the algal inhibitor.
  • the preferable coating agent is not particularly limited, and specifically, for example, hydrophobic members such as ethylcellulose (EC), cellulose, fumed silica (FS), beeswax, shellac, etc .; calcium carboxymethylcellulose, calcium alginate, hydroxypropyl Examples include compounds selected from the group consisting of gelling substances such as methyl cellulose. One selected from these can be used alone or in combination of two or more. Such a compound is preferable from the above-mentioned point, and ethyl cellulose or fumed silica is particularly preferable from the above-mentioned point. As the fumed silica, hydrophilic ones and hydrophobic ones are preferably used.
  • hydrophilicity and hydrophobicity can be controlled. Although the above effects are exhibited in any surface state, those subjected to hydrophobic treatment are preferably used. Hydrophobic-treated fumed silica exerts the above-mentioned effects in particular, and the strength of hydrophobicity can control the sustained release rate.
  • the type of fumed silica can be appropriately selected according to the application.
  • the method for applying the coating agent to the core agent is not particularly limited as long as the method can suitably cover the surface of the core agent, but the solution can be made into a solution and applied to the surface of the core agent, Then, the method of evaporating a solvent is preferable. In addition, it is preferable to externally add the fumed silica, cellulose and the like to the surface of the core agent as it is difficult to make a solution easily.
  • the algae inhibitor of the present invention is solid, and its shape can be appropriately selected according to the purpose. Specifically, granules, flakes, tablets, granules and the like can be mentioned.
  • the algal inhibitor is in the form of granules, tablets or granules, the number average diameter is 0 in view of the control of the sustained release rate of the medicinal ingredient and the floatability and dispersibility of the algal inhibitor on the water surface.
  • the thickness is preferably in the range of 0.05 mm to 30 mm, more preferably in the range of 0.1 mm to 15 mm, and particularly preferably in the range of 0.5 mm to 10 mm.
  • the thickness is preferably 0.03 mm to 3 mm, from the viewpoint of controlling the sustained release rate of the medicinal ingredient and floating properties of the algal inhibitor on the water surface, It is more preferably 0.05 to 2 mm, and particularly preferably 0.1 to 1 mm.
  • the ratio of the total mass of “malonic acid and malonate” to the total mass of “lysine and lysine salt” among the above medicinal ingredients is not particularly limited, but the ratio is preferably 0.1 or more and 2 or less, More preferably, it is 0.2 or more and 1.8 or less, and particularly preferably 0.3 or more and 1.5 or less.
  • total mass includes the concept in the case where only one of “lysine and lysine salt” is contained, and the case in which only “one of malonic acid and malonate” is contained.
  • the content of the above pharmaceutically active ingredient is not particularly limited when the whole core agent is 100 parts by mass, and can be appropriately selected according to the purpose, but the content of the above pharmaceutically active ingredient is 10 to 90 parts by mass Preferably, 15 to 80 parts by mass is more preferable, and 20 to 70 parts by mass is particularly preferable.
  • the suitable amount of the algae inhibitor to be dispersed may be reduced, and it may be difficult to uniformly disperse on the water surface, or the sustained release may not be achieved.
  • the content of the medicinal component is too small, the amount of the algae inhibitor to be dispersed may increase, or the environmental load due to the too large binder may occur.
  • the core agent in the algae inhibitor of the present invention may contain "other components” in addition to the medicinal component and the binder.
  • other components There is no restriction
  • the content of the coating agent is preferably 1 part by mass or more and 10 parts by mass or less, more preferably 1 part by mass or more and 8 parts by mass or less, and 1 part by mass or more and 7 parts by mass or less. Particularly preferred.
  • the algae inhibitor of the present invention can "mix other components, etc.” with “other components”.
  • other components There is no restriction
  • the production method of the present invention is a method for producing the above algal inhibitor, wherein the mixed powder of “a pharmaceutically active ingredient consisting of“ lysine or lysine salt ”and“ malonic acid or malonate ”” is derived from the above natural product
  • the method is characterized by including a step of adding a polymer and water to form a slurry, a step of drying the slurry, and a step of granulating.
  • the production method of the present invention is a method for producing the above-mentioned algae inhibitor, and it is preferable to use the mixed powder of “a medicinal component comprising“ lysine or lysine salt ”and“ malonic acid or malonate ”” in the non-environment
  • the method is characterized by including the steps of adding a contaminant and water to form a solution, adding a gelling agent to the solution to form a gel, drying the gel, and granulating.
  • the slurry or gel can be dried using known drying equipment. Drying conditions (temperature, time, etc.) can be appropriately selected according to the purpose.
  • the slurry or gel may be granulated after drying, granulated and then dried, or may be granulated while being dried, and can be appropriately selected depending on the purpose. If the water evaporates during drying and air bubbles remain in the algae inhibitor, the algae inhibitor can be suspended on the water surface for a long time or favorably because the specific gravity of the algae inhibitor is smaller than that of water.
  • the production method of the present invention includes the step of coating the above-mentioned coating agent on a core agent (preferably dried).
  • the coating agent may be applied to the core by any known method. For example, there is a method in which a coating agent is dissolved in a solvent and then sprayed onto a molded core to coat, or a method in which a solid coating agent is coated or externally attached to a molded core.
  • the method for suppressing algae according to the present invention is a method for suppressing algae using the above-mentioned algae inhibitor, wherein 1 g to 100 g of the algae inhibitor is added per 1 m 2 of water, and the sustained release of the active ingredient by the coating agent It is characterized in that the rate is controlled and the active ingredient continues to be eluted from the algal inhibitor on the water surface for 30 minutes or more after spraying.
  • algal algae such as algal will rise from the water and float on the water surface when there is sunshine, so Medicinal active ingredients from the present algal inhibitors of the present invention have a direct effect on the algae and are preferred.
  • dissolution of the active ingredient is completed in less than 30 minutes, the proportion of active ingredient that diffuses into the water below the water surface is high, as in the above-mentioned "dispersion (use) of the aqueous solution of active ingredient".
  • the drug component from the floating algae inhibitor of the present invention is added to the algae In some cases, the drug effect can not be achieved directly, and the release of the drug component outside sunshine hours may be wasted. It is preferably 30 minutes to 9 hours of sunshine duration, more preferably 1 hour to 8 hours of sunshine duration, and particularly preferably 2 hours to 7 hours of sunshine duration.
  • the algal inhibitor after release of the medicinal ingredient may or may not retain its shape, but usually retains that shape.
  • the binder or coating agent after the release of the active ingredient is usually decomposed by microorganisms in water or the like, or does not affect the environment.
  • the algae control method of the present invention can be used in a water environment where it is desired to inhibit algae and / or inhibit algae generation.
  • water environments include ponds, swamps, lakes, rivers, dams, and the sea.
  • Application rate of algae inhibitor, lysine or malonic acid terms contained in algal inhibitor preferably 0.1 ⁇ 50g / m 2, more preferably 1 ⁇ 40g / m 2, is 10 ⁇ 30g / m 2 Particularly preferred. If the application rate is too high, the algae inhibitor may be wasted, while if the application rate is too low, the algae may not be well suppressed.
  • the algae inhibitor it is preferable to add 1 g or more and 100 g or less of the algae inhibitor, more preferably 5 g or more and 90 g or less, and particularly preferably 10 g or more and 80 g or less, per 1 m 2 of water. If the application rate is too high, the algae inhibitor may be wasted, while if the application rate is too low, the algae may not be well suppressed.
  • Example 1 [Examination of core agent] The following various binders were added to the medicinal component which consists of a lysine hydrochloride and malonic acid, and the algae inhibitor was created.
  • Carboxymethylcellulose sodium (CMCNa) which is a salt of carboxymethylcellulose as “non-environmental pollutant”
  • calcium chloride (CaCl 2 ) as “gelling agent”
  • pectin which is a polymer derived from a natural product” and is polysaccharide
  • PVA polyvinyl alcohol
  • the composition of the algal inhibitor was 35% by mass of lysine hydrochloride, 35% by mass of malonic acid, 28% by mass of the binder, and 1% by mass of the coating agent based on the total amount of the algal inhibitor.
  • Ethyl cellulose (EC) was used as a coating agent.
  • CMCNa carboxymethylcellulose
  • CaCl 2 calcium chloride
  • PVA polyvinyl alcohol
  • Ethylcellulose (EC) was dissolved in an acetone solution to prepare a 10% by mass solution, and the solution was sprayed to coat the core agent to prepare an algal inhibitor.
  • malonic acid elution rate was measured with time.
  • the malonic acid concentration was determined using capillary electrophoresis (manufactured by Otsuka Electronics Co., Ltd.).
  • the "malonic acid elution rate" was determined by measuring and calculating the mass of malonic acid in the water tank and dividing by the total mass of malonic acid contained in the used algal inhibitor.
  • malonic acid was measured as a representative of the pharmacologically active ingredient, even if it is not malonic acid, even if it is malonic acid salt, lysine, and lysine salt, only the water solubility is slightly different. The tendency of release was almost the same in the experiment conducted separately.
  • the buoyant in water, the control of the dissolution rate, when comprehensively considering the environmental load, etc., from the viewpoint of control of elution rate, rather than the PVA does not become gelled, the gelled "CMCNa + CaCl 2" without using or pectin as well, among them, it has been found preferable to use "CMCNa + CaCl 2" in terms of floating.
  • PVA has the fault that environmental load is large compared with others.
  • polysaccharides, carboxymethylcellulose, silicic acid or their salts were confirmed to be excellent in controlling the floatability and elution rate in water, but collagen or their salts also suspended in water. Excellent in control of the viscosity and dissolution rate.
  • Example 2 [Examination of particle size of algae inhibitor] Next, the algae inhibitor was granulated, and the change in the elution rate of the medicinal ingredient when the particle size was changed was examined.
  • the composition of the algal inhibitor was 34% by mass of lysine hydrochloride, 34% by mass of malonic acid, 15% by mass of CMCNa, 15% by mass of calcium chloride, 1% by mass of EC, and 1% by mass of water based on the whole algae inhibitor.
  • the particle size of the algae inhibitor was produced about 7 mm, 5 mm, and 3 mm, respectively. Then, the malonic acid elution rate per hour was measured in the same manner as in Example 1.
  • Example 3 [Examination of coating amount of coating agent] The effect of the amount of ethyl cellulose (EC) coated on the dissolution rate of the active ingredient was examined.
  • the core agent was obtained by The composition of the core after drying was 35% by mass of lysine hydrochloride, 35% by mass of malonic acid, 14% by mass of CMCNa, 14% by mass of calcium chloride, and 2% by mass of water based on the whole algae inhibitor.
  • the dried core agent was coated with EC as a coating agent at 1% by mass, 3% by mass, 5% by mass, and 10% by mass with respect to the total mass of the algal inhibitor to prepare an algal inhibitor .
  • An algae inhibitor (0% by mass of coating agent) not coated with EC was also prepared as a comparison. Then, in the same manner as in Example 1, the malonic acid elution rate per hour was measured.
  • Example 4 [Examination of coating amount of coating agent] The same experiment as in Example 3 was carried out, and when fumed silica (hydrophobic silica RX 300-5, manufactured by Nippon Aerosil Co., Ltd.) was used as a coating agent, the influence of the coating amount on the dissolution rate of the medicinal ingredient was examined. . Lysine hydrochloride and malonic acid were dissolved in equal amounts in pure water, and sodium silicate No. 3 was added thereto to cause gelation. The gelation can be suitably caused by adding so that the converted mass of the component of the formula Na 2 O contained in sodium silicate becomes the same as the mass of malonic acid.
  • fumed silica hydrophobic silica RX 300-5, manufactured by Nippon Aerosil Co., Ltd.
  • the gelled product was granulated and dried to prepare a core.
  • An algae inhibitor was produced by coating the produced core agent with fumed silica (FS) as a coating agent.
  • the coating amount of FS was 1 mass%, 3 mass%, 5 mass%, 7 mass%, and 9 mass% with respect to the mass of the whole algae inhibitor, respectively. Then, the malonic acid elution rate per hour was measured in the same manner as in Example 1.
  • the coating amount of the coating agent is 10% by mass and 9% by mass, respectively, the elution rate per hour is low, so the coating amount of the coating agent is It has been found that about 1% by mass to about 7% by mass is a particularly preferable range with respect to the mass.
  • the algae inhibitor of the present invention can be used to control algae and algae reproduction under various water environments, and therefore the water environment can be managed and adjusted by countries, public organizations, management organizations, companies, etc. Widely used in the field of

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Abstract

The present invention relates to: an algae inhibitor, which is to be floated on water so as to inhibit algae floating thereon, characterized by comprising at least an algaecide component comprising lysine or a lysine salt and malonic acid or a malonic acid salt, a core agent which contains a binder for carrying the algaecide component, and a coating agent which exists on the surface of the core agent and controls the sustained release properties of the algaecide component; a method for producing the algae inhibitor; and an algae inhibition method. The binder is preferably a component selected from the group consisting of "polymers derived from natural materials" and "materials causing no environmental pollution".

Description

藻類抑制剤、該藻類抑制剤の製造方法及び藻類の抑制方法ALGAE INHIBITOR, METHOD FOR PRODUCING THE ALGAE INHIBITOR AND METHOD FOR INHIBITING ALGAE
 本発明は、特定の薬効成分を含有する芯剤とコーティング剤とを少なくとも有する藻類抑制剤、該藻類抑制剤の製造方法及び藻類の抑制方法に関する。 The present invention relates to an algal inhibitor containing at least a core agent containing a specific medicinal component and a coating agent, a method for producing the algal inhibitor, and a method for suppressing algae.
 近年、湖沼やダム等の水環境下で、アオコ等の藻類の大量増殖による、生態系の破壊、悪臭、水質悪化等が問題となっている。特にアオコ等は毒性を有する物質を産生し、それによって多くの水中動物のみならず陸上動物も死ぬケースが報告されている。また、アオコ等は日照時に水面に浮揚することで光合成により増殖するため、水中への光路を遮閉し、他の光合成生物の光合成を阻害する。日照後は水中に滞留して呼吸することにより水中の溶存酸素を吸収するため、水中の溶存酸素が低下し、他の水中生物の呼吸を阻害する。
 そこで、藻類の抑制や藻類の繁殖を抑制する手段の開発が早急に望まれ、これまでにも多くの研究が行われている。
In recent years, under the water environment of lakes and lakes, dams and the like, there has been a problem of destruction of the ecosystem, odor and deterioration of water quality due to large-scale growth of algae such as blue-green algae. In particular, it has been reported that blue-green algae produce toxic substances, thereby killing not only many aquatic animals but also land animals. In addition, since algae blooms by photosynthesis by floating on the water surface at the time of sunshine, it blocks the light path to the water and inhibits the photosynthesis of other photosynthetic organisms. After sunshine, it stays in water and breathes to absorb the dissolved oxygen in the water, so the dissolved oxygen in the water decreases and inhibits the respiration of other aquatic organisms.
Therefore, development of means for suppressing algae and algae reproduction is urgently required, and many studies have been conducted so far.
 主に行われている藻類の除去手段としては、例えば、池の水を全部抜いて水を置き換える、長時間に亘り濾過をし続ける、浚渫を実施する、物理的なエネルギーにより強制的に対流を起こし撹拌する、凝集沈降剤を散布し底面に沈降させる等が挙げられるが、何れも時間やコストがかかり過ぎたり、環境負荷が大き過ぎたりして有効ではなかった。
 そこで、低コスト且つ環境負荷の低い藻類の除去手段が望まれている。
The main means of algae removal is, for example, draining all the water in the pond and replacing the water, continuing filtration for a long time, carrying out the weir, forcing convection by physical energy There is a case of raising and stirring, dispersing a flocculant and settling on the bottom, etc., but all of them are not effective because they are time-consuming and costly and environmental load is too large.
Therefore, a means for removing algae that has low cost and low environmental impact is desired.
 例えば、特許文献1には、リジンとマロン酸が混合された液体を用いた藻類制御方法が開示されている。また、リジンとマロン酸を併用することによって、藍藻類を効率的に抑制できることが開示されている。
 しかしながら、リジン及びマロン酸が混合された水溶液等の液体を散布して藍藻類を抑制するためには、水中への拡散による希釈の影響を考慮して、大量の水溶液を散布するか、藻類に該液体を直接散布する必要があった。
For example, Patent Document 1 discloses an algae control method using a liquid in which lysine and malonic acid are mixed. Moreover, it is disclosed that the cyanobacteria can be efficiently suppressed by using lysine and malonic acid in combination.
However, in order to suppress cyanobacteria by spraying a liquid such as an aqueous solution in which lysine and malonic acid are mixed, the large amount of aqueous solution may be sprayed or algae may be dispersed in consideration of the dilution effect due to diffusion into water. It was necessary to spray the liquid directly.
 また、アオコ等の藍藻類は、日照時間中は水面に浮く一方、日照時間を過ぎると沈むという特性があり、抑制の際はその点を考慮する必要があるが、特許文献1の方法ではその特性が考慮できていなかった。
 更に、藍藻類は、浮遊しているときは風に流されて移動するため、液体の抑制剤を散布する場合は、日中に藍藻類の繁殖場所に直接散布しなくてはならない。したがって、例えば藍藻類が風で移動してしまうと、再度その移動場所に散布しなければならないという問題点があった。
In addition, cyanobacteria such as algal bloom float on the surface of the water during sunshine hours and sink when they exceed sunshine hours, and it is necessary to consider that point in the case of suppression, but in the method of Patent Document 1, Characteristics could not be considered.
Furthermore, since cyanobacteria move by being blown by the wind when floating, when a liquid inhibitor is sprayed, it has to be sprayed directly to the cyanobacteria breeding site during the day. Therefore, for example, if cyanobacteria were moved by wind, there was a problem that they had to be scattered again at the moving place.
 特許文献2には、有機質材とアオコ抑制剤と比重調整材とバインダーとの混合物を多孔質粒状に造粒した池沼用浮遊性アオコ抑制粒材が開示されている。該アオコ抑制粒材は、水面に浮く固体のアオコ抑制剤ではあるが、徐放性については考慮されておらず、薬効成分を溶出し続けさせる手段については記載も示唆もされていない。
 また、特許文献2のアオコ抑制粒材の有効成分は、亜鉛の水酸化物や銅の水酸化物等の無機化合物であって環境負荷が大きいものであり、しかもその技術は、有機物である「リジン若しくはリジン塩」及び「マロン酸若しくはマロン酸塩」からなる有効成分に対しては適用できるものではなかった。
Patent Document 2 discloses a floating water repellant granule material for ponds and mars, in which a mixture of an organic material, a water bloom inhibitor, a specific gravity adjusting material, and a binder is granulated into porous particles. The water-repellant-suppressing granular material is a solid water-repellant water-floating agent which is not considered for sustained release, and there is no description or suggestion about means for continuing elution of the medicinal ingredient.
In addition, the active ingredient of the water-bloom-suppressing granular material of Patent Document 2 is an inorganic compound such as a hydroxide of zinc or a hydroxide of copper and has a large environmental load, and the technology is an organic substance “ It was not applicable to active ingredients consisting of lysine or lysine salt "and" malonic acid or malonic acid salt ".
 特許文献3には、水に浮遊し、一定濃度の過酸化水素を徐放することによって植物プランクトンの増殖を抑制する浮上性包装体が開示されている。しかしながら、過酸化水素はアオコ等の藍藻類にのみ特異的に抑制するわけではなく、湖沼の生物に悪影響を与える可能性があった。
 また、過酸化水素を一定濃度になるように放出することは開示されているが、その速度の調節(方法)に関しては、具体的に記載も示唆もされていない。
 更に、過酸化水素を徐放する技術が、有機物である「リジン若しくはリジン塩」及び「マロン酸若しくはマロン酸塩」からなる有効成分に対して適用できるものではなかった。
Patent Document 3 discloses a floating package which floats in water and suppresses the growth of phytoplankton by releasing hydrogen peroxide at a constant concentration. However, hydrogen peroxide is not only specifically suppressed to blue-green algae such as blue-green algae, but it may have adverse effects on lake organisms.
In addition, although the release of hydrogen peroxide to a constant concentration is disclosed, the control of the rate (method) is not specifically described or suggested.
Furthermore, the technology for slow release of hydrogen peroxide was not applicable to the active ingredients consisting of the organic substance "lysine or lysine salt" and "malonic acid or malonic acid salt".
 すなわち、上記の何れの特許文献にも、水面に浮きかつ薬効成分の溶出時間が調節された薬剤や該薬剤を用いた藻類の抑制方法について具体的に開示されていないことは勿論、藻類の特性、それに対応した藻類抑制剤の構成・物性等についての課題、解決目的、問題意識等が殆ど記載されていない。 That is, it is a matter of course that any of the above-mentioned patent documents does not specifically disclose a drug floating on the surface of the water and having a controlled elution time of the active ingredient and a method of suppressing algae using the drug, There is almost no description of problems, purpose of solution, awareness of problems, etc. regarding the composition, physical properties, etc. of the algae inhibitor corresponding thereto.
 環境負荷が小さく効率の良い(抑制効果の高い)藻類抑制剤への要求は、近年ますます高くなってきているが、上記公知技術では、藻類の好適な抑制は不十分であり、更なる改善の余地があった。 The demand for efficient (low inhibitory) algal inhibitors with low environmental impact has been increasing in recent years, but with the above-mentioned known technologies, adequate suppression of algae is insufficient and further improvement There was room for
特開2005-246144号公報JP, 2005-246144, A 特開2003-113012号公報Japanese Patent Application Publication No. 2003-113012 特開2013-209326号公報JP, 2013-209326, A
 本発明は上記背景技術に鑑みてなされたものであり、その課題は、前記問題点を解決し、水に浮き、かつ薬効成分の溶出時間が調節された薬剤を開発し、簡便で効率良く、環境負荷の少ない、アオコ等の藻類の抑制剤を提供すること等である。 The present invention has been made in view of the above background art, and its problems are solved by solving the above-mentioned problems, developing a drug which floats in water and in which the elution time of the medicinal active ingredient is controlled, and is simple and efficient It is to provide an inhibitor of algae such as green algae which has a low environmental load.
 本発明者らは、上記の課題を解決すべく鋭意検討を重ねた結果、抑制剤に特定の薬効成分及び特定の成分を含有させて芯剤とし、更に、該芯剤の表面をコーティング剤でコーティングすることにより、芯剤に含まれる薬効成分を徐放性にすることで、アオコの生態に併せて効果を発揮することが可能となり、さらに該抑制剤を水面に浮遊させ、「同じく該水面に浮遊するアオコ」を効率よく抑制する効果を付与できることを見出した。
 また、芯剤の組成やコーティング剤の被覆量等により、更に藻類の特性に対応した所望の徐放性(溶出速度)を有する藻類抑制剤が得られることを見出して本発明を完成するに至った。
As a result of intensive studies to solve the above problems, the present inventors made the inhibitor contain a specific medicinal component and a specific component as a core agent, and further, the surface of the core agent was coated with a coating agent. By coating the drug active ingredient contained in the core agent in a sustained release manner, it becomes possible to exert an effect along with the ecology of the blue-green algae, and further, the inhibitor is suspended on the water surface, It has been found that it is possible to effectively suppress the floating blue-green algae).
In addition, it has been found that an algae inhibitor having a desired sustained release (elution rate) further corresponding to the characteristics of algae can be obtained by the composition of the core agent, the coating amount of the coating agent, etc. The
 すなわち、本発明は、水面に浮遊させて該水面に浮遊する藻類を抑制する藻類抑制剤であって、
 少なくとも、リジン若しくはリジン塩及びマロン酸若しくはマロン酸塩からなる薬効成分、並びに、該薬効成分を保持するバインダーを含有する芯剤と、
 該芯剤の表面に存在し薬効成分の徐放性を制御するコーティング剤と、
を有してなるものであることを特徴とする藻類抑制剤である。
That is, the present invention is an algae inhibitor which floats on the water surface and suppresses algae floating on the water surface,
A pharmaceutically active ingredient comprising at least a lysine or lysine salt and malonic acid or malonate, and a core agent containing a binder for retaining the pharmaceutically active ingredient,
A coating agent which is present on the surface of the core agent and controls the sustained release of the pharmacologically active ingredient;
It is an algal inhibitor characterized by having.
 また、本発明は、上記藻類抑制剤の製造方法であって、
 リジン若しくはリジン塩及びマロン酸若しくはマロン酸塩からなる薬効成分の混合粉体に、上記天然物由来の高分子と水を加えてスラリー状にする工程、該スラリーを乾燥する工程、及び、造粒する工程とを含むことを特徴とする藻類抑制剤の製造方法である。
Moreover, the present invention is a method for producing the above-mentioned algae inhibitor,
A step of adding a polymer derived from the above-mentioned natural product and water to a mixed powder of lysine or lysine salt and a medicinal component consisting of malonic acid or malonate to form a slurry, drying the slurry, and granulation And a process of producing an algal inhibitor.
 また、本発明は、上記藻類抑制剤の製造方法であって、
 リジン若しくはリジン塩及びマロン酸若しくはマロン酸塩からなる薬効成分の混合粉体に、上記非環境汚染物質と水を加えて溶液状にした後、該溶液にゲル化剤を加えてゲル状にする工程、該ゲルを乾燥する工程、及び、造粒する工程とを含むことを特徴とする藻類抑制剤の製造方法である。
Moreover, the present invention is a method for producing the above-mentioned algae inhibitor,
The above non-environmental pollutants and water are added to a mixed powder of lysine or lysine salt and a medicinal component consisting of malonic acid or malonate to form a solution, and then a gelling agent is added to the solution to form a gel. A process for producing an algal inhibitor, comprising the steps of: drying the gel; and granulating.
 また、本発明は、上記藻類抑制剤を使用した藻類の抑制方法であって、
 水1m当たりに、該藻類抑制剤を1g以上100g以下投入し、
 コーティング剤によって薬効成分の徐放速度を制御し、散布後30分以上に亘り、該水面に該藻類抑制剤から薬効成分を溶出し続けさせることを特徴とする藻類の抑制方法である。
Further, the present invention is a method of suppressing algae using the above-mentioned algae inhibitor,
Add 1 g or more and 100 g or less of the algae inhibitor per 1 m 2 of water,
The method for controlling algae is characterized in that the coating agent controls the sustained release rate of the medicinal ingredient, and the medicinal ingredient is continuously eluted from the algae inhibitor on the water surface for 30 minutes or more after the application.
 本発明によれば、前記問題点や上記課題を解決し、池や湖沼等に発生するアオコ等の藻類を抑制することができる。特に、本発明の藻類抑制剤は水面に浮遊するため、該水面に浮遊する藻類を効率的に抑制することができる。 According to the present invention, it is possible to solve the above-mentioned problems and the above-mentioned problems, and to control algae such as water bloom generated in a pond, a lake or the like. In particular, since the algae inhibitor of the present invention floats on the water surface, algae floating on the water surface can be efficiently suppressed.
 本発明の藻類抑制剤は、薬効成分を保持するバインダーを含有し、更に「薬効成分とバインダーを含有する芯剤」がコーティング剤によりコーティングされているので、薬効成分の徐放速度を調節することができる。徐放速度を調節することによって、藻類を効率的に抑制することができる。
 例えば、徐放速度は、藻類抑制剤を水面に投入した際に、該藻類抑制剤から水中に放出される薬効成分の単位時間当たりの放出量等により規定される。
The algae inhibitor of the present invention contains a binder that holds a medicinal ingredient, and further, since the "core agent containing a medicinal ingredient and a binder" is coated with a coating agent, the controlled release rate of the medicinal ingredient is controlled. Can. By controlling the sustained release rate, algae can be efficiently suppressed.
For example, the sustained release rate is defined by the release amount per unit time of the pharmacologically active ingredient released from the algal inhibitor into water when the algal inhibitor is introduced into the water surface.
 該徐放速度は、該藻類抑制剤の芯剤の組成、コーティング剤の組成や被覆量、該藻類抑制剤の形状や大きさ等によって所望の速度にコントロールすることができるので、目的や環境等に応じた藻類抑制剤を提供することができる。 The sustained release rate can be controlled to a desired rate by the composition of the core agent of the algal inhibitor, the composition and coating amount of the coating agent, the shape and size of the algal inhibitor, and the like. Algae inhibitors can be provided according to
 本発明の藻類抑制剤の薬効成分である「リジン若しくはリジン塩及びマロン酸若しくはマロン酸塩」は、水に溶解して水中に拡散したり、藻類の存在しない水面に独立して拡散したりする場合があるが、本発明の態様の藻類抑制剤に配合することにより、水面に滞在させることができ、また、風、波、水流等によって水面に浮遊する藻類と共に移動できるようになり、該藻類を効率的に抑制することができる。
 また、「リジン若しくはリジン塩及びマロン酸若しくはマロン酸塩」は、水に対する溶解度が高く、水にすぐ溶解し拡散してしまうが、本発明の態様を有する藻類抑制剤に配合することにより、徐放速度を調節することができ、アオコ等の藻類の特性に合った抑制が可能になる。
"Lysine or lysine salt and malonic acid or malonate", which is a medicinal component of the algal inhibitor of the present invention, dissolves in water and diffuses in water, or independently spreads on water surface where algae do not exist In some cases, it can be made to stay on the water surface by blending it with the algae inhibitor of the embodiment of the present invention, and it becomes possible to move together with the algae floating on the water surface by wind, waves, water flow etc. Can be efficiently suppressed.
In addition, although “lysine or lysine salt and malonic acid or malonic acid salt” have high solubility in water, they dissolve and diffuse immediately in water, but they can be dissolved by mixing them with the algae inhibitor having the aspect of the present invention. The release rate can be controlled, and the suppression suitable for the characteristics of algae such as algal bloom is possible.
 また、本発明の藻類抑制剤は、表面にコーティング剤を有するものであるため、該藻類抑制剤を抑制したい池や湖沼等に投下後、長時間にわたり薬効を持続させることができると共に、風等によって藻類と共に水面を移動させることができ、該薬効を効率的に使うことができる。したがって、少量の藻類抑制剤で効率的に藻類の繁殖抑制をすることができる。特に夏場に水面に浮揚してきたときにだけ薬効成分を藻類に接触させるようにできるので、極めて効率的に藻類の抑制ができる。
 また、本発明の藻類抑制剤は、風等によって水面を移動するため、直接散布が難しい場所の藻類を抑制することができる。
Moreover, since the algae inhibitor of the present invention has a coating agent on the surface, it can maintain medicinal effects for a long time after being dropped in a pond, a lake, etc. where the algae inhibitor is to be inhibited. Can move the water surface together with the algae, and the medicinal effect can be used efficiently. Therefore, reproduction of algae can be efficiently suppressed with a small amount of algae inhibitor. In particular, since the medicinal component can be brought into contact with the algae only when it floats to the water surface in summer, algae can be suppressed extremely efficiently.
Moreover, since the algae inhibitor of this invention moves the water surface by a wind etc., it can suppress the algae of the place where direct spraying is difficult.
 また、本発明の藻類抑制剤の薬効成分は藻類の中の特定の藍藻類にのみ効果があるので、他の生態に悪影響を及ぼすことはない。また、該薬効成分は溶解性が高く、藻類抑制剤を構成する他の物質は生分解性又は低環境負荷性の物質であることより、本発明の藻類抑制剤は環境への負荷が少ない。 In addition, since the medicinal component of the algal inhibitor of the present invention is effective only on specific cyanobacteria in algae, it does not adversely affect other ecology. In addition, since the pharmaceutically active ingredient is highly soluble and the other substance constituting the algal inhibitor is a biodegradable or low environmental load substance, the algal inhibitor of the present invention has less environmental load.
芯剤の組成を変えた時の薬効成分の溶出率の変化を示すグラフである。It is a graph which shows the change of the elution rate of a pharmacologically active ingredient when the composition of a core agent is changed. 藻類抑制剤の粒径を変えた時の薬効成分の溶出率の変化を示すグラフである。It is a graph which shows the change of the elution rate of a pharmacologically active ingredient when the particle size of an algae inhibitor is changed. コーティング剤(EC)の被覆量を変えた時の薬効成分の溶出率の変化を示すグラフである。It is a graph which shows the change of the elution rate of a pharmacologically active ingredient when the coating amount of coating agent (EC) is changed. コーティング剤(フュームドシリカ)の被覆量を変えた時の薬効成分の溶出率の変化を示すグラフである。It is a graph which shows the change of the elution rate of a medicinal active ingredient when the amount of coating of a coating agent (fumed silica) is changed.
 以下、本発明について説明するが、本発明は、以下の具体的形態に限定されるものではなく、技術的思想の範囲内で任意に変形することができる。 Hereinafter, the present invention will be described, but the present invention is not limited to the following specific embodiments, and can be arbitrarily modified within the scope of the technical idea.
<藻類抑制剤>
 本発明の藻類抑制剤は、水面に浮遊させて該水面に浮遊する藻類を抑制する藻類抑制剤であって、少なくとも、リジン若しくはリジン塩及びマロン酸若しくはマロン酸塩からなる薬効成分、並びに、該薬効成分を保持するバインダーを含有する芯剤と、該芯剤の表面に存在し薬効成分の徐放性を制御するコーティング剤と、を有してなるものであることを特徴とする。
<Algal inhibitor>
The algal inhibitor of the present invention is an algal inhibitor which is suspended on water and suppresses algae floating on the water, and is at least a lysine or lysine salt and a medicinal component comprising malonic acid or malonate, and It is characterized in that it comprises a core agent containing a binder which holds a medicinal component, and a coating agent which is present on the surface of the core agent and controls the sustained release of the medicinal component.
 本発明の藻類抑制剤は、藻類の増殖制御や浮遊性の制御等に用いられるものである。ここで「抑制」とは数や密度の減少を意味する。本発明の藻類抑制剤は繁殖抑制等によって藻類を減少させ抑制するものである。
 藻類の中でも、藍藻類の抑制に用いられることが好ましく、ミクロキスティス(Microcystis)属の藍藻類の抑制に用いられることがより好ましく、アオコの抑制に用いられることが特に好ましい。
 アオコを形成する種として、ミクロキスティス・ビリディス(Microcystis viridis)、ミクロキスティス・エルギノーザ(Microcystis aeruginosa)、ミクロキスティス・ウェーゼンベルギー(Microcystis wesenbergii)等が挙げられ、何れにも選択的に抑制効果が高いので特に好ましい。
The algae inhibitor of the present invention is used for control of growth of algae, control of buoyancy and the like. Here, "suppression" means decrease in number or density. The algae inhibitor of the present invention is to reduce and inhibit algae by suppressing reproduction.
Among algae, it is preferably used for suppression of cyanobacteria, more preferably for suppression of cyanobacteria of the genus Microcystis, and particularly preferably used for suppression of algae.
As species forming blue-green algae, Microcystis viridis (Microcystis viridis), Microcystis aeruginosa (Microcystis aeruginosa), Microcystis wesenbergii etc. can be mentioned, and any of them is highly selective. Especially preferred.
 本発明の藻類抑制剤は水面に浮遊するので、同様に水面に浮遊する藻類を抑制することが特徴ではあるが、水中の藻類の抑制を排除するものではなく、水中や水底での藻類の抑制にも使用可能である。該藻類抑制剤は、水底でも薬効成分により、該水底に存在する堡塁に付着した藻類等を抑制することができる。 Since the algae inhibitor of the present invention floats on the water surface, it is characterized by suppressing algae floating on the water surface as well, but it does not exclude the suppression of algae in the water, but suppresses algae in the water or in the water bottom. Can also be used. The algal inhibitor can suppress algae and the like attached to moss existing on the bottom of the bottom of the bottom of the bottom of the bottom by a medicinal ingredient.
 本発明の藻類抑制剤は芯剤を有する。該芯剤は薬効成分及び薬効成分を保持するバインダーを含有する。 The algae inhibitor of the present invention has a core. The core agent contains a medicinal ingredient and a binder holding the medicinal ingredient.
 上記薬効成分は、リジン若しくはリジン塩、及び、マロン酸若しくはマロン酸塩からなる。
 上記「リジン若しくはリジン塩」としては、限定はされないが、具体的には、例えば、リジン、リジン塩酸塩、リジン酢酸塩、リジングルタミン酸塩、リジンアスパラギン酸塩等が挙げられる。上記「リジン若しくはリジン塩」として、リジン塩酸塩を用いることが特に好ましい。
 上記「マロン酸若しくはマロン酸塩」としては、限定はされないが、具体的には、例えば、マロン酸、マロン酸ナトリウム、マロン酸カリウム、マロン酸マグネシウム、マロン酸カルシウム等が挙げられる。上記「マロン酸若しくはマロン酸塩」として、マロン酸を用いることが特に好ましい。
The active ingredient consists of lysine or lysine salt, and malonic acid or malonate.
Examples of the above-mentioned "lysine or lysine salt" include, but are not limited to, specifically, lysine, lysine hydrochloride, lysine acetate, lysine glutamate, lysine aspartate and the like. It is particularly preferable to use lysine hydrochloride as the above-mentioned "lysine or lysine salt".
Examples of the "malonic acid or malonic acid salt" include, but are not limited to, malonic acid, sodium malonate, potassium malonate, magnesium malonate, calcium malonate and the like. It is particularly preferable to use malonic acid as the above-mentioned "malonic acid or malonic acid salt".
 「リジン若しくはリジン塩」とは、リジンとリジン塩の一方のみを用いてもよいし、両方を混合して用いてもよいことは言うまでもない。また、「マロン酸若しくはマロン酸塩」とは、マロン酸とマロン酸塩の一方のみを用いてもよいし、両方を混合して用いてもよいことは言うまでもない。 It is needless to say that as the "lysine or lysine salt", only one of lysine and lysine salt may be used, or both may be used as a mixture. Moreover, it is needless to say that as "malonic acid or malonic acid salt", only one of malonic acid and malonic acid salt may be used, or both may be mixed and used.
 上記バインダーは、「天然物由来の高分子」及び「非環境汚染物質」からなる群より選ばれる成分であることが好ましい
 「天然物由来の高分子」又は「非環境汚染物質」を単独で使用してもよく、「天然物由来の高分子」及び「非環境汚染物質」を組み合わせて使用してもよい。
The binder is preferably a component selected from the group consisting of "naturally-derived polymers" and "non-environmental pollutants" Use of "naturally-derived polymers" or "non-environmental pollutants" alone The “naturally-derived macromolecule” and the “non-environmental pollutant” may be used in combination.
 また、上記天然物由来の高分子としては、カラギーナン、ゼラチン、ペクチン、アガロース、デンプン、コラーゲン、プルラン、マンナン、デキストリン、セルロース等が、毒性がない、環境負荷が比較的少ない、水を吸収してゲルになるゲル化性能に優れる、自然分解しやすい等の点から好ましい。
 これらから選ばれる1種を単独で又は2種以上を組み合わせて使用することができる。
In addition, carrageenan, gelatin, pectin, agarose, starch, collagen, pullulan, mannan, dextrin, cellulose, etc., as the above-mentioned polymers derived from natural products, have no toxicity, relatively low environmental impact, absorb water It is preferable from the point of being excellent in the gelation performance which turns into a gel, and easy to be decomposed naturally.
One selected from these can be used alone or in combination of two or more.
 また、上記非環境汚染物質としては、環境負荷の低い物質であり、飼料添加物や食品添加物への使用が認められている物質や自然界に多量に存在する粘土鉱物からなる物質等が挙げられる。具体的には、ケイ酸ナトリウム等のケイ酸塩、カルボキシメチルセルロース、カルボキシメチルセルロースナトリウム、アルギン酸ナトリウム等が挙げられる。
 これらから選ばれる1種を単独で又は2種以上を組み合わせて使用することができる。
 上記非環境汚染物質は、ゲル化剤を含んでいることが好ましい。
 例えば、上記したケイ酸塩等は、ゲル化剤として、無機酸又は有機酸を含んでいることが好ましい。該無機酸又は有機酸は、中和することにより該ケイ酸塩をゲル化させることができる。
 また、上記したカルボキシメチルセルロース、カルボキシメチルセルロースナトリウム、アルギン酸ナトリウム等は、ゲル化剤として、塩化カルシウム、塩化マグネシウム、塩化アルミニウム等の多価陽イオン含有化合物を含んでいることが好ましい。
 したがって、上記非環境汚染物質に含まれるゲル化剤としては、無機酸若しくは有機酸、多価陽イオン含有化合物が特に好ましい。該ゲル化剤は、上記薬効成分が兼ねていてもよい。
Moreover, as the non-environmental pollutants mentioned above, substances having low environmental impact, such as substances approved for use as feed additives and food additives, and substances consisting of clay minerals present in large amounts in the natural world, etc. can be mentioned. . Specifically, silicates such as sodium silicate, carboxymethylcellulose, sodium carboxymethylcellulose, sodium alginate and the like can be mentioned.
One selected from these can be used alone or in combination of two or more.
The non-environmental pollutants preferably contain a gelling agent.
For example, the above-mentioned silicates and the like preferably contain an inorganic acid or an organic acid as a gelling agent. The inorganic acid or organic acid can gelate the silicate by neutralization.
The above-mentioned carboxymethylcellulose, carboxymethylcellulose sodium, sodium alginate and the like preferably contain polyvalent cation-containing compounds such as calcium chloride, magnesium chloride and aluminum chloride as gelling agents.
Therefore, as the gelling agent contained in the above non-environmental pollutants, inorganic acids or organic acids, and compounds containing polyvalent cations are particularly preferable. The gelling agent may be combined with the above-mentioned medicinal component.
 好ましいバインダーは、前記理由から、具体的には、ケイ酸、多糖類、カルボキシメチルセルロース及びコラーゲンからなる群より選ばれる化合物若しくはその塩である。
 ここで、上記「多糖類」には複合多糖類も含まれる。また、上記「ケイ酸の塩」には、組成式(NaO)(SiO)やNaSiOで表されるメタケイ酸のナトリウム塩が含まれる。
Preferred binders are, for the aforementioned reasons, in particular compounds or salts thereof selected from the group consisting of silicic acid, polysaccharides, carboxymethylcellulose and collagen.
Here, the above-mentioned "polysaccharide" also includes complex polysaccharides. Further, the above-mentioned “salt of silicic acid” includes sodium salts of metasilicic acid represented by the composition formula (Na 2 O) (SiO 2 ) or Na 2 SiO 3 .
 特に好ましいバインダーは、前記理由から具体的には以下が挙げられる。
 上記「ケイ酸若しくはその塩」として、ケイ酸、ケイ酸ナトリウム、ケイ酸ナトリウムと酸とを反応させて得られるもの(水溶液は水ガラス1~4号等)等が挙げられる。
 上記「多糖類若しくはその塩」として、アミロース(デンプン)、セルロース、アガロース、カラギーナン、ペクチン、アルギン酸ナトリウム、「アルギン酸ナトリウム、ペクチン等と2価以上の陽イオン含有物とを反応させて得られるもの」等が挙げられる。
 上記カルボキシメチルセルロース若しくはその塩として、カルボキシメチルセルロース、「カルボキシメチルセルロースと2価以上の陽イオン含有物とを反応させて得られるもの」等が挙げられる。
 上記「コラーゲン若しくはその塩」として、ゼラチン等が挙げられる。
Particularly preferred binders are, for the above reasons, specifically the following.
Examples of the above-mentioned "silicic acid or salt thereof" include silicic acid, sodium silicate, and those obtained by reacting sodium silicate with an acid (aqueous solution is water glass No. 1 to 4 etc.).
As the above-mentioned "polysaccharides or salts thereof", amylose (starch), cellulose, agarose, carrageenan, pectin, sodium alginate, "a product obtained by reacting sodium alginate, pectin and the like with a cation-containing substance having a valence of 2 or more" Etc.
Examples of the above-mentioned carboxymethylcellulose or a salt thereof include carboxymethylcellulose, "a product obtained by reacting carboxymethylcellulose with a cation-containing substance having a valency of 2 or more", and the like.
Gelatin etc. are mentioned as said "collagen or its salt".
 上記薬効成分の徐放速度の調節や環境負荷の低減等の点から、上記バインダーは生分解性の高い及び/又は環境負荷の低い物質を用いることがより好ましい。より好ましいバインダーとして、ケイ酸ソーダ、アミロース(デンプン)、アガロース、カラギーナン、ペクチン、アルギン酸ナトリウム、「カルボキシメチルセルロースと2価以上の陽イオン含有物とを反応させて得られるもの」、コラーゲン、ゼラチン等が挙げられる。 It is more preferable to use a highly biodegradable material and / or a material with a low environmental load, from the viewpoint of controlling the sustained release rate of the pharmaceutically active ingredient and reducing the environmental load. More preferable binders include sodium silicate, amylose (starch), agarose, carrageenan, pectin, sodium alginate, "obtained by reacting carboxymethyl cellulose with a cation-containing substance having a valency of 2 or more", collagen, gelatin, etc. It can be mentioned.
 また、上記薬効成分の徐放速度の調節や環境負荷の低減等の点から、上記バインダーは生分解性の高い及び/又は環境負荷の低い物質を用いることがより好ましい。その点から、より好ましいバインダーとして、ペクチン、ゼラチン、デンプン、「カルボキシメチルセルロースナトリウムと塩化カルシウム」、「ケイ酸塩と酸」、アルギン酸ナトリウムと塩化カルシウム等が挙げられる。 Further, it is more preferable to use a highly biodegradable material and / or a substance having a low environmental load, from the viewpoint of controlling the sustained release rate of the pharmaceutically active ingredient and reducing the environmental load. From this point of view, pectin, gelatin, starch, "carboxymethylcellulose sodium and calcium chloride", "silicate and acid", sodium alginate and calcium chloride and the like are mentioned as more preferable binders.
 バインダーの調製に関しては、「天然物由来の高分子」及び「非環境汚染物質」は、それらを水にスラリー状に分散させたり溶解させたりすることで行うことが好ましい。
 また、「非環境汚染物質」とゲル化剤を併せて使用する場合、ゲル化剤も水溶液(又は微分散液)にしておいてから、互いに混合することによって行うことが好ましい。
 何れも、その後、乾燥させ、乾燥後に顆粒状又はフレーク状になっていなければ(必要ならば)粉砕して顆粒状又はフレーク状にし、得られたものを芯剤(又は芯剤の成分)とすることが好ましい。
 「天然物由来の高分子」や「非環境汚染物質」の水溶液中に、薬効成分も溶解させ、それらを乾燥させ、上記方法で芯剤を作製することが、芯剤の内部に薬効成分を封じ込めて、芯剤の内部に存在する薬効成分が徐放性になる点から好ましい。
With regard to the preparation of the binder, it is preferable to carry out "naturally-derived polymers" and "non-environmental pollutants" by dispersing or dissolving them in water in water.
When "non-environmental pollutants" and a gelling agent are used in combination, the gelling agent is also preferably made into an aqueous solution (or a fine dispersion) and then mixed with each other.
Both are then dried, and if dry they are not granulated or flaked (if necessary) and crushed (if necessary) to granulate or flaked, and the obtained one with a core agent (or a component of the core agent) It is preferable to do.
It is also possible to dissolve medicinal ingredients in an aqueous solution of "naturally-derived polymer" or "non-environmental pollutants", dry them, and prepare a core agent by the above method. It is preferable from the viewpoint that it will be contained and the active ingredient present inside the core agent will be sustained release.
 本発明の藻類抑制剤は、必須部材として「上記芯剤の表面に存在し薬効成分の徐放性を制御するコーティング剤」を有する。
 本明細書において、「コーティング」とは、「被覆、付与、外添、塗布」という意味を含む。
 上記コーティング剤は、水面への浮遊性、上記薬効成分の徐放速度の調節や環境負荷の低減等の点から、生分解性の高い及び/又は環境負荷の低い物質を用いることが好ましい。なお、コーティング剤が取れると水に浮遊し難くなるが、水底で薬効成分を放出することにより水底に存在する藻類を抑制することもできる。
The algae inhibitor of the present invention has "a coating agent which is present on the surface of the above-mentioned core and controls the sustained release of the medicinal ingredient" as an essential member.
In the present specification, "coating" includes the meaning of "coating, application, external addition, application".
As the coating agent, it is preferable to use a highly biodegradable and / or low environmental load material from the viewpoint of floating on the water surface, adjustment of the sustained release rate of the medicinal ingredient, reduction of environmental load and the like. In addition, although it will become difficult to float in water if a coating agent is removed, the algae which are present in the bottom of a water can also be suppressed by releasing a medicinal ingredient in the bottom of a water.
 上記コーティング剤は、上記薬効成分の徐放速度を制御し、藻類抑制剤の散布後30分以上に亘り上記薬効成分を溶出し続けさせるものであることが好ましく、藻類抑制剤の散布後1時間以上に亘り上記薬効成分を溶出し続けさせるものであることがより好ましく、藻類抑制剤の散布後2時間以上に亘り上記薬効成分を溶出し続けさせるものであることが特に好ましい。 It is preferable that the coating agent controls the sustained release rate of the pharmaceutically active ingredient and continuously elutes the pharmaceutically active ingredient over 30 minutes after the application of the algal inhibitor, and one hour after the application of the algal inhibitor It is more preferable that the pharmaceutically active ingredient be continuously eluted over the above, and it is particularly preferable that the pharmaceutically active ingredient be continuously eluted for 2 hours or more after the application of the algal inhibitor.
 好ましいコーティング剤として、特に限定はないが、具体的には、例えば、エチルセルロース(EC)、セルロース、フュームドシリカ(FS)、蜜蝋、シェラック等の疎水性部材;カルボキシメチルセルロースカルシウム、アルギン酸カルシウム、ヒドロキシプロピルメチルセルロース等のゲル化物質からなる群から選ばれる化合物が挙げられる。これらから選ばれる1種を単独で又は2種以上を組み合わせて使用することができる。
 かかる化合物であることは上記点から好ましく、エチルセルロース又はフュームドシリカが上記点から特に好ましい。
 フュームドシリカは、親水性のものも疎水性のものも好適に用いられる。フュームドシリカの表面処理を行うことで、親水性、疎水性をコンロールできる。何れの表面状態でも上記効果を発揮するが、疎水性処理したものが好適に用いられる。疎水性処理されたフュームドシリカは上記効果を特に発揮し、疎水性の強さにより、徐放速度をコントロールすることができる。使用用途に応じて、フュームドシリカの種類を適宜選択することができる。
The preferable coating agent is not particularly limited, and specifically, for example, hydrophobic members such as ethylcellulose (EC), cellulose, fumed silica (FS), beeswax, shellac, etc .; calcium carboxymethylcellulose, calcium alginate, hydroxypropyl Examples include compounds selected from the group consisting of gelling substances such as methyl cellulose. One selected from these can be used alone or in combination of two or more.
Such a compound is preferable from the above-mentioned point, and ethyl cellulose or fumed silica is particularly preferable from the above-mentioned point.
As the fumed silica, hydrophilic ones and hydrophobic ones are preferably used. By performing surface treatment of fumed silica, hydrophilicity and hydrophobicity can be controlled. Although the above effects are exhibited in any surface state, those subjected to hydrophobic treatment are preferably used. Hydrophobic-treated fumed silica exerts the above-mentioned effects in particular, and the strength of hydrophobicity can control the sustained release rate. The type of fumed silica can be appropriately selected according to the application.
 芯剤へのコーティング剤の付与方法は、該芯剤の表面を好適に覆うことができる方法であれば特に限定はないが、溶液にできるものは溶液にして、芯剤の表面に付与し、その後、溶媒を蒸発させる方法が好ましい。
 また、フュームドシリカ、セルロース等の容易に溶液にしにくいものは、芯剤の表面にそのまま外添する方法が好ましい。
The method for applying the coating agent to the core agent is not particularly limited as long as the method can suitably cover the surface of the core agent, but the solution can be made into a solution and applied to the surface of the core agent, Then, the method of evaporating a solvent is preferable.
In addition, it is preferable to externally add the fumed silica, cellulose and the like to the surface of the core agent as it is difficult to make a solution easily.
 本発明の藻類抑制剤は固形状であり、その形状は、目的に応じて適宜選択することができる。具体的には、顆粒状、フレーク状、タブレット状、粒状等が挙げられる。
 上記藻類抑制剤が、顆粒状、タブレット状又は粒状のときは、該薬効成分の徐放速度の調節や藻類抑制剤の水面での浮遊性や分散性等の点から、その数平均直径が0.05mm~30mmであることが好ましく、0.1mm~15mmであることがより好ましく、0.5mm~10mmであることが特に好ましい。
 上記藻類抑制剤がフレーク状のときは、該薬効成分の徐放速度の調節や藻類抑制剤の水面での浮遊性等の点から、その厚さが0.03mm~3mmであることが好ましく、0.05~2mmであることがより好ましく、0.1mm~1mmであることが特に好ましい。
The algae inhibitor of the present invention is solid, and its shape can be appropriately selected according to the purpose. Specifically, granules, flakes, tablets, granules and the like can be mentioned.
When the algal inhibitor is in the form of granules, tablets or granules, the number average diameter is 0 in view of the control of the sustained release rate of the medicinal ingredient and the floatability and dispersibility of the algal inhibitor on the water surface. The thickness is preferably in the range of 0.05 mm to 30 mm, more preferably in the range of 0.1 mm to 15 mm, and particularly preferably in the range of 0.5 mm to 10 mm.
When the algal inhibitor is in the form of flakes, the thickness is preferably 0.03 mm to 3 mm, from the viewpoint of controlling the sustained release rate of the medicinal ingredient and floating properties of the algal inhibitor on the water surface, It is more preferably 0.05 to 2 mm, and particularly preferably 0.1 to 1 mm.
 上記薬効成分中、「リジンとリジン塩」の合計質量に対する「マロン酸とマロン酸塩」の合計質量の割合は特に制限はないが、該割合は、好ましくは0.1以上2以下であり、より好ましくは0.2以上1.8以下であり、特に好ましくは0.3以上1.5以下である。
 該「合計質量」には、「リジンとリジン塩」の一方のみしか含有しない場合も、「マロン酸とマロン酸塩」の一方のみしか含有しない場合も概念として含まれる。
The ratio of the total mass of “malonic acid and malonate” to the total mass of “lysine and lysine salt” among the above medicinal ingredients is not particularly limited, but the ratio is preferably 0.1 or more and 2 or less, More preferably, it is 0.2 or more and 1.8 or less, and particularly preferably 0.3 or more and 1.5 or less.
The term “total mass” includes the concept in the case where only one of “lysine and lysine salt” is contained, and the case in which only “one of malonic acid and malonate” is contained.
 上記芯剤全体を100質量部としたときの、上記薬効成分の含有量は特に制限がなく、目的に応じて適宜選択することができるが、上記薬効成分の含有量は10~90質量部が好ましく、15~80質量部がより好ましく、20~70質量部が特に好ましい。
 薬効成分の含有量が多過ぎると、散布する藻類抑制剤の好適量が減少し、水面に均等に分散し難くなる場合や徐放性にならなくなる場合等がある。一方、薬効成分の含有量が少な過ぎると、散布する藻類抑制剤の量が増加する場合や多過ぎるバインダーによる環境負荷が生じる場合等がある。
The content of the above pharmaceutically active ingredient is not particularly limited when the whole core agent is 100 parts by mass, and can be appropriately selected according to the purpose, but the content of the above pharmaceutically active ingredient is 10 to 90 parts by mass Preferably, 15 to 80 parts by mass is more preferable, and 20 to 70 parts by mass is particularly preferable.
When the content of the medicinal ingredient is too large, the suitable amount of the algae inhibitor to be dispersed may be reduced, and it may be difficult to uniformly disperse on the water surface, or the sustained release may not be achieved. On the other hand, when the content of the medicinal component is too small, the amount of the algae inhibitor to be dispersed may increase, or the environmental load due to the too large binder may occur.
 また、本発明の藻類抑制剤における芯剤には、薬効成分及びバインダーの他に、「その他の成分」を含有することができる。「その他の成分」としては、特に制限はなく、本発明の効果を損なわない範囲内で目的に応じて適宜選択することができ、例えば、活性炭、酸化鉄、酸化カルシウム(リンの吸着等の水質改善目的)、おが屑、木粉、水生植物の種子等が挙げられる。 Moreover, the core agent in the algae inhibitor of the present invention may contain "other components" in addition to the medicinal component and the binder. There is no restriction | limiting in particular as "other components", According to the objective, it can select suitably in the range which does not impair the effect of this invention, For example, activated carbon, iron oxide, calcium oxide (The water quality of adsorption of phosphorus etc. For the purpose of improvement), sawdust, wood flour, seeds of aquatic plants, etc. can be mentioned.
 上記藻類抑制剤全体を100質量部としたときに、上記コーティング剤の含有量は特に制限がなく、目的に応じて適宜選択することができる。水面への浮遊性の調節等から、上記コーティング剤の含有量は、1質量部以上10質量部以下が好ましく、1質量部以上8質量部以下がより好ましく、1質量部以上7質量部以下が特に好ましい。 There is no restriction | limiting in particular in the content of the said coating agent, when the whole said algae inhibitor is 100 mass parts, According to the objective, it can select suitably. The content of the coating agent is preferably 1 part by mass or more and 10 parts by mass or less, more preferably 1 part by mass or more and 8 parts by mass or less, and 1 part by mass or more and 7 parts by mass or less. Particularly preferred.
 また、本発明の藻類抑制剤は、芯剤及びコーティング剤の他に、「その他の部材」を「外添等の混合」をすることができる。「その他の部材」としては、特に制限はなく、本発明の効果を損なわない範囲内で目的に応じて適宜選択することができ、例えば、活性炭、酸化鉄、酸化カルシウム、おが屑、木粉、水生植物の種子等が挙げられる。 In addition to the core agent and the coating agent, the algae inhibitor of the present invention can "mix other components, etc." with "other components". There is no restriction | limiting in particular as "other members", According to the objective, it can select suitably in the range which does not impair the effect of this invention, For example, activated carbon, iron oxide, calcium oxide, sawdust, wood flour, aquatic Plant seeds and the like can be mentioned.
<製造方法>
 本発明の製造方法は、上記藻類抑制剤の製造方法であって、「『リジン若しくはリジン塩』及び『マロン酸若しくはマロン酸塩』からなる薬効成分」の混合粉体に、上記天然物由来の高分子と水を加えてスラリー状にする工程、該スラリーを乾燥する工程、及び、造粒する工程を含むことを特徴とする。
<Manufacturing method>
The production method of the present invention is a method for producing the above algal inhibitor, wherein the mixed powder of “a pharmaceutically active ingredient consisting of“ lysine or lysine salt ”and“ malonic acid or malonate ”” is derived from the above natural product The method is characterized by including a step of adding a polymer and water to form a slurry, a step of drying the slurry, and a step of granulating.
 また、本発明の製造方法は、上記藻類抑制剤の製造方法であって、「『リジン若しくはリジン塩』及び『マロン酸若しくはマロン酸塩』からなる薬効成分」の混合粉体に、上記非環境汚染物質と水を加えて溶液状にした後、該溶液にゲル化剤を加えてゲル状にする工程、該ゲルを乾燥する工程、及び、造粒する工程を含むことを特徴とする。 In addition, the production method of the present invention is a method for producing the above-mentioned algae inhibitor, and it is preferable to use the mixed powder of “a medicinal component comprising“ lysine or lysine salt ”and“ malonic acid or malonate ”” in the non-environment The method is characterized by including the steps of adding a contaminant and water to form a solution, adding a gelling agent to the solution to form a gel, drying the gel, and granulating.
 公知の乾燥装置を使用して、上記スラリー又はゲルを乾燥させることができる。乾燥条件(温度や時間等)は、目的に応じて適宜選択することができる。
 上記スラリー又はゲルを乾燥後に造粒しても、造粒してから乾燥させても、又は、乾燥させながら造粒させてもよく、目的に応じて適宜選択することができる。
 乾燥時に水分が蒸発し、藻類抑制剤中に気泡が残るようにすると、該藻類抑制剤の比重が水より軽くなることにより、長時間又は良好に水面に浮遊させることができる。
The slurry or gel can be dried using known drying equipment. Drying conditions (temperature, time, etc.) can be appropriately selected according to the purpose.
The slurry or gel may be granulated after drying, granulated and then dried, or may be granulated while being dried, and can be appropriately selected depending on the purpose.
If the water evaporates during drying and air bubbles remain in the algae inhibitor, the algae inhibitor can be suspended on the water surface for a long time or favorably because the specific gravity of the algae inhibitor is smaller than that of water.
 本発明の製造方法には、上記コーティング剤を、(好ましくは乾燥させた)芯剤にコーティングする工程等を含んでいる。
 コーティング剤を芯剤に塗布する手段は公知の手段を用いることができる。例えば、コーティング剤を溶媒に溶解後、成形した芯剤に吹き付けてコーティングする方法や、固体状のコーティング剤を成形した芯剤に塗布又は外添付与する方法等がある。
The production method of the present invention includes the step of coating the above-mentioned coating agent on a core agent (preferably dried).
The coating agent may be applied to the core by any known method. For example, there is a method in which a coating agent is dissolved in a solvent and then sprayed onto a molded core to coat, or a method in which a solid coating agent is coated or externally attached to a molded core.
<藻類の抑制方法>
 本発明の藻類の抑制方法は、上記藻類抑制剤を使用した藻類の抑制方法であって、水1m当たりに、該藻類抑制剤を1g以上100g以下投入し、コーティング剤によって薬効成分の徐放速度を制御し、散布後30分以上に亘り、該水面に該藻類抑制剤から薬効成分を溶出し続けさせることを特徴とする。
<Method to control algae>
The method for suppressing algae according to the present invention is a method for suppressing algae using the above-mentioned algae inhibitor, wherein 1 g to 100 g of the algae inhibitor is added per 1 m 2 of water, and the sustained release of the active ingredient by the coating agent It is characterized in that the rate is controlled and the active ingredient continues to be eluted from the algal inhibitor on the water surface for 30 minutes or more after spraying.
 日照時間の内に上記藻類抑制剤を散布し30分以上に亘り薬効成分が溶出し続けると、日照があるとアオコ等の藻類は水中から上昇し水面に浮遊するようになるので、同じく浮遊している本発明の藻類抑制剤からの薬効成分が該藻類に直接的に薬効を及ぼすようになり好ましい。
 30分未満で薬効成分が溶出し終わってしまうと、前記した「薬効成分の水溶液を散霧(使用)したとき」のように、水面より下の水中に拡散してしまう薬効成分の割合が多くなる場合がある。一方、日照時間外に亘り薬効成分が溶出し続けると、日照時間外はアオコ等の藻類は水中に没しているため、浮遊している本発明の藻類抑制剤からの薬効成分が該藻類に直接的に薬効を及ぼせない場合があり、日照時間外の薬効成分の放出が無駄になる場合がある。
 好ましくは日照時間の内の30分以上9時間以下、より好ましくは日照時間の内の1時間以上8時間以下、特に好ましくは日照時間の内の2時間以上7時間以下である。
If the above-mentioned algae inhibitor is sprayed within the sunshine time and the medicinal ingredient continues to elute for 30 minutes or more, algal algae such as algal will rise from the water and float on the water surface when there is sunshine, so Medicinal active ingredients from the present algal inhibitors of the present invention have a direct effect on the algae and are preferred.
When dissolution of the active ingredient is completed in less than 30 minutes, the proportion of active ingredient that diffuses into the water below the water surface is high, as in the above-mentioned "dispersion (use) of the aqueous solution of active ingredient". May be On the other hand, when the drug component continues to elute over the sunshine period, since algae such as algal blooms are submerged in the sunshine period, the drug component from the floating algae inhibitor of the present invention is added to the algae In some cases, the drug effect can not be achieved directly, and the release of the drug component outside sunshine hours may be wasted.
It is preferably 30 minutes to 9 hours of sunshine duration, more preferably 1 hour to 8 hours of sunshine duration, and particularly preferably 2 hours to 7 hours of sunshine duration.
 ただし、夜(日照時間外)まで徐放し続ける又は2日以上に亘り日照時間に徐放する態様も、本発明の藻類の抑制方法としてあり得るものであり、本発明の藻類の抑制方法から排除されるものではない。 However, a mode in which sustained release until night (outside sunshine time) or sustained release in sunshine time over 2 days is also possible as a method of controlling algae of the present invention and excluded from the method of inhibiting algae of the present invention It is not something to be done.
 薬効成分が放出した後の藻類抑制剤は、その形状を保っていてもいなくてもよいが、通常は該形状を保っている。薬効成分が放出した後のバインダーやコーティング剤は、通常は水中の微生物等によって分解されるか又は環境には影響を与えない。 The algal inhibitor after release of the medicinal ingredient may or may not retain its shape, but usually retains that shape. The binder or coating agent after the release of the active ingredient is usually decomposed by microorganisms in water or the like, or does not affect the environment.
 本発明の藻類の抑制方法は、藻類を抑制及び/又は藻類の発生を抑制したい水環境で使用することができる。水環境の例として、池、沼、湖、川、ダム、海、等が挙げられる。 The algae control method of the present invention can be used in a water environment where it is desired to inhibit algae and / or inhibit algae generation. Examples of water environments include ponds, swamps, lakes, rivers, dams, and the sea.
 藻類抑制剤の散布量は、該藻類抑制剤に含まれるリジン又はマロン酸換算で、0.1~50g/mが好ましく、1~40g/mがより好ましく、10~30g/mが特に好ましい。
 散布量が多過ぎると、藻類抑制剤が無駄になる場合があり、一方、散布量が少な過ぎると藻類が良好に抑制できない場合がある。
Application rate of algae inhibitor, lysine or malonic acid terms contained in algal inhibitor, preferably 0.1 ~ 50g / m 2, more preferably 1 ~ 40g / m 2, is 10 ~ 30g / m 2 Particularly preferred.
If the application rate is too high, the algae inhibitor may be wasted, while if the application rate is too low, the algae may not be well suppressed.
 また、水1m当たりに、該藻類抑制剤を1g以上100g以下投入することが好ましく、5g以上90g以下投入することがより好ましく、10g以上80g以下投入することが特に好ましい。散布量が多過ぎると、藻類抑制剤が無駄になる場合があり、一方、散布量が少な過ぎると藻類が良好に抑制できない場合がある。 Moreover, it is preferable to add 1 g or more and 100 g or less of the algae inhibitor, more preferably 5 g or more and 90 g or less, and particularly preferably 10 g or more and 80 g or less, per 1 m 2 of water. If the application rate is too high, the algae inhibitor may be wasted, while if the application rate is too low, the algae may not be well suppressed.
 藻類抑制剤の効果を発揮させる等の点から、散布時期はアオコが繁殖する時期に行うことが好ましく、水温が15℃以上になる時期に散布することが好ましい。 From the point of exerting the effect of the algae inhibitor etc., it is preferable to carry out the spraying time at the time when the algae bloom reproduces, and it is preferable to spray it at the time when the water temperature becomes 15 ° C. or more.
 以下に、実施例及び比較例を挙げて本発明を更に具体的に説明するが、本発明は、その要旨を超えない限りこれらの実施例に限定されるものではない。 EXAMPLES The present invention will be more specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded.
実施例1
[芯剤の検討]
 リジン塩酸塩及びマロン酸からなる薬効成分に、以下の各種バインダーを加え、藻類抑制剤を作成した。「非環境汚染物質」としてカルボキシメチルセルロースの塩であるカルボキシメチルセルロースナトリウム(CMCNa)、「ゲル化剤」として塩化カルシウム(CaCl)、「天然物由来の高分子」であって、多糖類であるペクチン、「天然物由来の高分子」でも「非環境汚染物質」でもないポリビニルアルコール(PVA)をそれぞれ使用し、芯剤の検討を行った。
 藻類抑制剤の組成は、藻類抑制剤全体に対して、リジン塩酸塩35質量%、マロン酸35質量%、バインダー28質量%、コーティング剤1質量%とした。
 コーティング剤として、エチルセルロース(EC)を用いた。
Example 1
[Examination of core agent]
The following various binders were added to the medicinal component which consists of a lysine hydrochloride and malonic acid, and the algae inhibitor was created. Carboxymethylcellulose sodium (CMCNa) which is a salt of carboxymethylcellulose as "non-environmental pollutant", calcium chloride (CaCl 2 ) as "gelling agent", "pectin which is a polymer derived from a natural product" and is polysaccharide The core agent was examined using polyvinyl alcohol (PVA) which is neither "naturally-derived polymer" nor "non-environmental pollutant".
The composition of the algal inhibitor was 35% by mass of lysine hydrochloride, 35% by mass of malonic acid, 28% by mass of the binder, and 1% by mass of the coating agent based on the total amount of the algal inhibitor.
Ethyl cellulose (EC) was used as a coating agent.
 リジン塩酸塩とマロン酸を混合し、該混合物にカルボキシメチルセルロースナトリウム(CMCNa)と塩化カルシウム(CaCl)を加えた。更に水を加えてスラリー状にし、該スラリーを乾燥後フレーク状に成形して芯剤を得た。
 ペクチンとポリビニルアルコール(PVA)も上記と同様にして芯剤を得た。
Lysine hydrochloride and malonic acid were mixed and sodium carboxymethylcellulose (CMCNa) and calcium chloride (CaCl 2 ) were added to the mixture. Further, water was added to form a slurry, and the slurry was dried and shaped into flakes to obtain a core.
Pectin and polyvinyl alcohol (PVA) were also obtained in the same manner as above to obtain a core.
 該芯剤に、エチルセルロース(EC)を、アセトン溶液に溶解させ10質量%溶液を調製し、該溶液を吹き付けるようにしてコーティングし、藻類抑制剤を作製した。 Ethylcellulose (EC) was dissolved in an acetone solution to prepare a 10% by mass solution, and the solution was sprayed to coat the core agent to prepare an algal inhibitor.
 作製した藻類抑制剤0.5gを水500gに投入し、時間毎のマロン酸溶出率を測定した。
 マロン酸濃度はキャピラリー電気泳動(大塚電子株式会社製)を用いて求めた。
 「マロン酸溶出率」は、水槽内のマロン酸の質量を測定・算出し、使用した藻類抑制剤に含まれるマロン酸の全質量で除することにより求めた。
 なお、マロン酸を薬効成分の代表として測定したが、マロン酸でなくても、マロン酸塩、リジン、リジン塩であっても、水溶性が若干異なるだけなので、薬効成分全体について、溶出(徐放性)の傾向は別途行った実験でほぼ同じであった。
0.5 g of the produced algal inhibitor was added to 500 g of water, and the malonic acid elution rate was measured with time.
The malonic acid concentration was determined using capillary electrophoresis (manufactured by Otsuka Electronics Co., Ltd.).
The "malonic acid elution rate" was determined by measuring and calculating the mass of malonic acid in the water tank and dividing by the total mass of malonic acid contained in the used algal inhibitor.
In addition, although malonic acid was measured as a representative of the pharmacologically active ingredient, even if it is not malonic acid, even if it is malonic acid salt, lysine, and lysine salt, only the water solubility is slightly different. The tendency of release was almost the same in the experiment conducted separately.
 結果を図1に示す。全てのバインダーで薬効成分の徐放性を確認できた。ペクチンは放出速度が遅く、徐々に薬効成分を放出する性能が高かった。一方、PVAは徐放性はあるものの最初の30分での溶出率が一番高かった。最初の30分での溶出率が高い順に、PVA、「CMCNa+CaCl」、ペクチンであった。
 また、水に投入してから6時間後の溶出率を比較すると、バインダーとして「CMCNa+CaCl」を用いた場合、まだ溶出率が100%に達していなかったことから、薬効成分を長時間溶出させることができ、徐放性に優れていることが示唆された。
The results are shown in FIG. The sustained release of the active ingredient was confirmed for all binders. Pectin has a slow release rate and has a high ability to gradually release the active ingredient. On the other hand, PVA had the highest release rate in the first 30 minutes although sustained release. PVA, “CMCNa + CaCl 2 ” and pectin were in descending order of elution rate in the first 30 minutes.
In addition, when the elution rate after 6 hours from charging into water is compared, when “CMCNa + CaCl 2 ” is used as the binder, the elution rate does not reach 100% yet, and therefore the medicinal ingredient is eluted for a long time It is suggested that it is possible to
 水への浮遊性は、バインダーとして「CMCNa+CaCl」を用いた場合、すべての藻類抑制剤のフレークが水に浮遊したが、PVAやペクチンを用いた場合は、水に浮くものと沈むものが存在した。 The floatability to water, when "CMCNa + CaCl 2 " is used as a binder, all algal inhibitor flakes float in water, but when PVA or pectin is used, there are floating and sinking in water did.
 以上の結果から、水への浮遊性、溶出速度の制御、環境負荷等を総合的に考慮すると、溶出速度の制御の点から、ゲル状にならないPVAではなく、ゲル状になる「CMCNa+CaCl」やペクチンを使用しなくてはならず、その中でも、浮遊性の点から「CMCNa+CaCl」を使用することがより好ましいことが分かった。また、PVAは他に比べて環境負荷が大きいという欠点がある。 From the above results, the buoyant in water, the control of the dissolution rate, when comprehensively considering the environmental load, etc., from the viewpoint of control of elution rate, rather than the PVA does not become gelled, the gelled "CMCNa + CaCl 2" without using or pectin as well, among them, it has been found preferable to use "CMCNa + CaCl 2" in terms of floating. Moreover, PVA has the fault that environmental load is large compared with others.
 上記の通り、多糖類、カルボキシメチルセルロース、ケイ酸又はそれらの塩が、水への浮遊性及び溶出速度の制御に優れていることが確認されたが、コラーゲン又はそれらの塩も、水への浮遊性及び溶出速度の制御に優れている。 As described above, polysaccharides, carboxymethylcellulose, silicic acid or their salts were confirmed to be excellent in controlling the floatability and elution rate in water, but collagen or their salts also suspended in water. Excellent in control of the viscosity and dissolution rate.
実施例2
[藻類抑制剤の粒径の検討]
 次に、藻類抑制剤を顆粒状にし、その粒径を変えた時の、薬効成分の溶出率の変化を検討した。
 リジン塩酸塩とマロン酸に、CMCNaと塩化カルシウムを加えて造粒したフレーク状の薬剤に、コーティング剤としてECを被覆し藻類抑制剤を作製した。藻類抑制剤の組成は、藻類抑制剤全体に対して、リジン塩酸塩34質量%、マロン酸34質量%、CMCNa15質量%、塩化カルシウム15質量%、EC1質量%、水分1質量%であった。
 また、藻類抑制剤の粒径は、それぞれ約7mm、5mm、3mmのものを作製した。
 そして、実施例1と同様の手順・方法で、時間毎のマロン酸溶出率を測定した。
Example 2
[Examination of particle size of algae inhibitor]
Next, the algae inhibitor was granulated, and the change in the elution rate of the medicinal ingredient when the particle size was changed was examined.
A flake-form drug obtained by adding CMCNa and calcium chloride to lysine hydrochloride and malonic acid and granulating them was coated with EC as a coating agent to prepare an algal inhibitor. The composition of the algal inhibitor was 34% by mass of lysine hydrochloride, 34% by mass of malonic acid, 15% by mass of CMCNa, 15% by mass of calcium chloride, 1% by mass of EC, and 1% by mass of water based on the whole algae inhibitor.
Moreover, the particle size of the algae inhibitor was produced about 7 mm, 5 mm, and 3 mm, respectively.
Then, the malonic acid elution rate per hour was measured in the same manner as in Example 1.
 結果を図2に示す。粒径が大きいほど薬効成分の溶出速度が遅かった。したがって、抑制剤の粒径を変更することで溶出時間を制御することが可能であることが分かった。 The results are shown in FIG. The larger the particle size, the slower the dissolution rate of the medicinal ingredient. Therefore, it was found that it is possible to control the elution time by changing the particle size of the inhibitor.
実施例3
[コーティング剤の被覆量の検討]
 エチルセルロース(EC)の被覆量によって薬効成分の溶出速度に与える影響を検討した。
 リジン塩酸塩5gとマロン酸5gを混合し、該混合物にカルボキシメチルセルロースナトリウム(CMCNa)2gと塩化カルシウム2gを加え、更に水4gを加えてスラリー状にし、該スラリーを乾燥後フレーク状に成形することにより芯剤を得た。
 乾燥後の芯剤の組成は、藻類抑制剤全体に対して、リジン塩酸塩35質量%、マロン酸35質量%、CMCNa14質量%、塩化カルシウム14質量%、水分2質量%であった。
Example 3
[Examination of coating amount of coating agent]
The effect of the amount of ethyl cellulose (EC) coated on the dissolution rate of the active ingredient was examined.
Mix 5 g of lysine hydrochloride and 5 g of malonic acid, add 2 g of sodium carboxymethylcellulose (CMCNa) and 2 g of calcium chloride to the mixture, add 4 g of water to make a slurry, and dry the slurry to form flakes. The core agent was obtained by
The composition of the core after drying was 35% by mass of lysine hydrochloride, 35% by mass of malonic acid, 14% by mass of CMCNa, 14% by mass of calcium chloride, and 2% by mass of water based on the whole algae inhibitor.
 乾燥した芯剤に、コーティング剤としてECを、藻類抑制剤全体の質量に対し、1質量%、3質量%、5質量%、10質量%となるようにそれぞれ被覆して藻類抑制剤を作製した。比較としてECを被覆しない藻類抑制剤(コーティング剤0質量%)も作製した。
 そして、実施例1と同様の手順で、時間毎のマロン酸溶出率を測定した。
The dried core agent was coated with EC as a coating agent at 1% by mass, 3% by mass, 5% by mass, and 10% by mass with respect to the total mass of the algal inhibitor to prepare an algal inhibitor . An algae inhibitor (0% by mass of coating agent) not coated with EC was also prepared as a comparison.
Then, in the same manner as in Example 1, the malonic acid elution rate per hour was measured.
 結果を図3に示す。比較として作製した「ECを被覆しない藻類抑制剤(0%)」は、約0.5時間でマロン酸溶出率が飽和してしまい、約1時間で溶出率80%までに到達したのに対し、ECを被覆した藻類抑制剤(1%、3%、5%、10%)は、マロン酸溶出率が飽和するまでの時間が長く、溶出率80%に達するまで3時間以上を要した。
 この結果から、コーティング剤(EC)を被覆することで薬効成分の溶出速度を抑えることができることが分かった。また、ECの被覆量が多くなると、該溶出速度がより遅くなることも示された。
 以上の結果から、コーティング剤(EC)の被覆量を調節することで、薬効成分の溶出速度を制御することが可能であることが分かった。
The results are shown in FIG. "Algal inhibitor (0%) which does not coat EC" prepared as a comparison, the malonic acid elution rate became saturated in about 0.5 hours, and it reached to the elution rate up to 80% in about 1 hour The EC-coated algal inhibitor (1%, 3%, 5%, 10%) took a long time to saturate the malonic acid elution rate, and required 3 hours or more to reach the elution rate of 80%.
From this result, it was found that the dissolution rate of the medicinal ingredient can be suppressed by coating the coating agent (EC). It was also shown that the higher the EC coverage, the slower the elution rate.
From the above results, it was found that it is possible to control the elution rate of the medicinal ingredient by adjusting the coating amount of the coating agent (EC).
実施例4
[コーティング剤の被覆量の検討]
 実施例3と同様の実験を行い、コーティング剤としてフュームドシリカ(疎水性シリカRX300-5、日本アエロジル株式会社製)を用いた場合、該被覆量による薬効成分の溶出速度に与える影響を検討した。
 純水にリジン塩酸塩とマロン酸を同量溶解させ、そこに3号ケイ酸ソーダを加えてゲル化させた。ケイ酸ソーダ中に含まれている組成式NaOの分の換算質量がマロン酸の質量と同じになるように加えることでゲル化を好適に起こさせることができる。
Example 4
[Examination of coating amount of coating agent]
The same experiment as in Example 3 was carried out, and when fumed silica (hydrophobic silica RX 300-5, manufactured by Nippon Aerosil Co., Ltd.) was used as a coating agent, the influence of the coating amount on the dissolution rate of the medicinal ingredient was examined. .
Lysine hydrochloride and malonic acid were dissolved in equal amounts in pure water, and sodium silicate No. 3 was added thereto to cause gelation. The gelation can be suitably caused by adding so that the converted mass of the component of the formula Na 2 O contained in sodium silicate becomes the same as the mass of malonic acid.
 ゲル化したものを造粒し乾燥させて芯剤を作製した。作製した芯剤に、コーティング剤としてフュームドシリカ(FS)を被覆することにより、藻類抑制剤を作製した。FSの被覆量は、藻類抑制剤全体の質量に対し、1質量%、3質量%、5質量%、7質量%、9質量%となるようにそれぞれ被覆した。
 そして、実施例1と同様の手順・方法で、時間毎のマロン酸溶出率を測定した。
The gelled product was granulated and dried to prepare a core. An algae inhibitor was produced by coating the produced core agent with fumed silica (FS) as a coating agent. The coating amount of FS was 1 mass%, 3 mass%, 5 mass%, 7 mass%, and 9 mass% with respect to the mass of the whole algae inhibitor, respectively.
Then, the malonic acid elution rate per hour was measured in the same manner as in Example 1.
 結果を図4に示す。FSの被覆量が増加するに従い、マロン酸の溶出速度が遅くなることが分かった。この結果から、FSの被覆量によって溶出速度の制御が可能であることが分かった。
 また、実施例3及び実施例4の結果から、藻類抑制剤表面をコーティング剤で被覆することで溶出速度を遅くし、溶出時間をコントロールすることが可能であることが分かった。
 なお、被覆量を増加させるにつれて薬効成分の溶出時間を延長させることも可能である一方、被覆量が過剰の場合、時間毎の薬効成分の濃度増加が少なく、該溶出率が下がることにより、藻類抑制の効果が低くなる可能性がある。
The results are shown in FIG. It was found that the dissolution rate of malonic acid became slower as the amount of FS coating increased. From this result, it was found that the dissolution rate can be controlled by the amount of FS coating.
Moreover, it turned out that it is possible to slow the elution rate and to control the elution time by coating the algae inhibitor surface with a coating agent from the results of Example 3 and Example 4.
In addition, while it is possible to extend the elution time of the medicinal ingredient as the coating amount is increased, when the coating amount is excessive, the concentration increase of the medicinal ingredient with time is small and the elution rate is lowered. The effectiveness of the suppression may be reduced.
 図3及び図4で示すように、コーティング剤の被覆量が、それぞれ10質量%や9質量%の場合は、時間毎の溶出率が低いため、コーティング剤の被覆量は、藻類抑制剤全体の質量に対し、1質量%~7質量%程度が特に好ましい範囲であることが分かった。 As shown in FIG. 3 and FIG. 4, when the coating amount of the coating agent is 10% by mass and 9% by mass, respectively, the elution rate per hour is low, so the coating amount of the coating agent is It has been found that about 1% by mass to about 7% by mass is a particularly preferable range with respect to the mass.
 上記のように、コーティング剤として、エチルセルロース(EC)及びフュームドシリカを用いることで、薬効成分の溶出速度を制御することが可能であることが確認されたが、カルボキシメチルセルロースカルシウム、アルギン酸カルシウム、ヒドロキシプロピルメチルセルロース、セルロース、蜜蝋及びシェラックでも、コーティング剤として使用することで、薬効成分の溶出速度の制御が可能である。 As described above, it has been confirmed that it is possible to control the elution rate of medicinal ingredients by using ethylcellulose (EC) and fumed silica as a coating agent, but calcium carboxymethylcellulose, calcium alginate, hydroxy By using propyl methyl cellulose, cellulose, beeswax and shellac as the coating agent, it is possible to control the dissolution rate of the medicinal ingredient.
 本発明の藻類抑制剤は、様々な水環境下における藻類の抑制や藻類の繁殖を抑制するために使用することができるので、国、公共団体、管理団体、会社等、水環境を管理・調整する分野で広く利用されるものである。 The algae inhibitor of the present invention can be used to control algae and algae reproduction under various water environments, and therefore the water environment can be managed and adjusted by countries, public organizations, management organizations, companies, etc. Widely used in the field of
 本願は、2015年12月17日に出願した日本の特許出願である特願2015-246428に基づくものであり、それらの出願の全ての内容はここに引用し、本願発明の明細書の開示として取り込まれるものである。

 
This application is based on Japanese Patent Application No. 2015-246428, which is a Japanese patent application filed on Dec. 17, 2015, the entire contents of those applications are incorporated herein by reference and disclosed in the specification of the present invention. It is taken in.

Claims (8)

  1.  水面に浮遊させて該水面に浮遊する藻類を抑制する藻類抑制剤であって、
     少なくとも、リジン若しくはリジン塩及びマロン酸若しくはマロン酸塩からなる薬効成分、並びに、該薬効成分を保持するバインダーを含有する芯剤と、
     該芯剤の表面に存在し薬効成分の徐放性を制御するコーティング剤と、
    を有してなるものであることを特徴とする藻類抑制剤。
    It is an algal inhibitor which is suspended on the water surface to suppress algae floating on the water surface,
    A pharmaceutically active ingredient comprising at least a lysine or lysine salt and malonic acid or malonate, and a core agent containing a binder for retaining the pharmaceutically active ingredient,
    A coating agent which is present on the surface of the core agent and controls the sustained release of the pharmacologically active ingredient;
    An algal inhibitor characterized by comprising.
  2.  上記バインダーが、「天然物由来の高分子」及び「非環境汚染物質」からなる群より選ばれる成分である請求項1に記載の藻類抑制剤。 The algae inhibitor according to claim 1, wherein the binder is a component selected from the group consisting of "polymers derived from natural products" and "non-environmental pollutants".
  3.  上記コーティング剤が、上記薬効成分の徐放速度を制御し、散布後30分以上に亘り上記薬効成分を溶出し続けさせるものである請求項1又は請求項2に記載の藻類抑制剤。 The algal inhibitor according to claim 1 or 2, wherein the coating agent controls the sustained release rate of the pharmaceutically active ingredient, and continuously elutes the pharmaceutically active ingredient for 30 minutes or more after the application.
  4.  上記薬効成分中、リジンとリジン塩の合計質量に対するマロン酸とマロン酸塩の合計質量の割合が0.1以上2以下である請求項1ないし請求項3の何れかの請求項に記載の藻類抑制剤。 The algae according to any one of claims 1 to 3, wherein the ratio of the total mass of malonic acid and malonate to the total mass of lysine and lysine salt is 0.1 or more and 2 or less in the above-mentioned medicinal ingredients. Inhibitor.
  5.  上記藻類抑制剤全体を100質量部としたとき、上記コーティング剤を、1質量部以上10質量部以下で有してなる請求項1ないし請求項4の何れかの請求項に記載の藻類抑制剤。 The algae inhibitor according to any one of claims 1 to 4, wherein the coating agent is contained in an amount of 1 to 10 parts by mass based on 100 parts by mass of the entire algae inhibitor. .
  6.  請求項1ないし請求項5の何れかの請求項に記載の藻類抑制剤の製造方法であって、
     リジン若しくはリジン塩及びマロン酸若しくはマロン酸塩からなる薬効成分の混合粉体に、上記天然物由来の高分子と水を加えてスラリー状にする工程、該スラリーを乾燥する工程、及び、造粒する工程とを含むことを特徴とする藻類抑制剤の製造方法。
    A method for producing an algal inhibitor according to any one of claims 1 to 5,
    A step of adding a polymer derived from the above-mentioned natural product and water to a mixed powder of lysine or lysine salt and a medicinal component consisting of malonic acid or malonate to form a slurry, drying the slurry, and granulation A process for producing an algal inhibitor, comprising the steps of
  7.  請求項1ないし請求項5の何れかの請求項に記載の藻類抑制剤の製造方法であって、
     リジン若しくはリジン塩及びマロン酸若しくはマロン酸塩からなる薬効成分の混合粉体に、上記非環境汚染物質と水を加えて溶液状にした後、該溶液にゲル化剤を加えてゲル状にする工程、該ゲルを乾燥する工程、及び、造粒する工程とを含むことを特徴とする藻類抑制剤の製造方法。
    A method for producing an algal inhibitor according to any one of claims 1 to 5,
    The above non-environmental pollutants and water are added to a mixed powder of lysine or lysine salt and a medicinal component consisting of malonic acid or malonate to form a solution, and then a gelling agent is added to the solution to form a gel. A method for producing an algal inhibitor, comprising the steps of: drying the gel; and granulating.
  8.  請求項1ないし請求項5の何れかの請求項に記載の藻類抑制剤を使用した藻類の抑制方法であって、
     水1m当たりに、該藻類抑制剤を1g以上100g以下投入し、
     コーティング剤によって薬効成分の徐放速度を制御し、散布後30分以上に亘り、該水面に該藻類抑制剤から薬効成分を溶出し続けさせることを特徴とする藻類の抑制方法。
     
     

     
    A method of suppressing algae using the algae inhibitor according to any one of claims 1 to 5,
    Add 1 g or more and 100 g or less of the algae inhibitor per 1 m 2 of water,
    A method for controlling algae, which comprises controlling the sustained release rate of a medicinal ingredient with a coating agent and continuously eluting the medicinal ingredient from the algae inhibitor on the water surface for 30 minutes or more after spraying.



PCT/JP2016/085033 2015-12-17 2016-11-25 Algae inhibitor, method for producing algae inhibitor and algae inhibition method WO2017104384A1 (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04200628A (en) * 1990-11-29 1992-07-21 Agency Of Ind Science & Technol Method of coating fine particulate by spray dry method
JPH05255067A (en) * 1991-04-25 1993-10-05 Takeda Chem Ind Ltd Floatable preparation and its production
WO1995031899A1 (en) * 1994-05-24 1995-11-30 Nippon Shinyaku Co., Ltd. Pesticide composition, pesticidal preparation, and production process
JPH11502229A (en) * 1995-03-17 1999-02-23 リー カウンティー モスキート コントロール ディストリクト Controlled feed composition and method of biological treatment in the environment
JP2005246144A (en) * 2004-03-01 2005-09-15 Kureha Techno Enji Kk Algae control method
JP2012036182A (en) * 2010-07-15 2012-02-23 Kyoyu Agri Kk Sustained-release microparticle and drug formulation containing the sustained-release microparticle

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS459560Y1 (en) * 1966-01-19 1970-05-04
JP3130141B2 (en) * 1991-09-27 2001-01-31 三共株式会社 Pesticide composition and method of application
JPH0656604A (en) * 1992-08-07 1994-03-01 Hodogaya Chem Co Ltd Herbicide for paddy field
JPH0790121A (en) * 1993-09-22 1995-04-04 Dai Ichi Kogyo Seiyaku Co Ltd Production of gel of sodium salt of carboxymethylcellulose
JPH07215803A (en) * 1994-02-03 1995-08-15 Sumitomo Chem Co Ltd Agrochemical composition
JPH09132503A (en) * 1995-11-08 1997-05-20 Hokko Chem Ind Co Ltd Elusion-controlled solid agrochemical formulation and its production
JP2002053405A (en) * 2000-08-08 2002-02-19 Aventis Cropscience Gmbh Agrochemical preparation floating on water surface
JP2005263858A (en) * 2004-03-16 2005-09-29 Research Institute Of Innovative Technology For The Earth Water absorbing material, method for producing the same and water absorbing article
CN100347102C (en) * 2005-12-31 2007-11-07 清华大学 Method for suppressing algae growth using giantreed
JP5449914B2 (en) * 2008-08-07 2014-03-19 石原産業株式会社 Agricultural composition for paddy field
CN101993149B (en) * 2009-08-31 2013-05-01 黄炽林 Water quality conditioner for inhibiting harmful algae and use method thereof
CN102351254B (en) * 2011-06-21 2013-09-18 淮安自来水有限公司 Method for killing water surface algae

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04200628A (en) * 1990-11-29 1992-07-21 Agency Of Ind Science & Technol Method of coating fine particulate by spray dry method
JPH05255067A (en) * 1991-04-25 1993-10-05 Takeda Chem Ind Ltd Floatable preparation and its production
WO1995031899A1 (en) * 1994-05-24 1995-11-30 Nippon Shinyaku Co., Ltd. Pesticide composition, pesticidal preparation, and production process
JPH11502229A (en) * 1995-03-17 1999-02-23 リー カウンティー モスキート コントロール ディストリクト Controlled feed composition and method of biological treatment in the environment
JP2005246144A (en) * 2004-03-01 2005-09-15 Kureha Techno Enji Kk Algae control method
JP2012036182A (en) * 2010-07-15 2012-02-23 Kyoyu Agri Kk Sustained-release microparticle and drug formulation containing the sustained-release microparticle

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