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

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

ALGAE INHIBITOR, METHOD FOR PRODUCING THE ALGAE INHIBITOR AND METHOD FOR INHIBITING ALGAE

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.

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.

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.

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.

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.

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 ".

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".

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.

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

JP, 2005-246144, A Japanese Patent Application Publication No. 2003-113012 JP, 2013-209326, A

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.

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

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.

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.

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.

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.

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.

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.

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.
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.

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.

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.

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. 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. 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. 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.

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.

<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.

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.

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.

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.
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".

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.

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.

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.

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.

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 .

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".

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.

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.

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.

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.

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.

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.

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.
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.

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.

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.

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.

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.

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.

<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.

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.

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.

<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.

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.

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.

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. Examples of 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.

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.

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.

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.

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.

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.

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.

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.

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

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.

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.

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.

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.

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.

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.

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.

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).

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.

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 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.

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.

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.

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

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. 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. 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. 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. 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. 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. 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. 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. 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.
   
   
   
   

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