JPWO2017104384A1 - Algae inhibitor, method for producing the algae inhibitor, and method for inhibiting algae - Google Patents

Abstract

The present invention relates to an algal inhibitor that floats on the water surface and suppresses algae floating on the water surface, and retains at least the medicinal component consisting of lysine or lysine salt and malonic acid or malonate, and the medicinal component An algae inhibitor comprising: a wicking agent containing a binder, and a coating agent that is present on the surface of the wicking agent and controls the sustained release of a medicinal component; and the algae The present invention relates to a method for producing an inhibitor and a method for inhibiting algae. The binder is preferably a component selected from the group consisting of “natural polymer-derived polymer” and “non-environmental pollutant”.

Description

  The present invention relates to an algae inhibitor having at least a core agent containing a specific medicinal component and a coating agent, a method for producing the algae inhibitor, and a method for inhibiting algae.

In recent years, in the water environment such as lakes and dams, destruction of ecosystems, bad odor, deterioration of water quality, etc. due to mass growth of algae such as blue sea cucumber have become problems. In particular, blue sea bream and the like have produced toxic substances, and as a result, many cases of terrestrial animals as well as underwater animals have been reported. In addition, blue sea bream etc. proliferate by photosynthesis by levitating on the water surface during sunlight, thus blocking the light path into water and inhibiting the photosynthesis of other photosynthetic organisms. After sunshine stays in the 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 growth is urgently desired, and many studies have been conducted so far.

The main algae removal methods include, for example, draining all the water from the pond and replacing the water, continuing to filter for a long time, implementing dredging, and forcing convection with physical energy. Examples include raising and stirring, spraying a coagulating sedimentation agent, and sedimenting on the bottom surface. However, none of them was effective because it took too much time and cost or the environmental load was too large.
Thus, a means for removing algae with low cost and low environmental load is desired.

For example, Patent Document 1 discloses an algal control method using a liquid in which lysine and malonic acid are mixed. It is also disclosed that 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 mixed with lysine and malonic acid, a large amount of aqueous solution is sprayed on the algae in consideration of the effect of dilution due to diffusion into water. It was necessary to spray the liquid directly.

In addition, blue-green algae such as blue-green algae float on the water surface during sunshine hours, but sink when the sunshine time is over, and it is necessary to consider this point when suppressing, but the method of Patent Document 1 The characteristics could not be considered.
Furthermore, cyanobacteria move by being blown by the wind when they are floating, so when spraying a liquid inhibitor, they must be sprayed directly to the breeding site of cyanobacteria during the day. Therefore, for example, when cyanobacteria move in the wind, there is a problem that it must be sprayed again at the moving place.

Patent Document 2 discloses a floating water-floor-suppressing granule material for pond marsh that is formed by granulating a mixture of an organic material, a water-filling inhibitor, a specific gravity adjusting material, and a binder into a porous granule. The aquatic suppressive granule is a solid aquatic inhibitor that floats on the surface of the water. However, the sustained release property is not taken into consideration, and there is no description or suggestion of means for continuing to elute medicinal ingredients.
Moreover, the active ingredient of the aiko suppression granule of patent document 2 is an inorganic compound, such as a hydroxide of zinc and a hydroxide of copper, and has a large environmental load, and the technology is an organic substance. It was not applicable to an active ingredient consisting of “lysine or lysine salt” and “malonic acid or malonate”.

Patent Document 3 discloses a floatable package that suppresses the growth of phytoplankton by floating in water and gradually releasing a constant concentration of hydrogen peroxide. However, hydrogen peroxide is not specifically suppressed only by cyanobacteria such as blue-green algae, and it may have an adverse effect on the organisms of the lake.
Moreover, although it is disclosed that hydrogen peroxide is released at a constant concentration, there is no specific description or suggestion regarding the adjustment (method) of the rate.
Furthermore, the technique for gradually releasing hydrogen peroxide has not been applicable to an active ingredient composed of “lysine or lysine salt” and “malonic acid or malonate” which are organic substances.

  That is, none of the above patent documents specifically disclose a drug that floats on the water surface and the elution time of a medicinal component is adjusted, and a method for suppressing algae using the drug. In addition, there are hardly any problems, objectives for solving problems, awareness of problems, etc. about the constitution / physical properties of algae inhibitors corresponding to the above.

  The demand for an algal inhibitor with low environmental impact and high efficiency (high inhibitory effect) has been increasing in recent years. However, with the above-mentioned known technologies, suitable suppression of algae is insufficient and further improvement is required. There was room for.

JP 2005-246144 A JP 2003-1113012 A JP2013-209326A

  The present invention has been made in view of the above-described background art, and its problem is to solve the above problems, develop a drug that floats on water and has a controlled elution time of medicinal ingredients, and is simple and efficient. It is to provide an algae-inhibiting agent with a small environmental impact.

As a result of intensive investigations to solve the above problems, the present inventors have made the inhibitor contain a specific medicinal component and a specific component to form a core, and further, the surface of the core is coated with a coating agent. By coating, the medicinal component contained in the core agent can be released slowly, so that it is possible to exert the effect in accordance with the ecology of the sea bream, and the inhibitor is suspended on the water surface. The present inventors have found that the effect of efficiently suppressing “Aokko floating on the surface” can be imparted.
In addition, the inventors have found that an algal inhibitor having a desired sustained release property (elution rate) corresponding to the characteristics of the algae can be obtained depending on the composition of the core agent, the coating amount of the coating agent, and the like, thereby completing the present invention. It was.

That is, the present invention is an algae inhibitor that floats on the water surface and suppresses algae floating on the water surface,
A core agent containing at least a medicinal component composed of lysine or lysine salt and malonic acid or malonate, and a binder holding the medicinal component;
A coating agent that is present on the surface of the core agent and controls the sustained release of the medicinal component;
It is an algae inhibitor characterized by comprising.

Further, the present invention is a method for producing the algae inhibitor,
A step of adding a polymer and water derived from the above natural product to a powder mixture of medicinal ingredients composed of lysine or lysine salt and malonic acid or malonate to form a slurry, a step of drying the slurry, and granulation A method for producing an algae inhibitor comprising the steps of:

Further, the present invention is a method for producing the algae inhibitor,
Add the above non-environmental pollutant and water to a powder mixture of medicinal ingredients composed of lysine or lysine salt and malonic acid or malonate to form a solution, and then add a gelling agent to the solution to form a gel. It is a manufacturing method of the algae inhibitor characterized by including the process, the process of drying this gel, and the process of granulating.

Further, the present invention is a method for inhibiting algae using the algae inhibitor,
1 g to 100 g of the algal inhibitor per 1 m ^{2 of} water,
The method for inhibiting algae is characterized in that the controlled release rate of a medicinal ingredient is controlled by a coating agent, and the medicinal ingredient is continuously eluted from the algae inhibitor on the water surface for 30 minutes or more after spraying.

  ADVANTAGE OF THE INVENTION According to this invention, the said problem and the said subject can be solved, and algae, such as a sea cucumber which generate | occur | produces in a pond, a lake, etc., can be suppressed. In particular, since the algal inhibitor of the present invention floats on the water surface, the algae floating on the water surface can be efficiently suppressed.

The algal inhibitor of the present invention contains a binder that retains a medicinal component, and further, a “core agent that contains a medicinal component and a binder” is coated with a coating agent, so that the sustained release rate of the medicinal component is adjusted. Can do. Algae can be efficiently suppressed by adjusting the sustained release rate.
For example, the sustained release rate is defined by the release amount per unit time of a medicinal component 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 depending on the composition of the core of the algal inhibitor, the composition and coating amount of the coating agent, the shape and size of the algal inhibitor, etc. The algal inhibitor according to the can be provided.

The lysine or lysine salt and malonic acid or malonate, which are medicinal components of the algal inhibitor of the present invention, dissolve in water and diffuse into water, or diffuse independently into the water surface where no algae are present. In some cases, by blending with the algal inhibitor of the embodiment of the present invention, it is possible to stay on the surface of the water, and to move with the algae floating on the surface of the water by wind, waves, water flow, etc. Can be efficiently suppressed.
In addition, “lysine or lysine salt and malonic acid or malonate” have high solubility in water and readily dissolve and diffuse in water. However, when added to the algal inhibitor having the aspect of the present invention, The release rate can be adjusted, and the suppression suitable for the characteristics of algae such as blue-green can be achieved.

In addition, since the algal inhibitor of the present invention has a coating agent on the surface, it can maintain a medicinal effect for a long time after being dropped on a pond or a lake where the algal inhibitor is to be suppressed, and wind etc. Can move the water surface together with algae, and the medicinal effect can be used efficiently. Therefore, algal reproduction can be efficiently suppressed with a small amount of algal inhibitor. In particular, since the medicinal component can be brought into contact with the algae only when it floats on the water surface in summer, the algae can be suppressed extremely efficiently.
Moreover, since the algae inhibitor of this invention moves a water surface with a wind etc., it can suppress the algae of the place where direct spraying is difficult.

  Moreover, since the medicinal component of the algal inhibitor of the present invention is effective only for specific cyanobacteria in the algae, it does not adversely affect other ecology. In addition, since the medicinal component is highly soluble and the other substances constituting the algal inhibitor are biodegradable or low environmental load substances, the algal inhibitor of the present invention has a low environmental load.

It is a graph which shows the change of the elution rate of a medicinal ingredient when the composition of a core agent is changed. It is a graph which shows the change of the elution rate of a medicinal ingredient when changing the particle size of an algal inhibitor. It is a graph which shows the change of the elution rate of a medicinal ingredient when the coating amount of a coating agent (EC) is changed. It is a graph which shows the change of the elution rate of a medicinal ingredient when changing the coating amount of a coating agent (fumed silica).

  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.

<Algae inhibitor>
The algal inhibitor of the present invention is an algal inhibitor that floats on the water surface and suppresses the algae floating on the water surface, at least a medicinal component consisting of lysine or lysine salt and malonic acid or malonate, and the It is characterized by comprising a core containing a binder that holds a medicinal component and a coating agent that exists on the surface of the core and controls the sustained release of the medicinal component.

The algal inhibitor of the present invention is used for algal growth control, floating control, and the like. Here, “suppression” means a decrease in number or density. The algae inhibitor of the present invention reduces and inhibits algae by inhibiting reproduction.
Among algae, it is preferably used for suppressing cyanobacteria, more preferably used for suppressing cyanobacteria belonging to the genus Microcystis, and particularly preferably used for suppressing blue-green algae.
Microcystis viridis, Microcystis aeruginosa, Microcystis wesenbergii, etc. are examples of the species that form blue sea bream. Therefore, it is particularly preferable.

  Since the algal inhibitor of the present invention floats on the water surface, it is also characterized by inhibiting algae floating on the water surface, but it does not exclude the suppression of algae in the water, but suppresses algae in the water or at the bottom of the water. Can also be used. The algae inhibitor can suppress algae and the like adhering to the cocoons present on the bottom of the water by a medicinal component.

  The algal inhibitor of the present invention has a core agent. The core contains a medicinal component and a binder that holds the medicinal component.

The medicinal component consists of lysine or lysine salt and malonic acid or malonate.
The “lysine or lysine salt” is not limited, and specific examples include lysine, lysine hydrochloride, lysine acetate, lysine glutamate, lysine aspartate, and the like. It is particularly preferable to use lysine hydrochloride as the “lysine or lysine salt”.
The “malonic acid or malonate” is not limited, but specific examples include malonic acid, sodium malonate, potassium malonate, magnesium malonate, calcium malonate, and the like. As the “malonic acid or malonic acid salt”, it is particularly preferable to use malonic acid.

  Needless to say, “lysine or lysine salt” may be one of lysine and lysine salt, or a mixture of both. Moreover, it goes without saying that “malonic acid or malonate” may be either malonic acid or malonate, or a mixture of both.

The binder is preferably a component selected from the group consisting of “natural product-derived polymer” and “non-environmental pollutant”. “Natural product-derived polymer” or “non-environmental pollutant” is used alone. Alternatively, “natural polymer-derived polymer” and “non-environmental pollutant” may be used in combination.

In addition, as the above-mentioned polymers derived from natural products, carrageenan, gelatin, pectin, agarose, starch, collagen, pullulan, mannan, dextrin, cellulose, etc. are non-toxic, have a relatively low environmental impact, and absorb water. It is preferable from the point of being excellent in the gelation performance to become a gel and being easily decomposed naturally.
One selected from these can be used alone or in combination of two or more.

Examples of the non-environmental pollutants include substances that have a low environmental impact and are approved for use in feed additives and food additives, and substances composed of clay minerals that exist in large quantities in nature. . Specific examples include silicates such as sodium silicate, carboxymethylcellulose, sodium carboxymethylcellulose, sodium alginate, and the like.
One selected from these can be used alone or in combination of two or more.
The non-environmental pollutant preferably contains a gelling agent.
For example, the silicate described above preferably contains an inorganic acid or an organic acid as a gelling agent. The inorganic acid or organic acid can gel the silicate by neutralization.
The carboxymethyl cellulose, sodium carboxymethyl cellulose, sodium alginate and the like preferably contain a polyvalent cation-containing compound such as calcium chloride, magnesium chloride or aluminum chloride as a gelling agent.
Accordingly, the gelling agent contained in the non-environmental pollutant is particularly preferably an inorganic acid or organic acid or a polyvalent cation-containing compound. The gelling agent may also serve as the medicinal component.

A preferred binder is, specifically, a compound selected from the group consisting of silicic acid, polysaccharides, carboxymethylcellulose, and collagen, or a salt thereof for the reasons described above.
Here, the “polysaccharide” includes complex polysaccharides. The “silicic acid salt” includes a sodium salt of metasilicic acid represented by a composition formula (Na ₂ O) (SiO ₂ ) or Na ₂ SiO ₃ .

Particularly preferable binders include the following for the above reasons.
Examples of the “silicic acid or a salt thereof” include silicic acid, sodium silicate, and those obtained by reacting sodium silicate with an acid (aqueous solutions are water glass Nos. 1-4).
As the above-mentioned “polysaccharide or salt thereof”, amylose (starch), cellulose, agarose, carrageenan, pectin, sodium alginate, “sodium alginate, pectin and the like obtained by reacting a cation-containing substance with a valence of 2 or more” Etc.
Examples of the carboxymethyl cellulose or a salt thereof include carboxymethyl cellulose, “obtained by reacting carboxymethyl cellulose with a divalent or higher cation-containing material”, and the like.
Gelatin etc. are mentioned as said "collagen or its salt."

  From the viewpoint of adjusting the sustained release rate of the medicinal component and reducing the environmental load, it is more preferable to use a material having a high biodegradability and / or a low environmental load as the binder. More preferable binders include sodium silicate, amylose (starch), agarose, carrageenan, pectin, sodium alginate, “obtained by reacting carboxymethyl cellulose with a divalent or higher cation-containing substance”, collagen, gelatin and the like. Can be mentioned.

  Moreover, it is more preferable to use a material having a high biodegradability and / or a low environmental load as the binder from the viewpoint of adjusting the sustained release rate of the medicinal component and reducing the environmental load. In this respect, more preferable binders include pectin, gelatin, starch, “carboxymethylcellulose sodium and calcium chloride”, “silicate and acid”, sodium alginate and calcium chloride, and the like.

Regarding the preparation of the binder, “natural polymer-derived polymer” and “non-environmental pollutant” are preferably carried out by dispersing or dissolving them in water as a slurry.
Further, when the “non-environmental pollutant” and the gelling agent are used in combination, it is preferable that the gelling agent is also made into an aqueous solution (or fine dispersion) and then mixed with each other.
In any case, after drying, if it is not granulated or flaked after drying (if necessary), it is pulverized into granules or flakes, and the resulting product is used as a core (or a component of the core). It is preferable to do.
It is possible to dissolve medicinal ingredients in an aqueous solution of “naturally occurring polymer” or “non-environmental pollutant”, dry them, and prepare a core by the above method. It is preferable from the viewpoint that the medicinal component contained inside the core becomes sustained-released.

The algal inhibitor of the present invention has “a coating agent that exists on the surface of the core agent and controls the sustained release of the medicinal component” as an essential member.
In this specification, “coating” includes the meanings of “coating, application, external addition, application”.
As the coating agent, it is preferable to use a substance having high biodegradability and / or low environmental load from the viewpoints of floatability on the water surface, adjustment of the sustained release rate of the medicinal component and reduction of environmental load. In addition, although it will become difficult to float on water if a coating agent is taken, the algae which exist in a water bottom can also be suppressed by releasing a medicinal component in a water bottom.

  The coating agent is preferably one that controls the sustained release rate of the medicinal component and continues to elute the medicinal component for 30 minutes or more after the algae inhibitor is sprayed. It is more preferable that the above-mentioned medicinal component is continuously eluted over the above, and it is particularly preferable that the above-mentioned medicinal component is continuously eluted for 2 hours or more after the algae inhibitor is sprayed.

Although it does not specifically limit as a preferable coating agent, For example, hydrophobic members, such as ethyl cellulose (EC), a cellulose, fumed silica (FS), beeswax, shellac, etc .; Carboxymethylcellulose calcium, calcium alginate, hydroxypropyl Examples thereof include compounds selected from the group consisting of gelling substances such as methylcellulose. One selected from these can be used alone or in combination of two or more.
Such a compound is preferable from the above point, and ethyl cellulose or fumed silica is particularly preferable from the above point.
As the fumed silica, either a hydrophilic one or a hydrophobic one is preferably used. By performing the surface treatment of fumed silica, hydrophilicity and hydrophobicity can be controlled. The above effects are exhibited in any surface state, but those subjected to hydrophobic treatment are preferably used. The fumed silica that has been hydrophobically treated exhibits the above-described effects in particular, and the sustained release rate can be controlled by the hydrophobicity. Depending on the intended use, the type of fumed silica can be selected as appropriate.

The method for applying the coating agent to the core agent is not particularly limited as long as it can cover the surface of the core agent suitably, but what can be made into a solution is applied to the surface of the core agent as a solution, Thereafter, a method of evaporating the solvent is preferred.
In addition, it is preferable to add fumed silica, cellulose or the like which is difficult to be easily made into a solution to the surface of the core as it is.

The algal inhibitor of the present invention is solid, and the shape thereof can be appropriately selected according to the purpose. Specific examples include granules, flakes, tablets, and granules.
When the algal inhibitor is granular, tablet, or granular, the number average diameter is 0 from the viewpoints of controlling the sustained release rate of the medicinal ingredient and the floating property and dispersibility of the algal inhibitor on the water surface. 0.05 mm to 30 mm is preferable, 0.1 mm to 15 mm is more preferable, and 0.5 mm to 10 mm is particularly preferable.
When the algal inhibitor is in the form of flakes, the thickness is preferably 0.03 mm to 3 mm from the viewpoint of adjusting the sustained release rate of the medicinal component and the floating property of the algal inhibitor on the water surface. It is more preferably 0.05 to 2 mm, and particularly preferably 0.1 mm to 1 mm.

The ratio of the total mass of “malonic acid and malonate” with respect to the total mass of “lysine and lysine salt” in the medicinal component 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, Most preferably, it is 0.3 or more and 1.5 or less.
The “total mass” includes the case where only one of “lysine and lysine salt” is contained and the case where only one of “malonic acid and malonate” is contained as a concept.

The content of the medicinal ingredient when the whole core is 100 parts by mass is not particularly limited and can be appropriately selected according to the purpose, but the content of the medicinal ingredient is 10 to 90 parts by mass. Preferably, 15 to 80 parts by mass are more preferable, and 20 to 70 parts by mass are particularly preferable.
When there is too much content of a medicinal ingredient, the suitable quantity of the alga inhibitor to spread | spread will reduce, and it may become difficult to disperse | distribute uniformly on the water surface, or it may not become sustained release property. On the other hand, if the content of the medicinal component is too small, the amount of algae inhibitor to be spread may increase, or an environmental load may be caused by too much binder.

  Moreover, the core agent in the algal inhibitor of the present invention can 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 does not impair the effect of this invention, For example, activated carbon, iron oxide, calcium oxide (Water quality, such as adsorption | suction of phosphorus, etc.) Improvement purpose), sawdust, wood flour, aquatic plant seeds and the like.

  When the total alga inhibitor is 100 parts by mass, the content of the coating agent is not particularly limited and can be appropriately selected depending on the purpose. 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 more preferably 1 part by mass or more and 7 parts by mass or less. Particularly preferred.

  Moreover, the algal inhibitor of the present invention can “mix other components” with “other members” in addition to the core agent and the coating agent. The “other member” is not particularly limited and may be appropriately selected depending on the purpose within a range not impairing the effects of the present invention. For example, activated carbon, iron oxide, calcium oxide, sawdust, wood flour, aquatic Examples include plant seeds.

<Manufacturing method>
The production method of the present invention is a method for producing the algae inhibitor described above, wherein a mixed powder of “medicine ingredient consisting of“ lysine or lysine salt ”and“ malonic acid or malonate ”” is derived from the natural product. It includes a step of adding a polymer and water to form a slurry, a step of drying the slurry, and a step of granulating.

  Further, the production method of the present invention is a method for producing the algae inhibitor described above, wherein the non-environmental mixture powder is mixed with a “medicinal ingredient comprising“ lysine or lysine salt ”and“ malonic acid or malonate ””. It includes a step of adding a pollutant and water to form a solution, then adding a gelling agent to the solution to form a gel, a step of drying the gel, and a step of granulating.

The slurry or gel can be dried using a known drying apparatus. 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 granulated while being dried, and may be appropriately selected according to the purpose.
When moisture evaporates during drying and air bubbles remain in the algal inhibitor, the specific gravity of the algal inhibitor becomes lighter than water, so that it can be floated on the water surface for a long time or better.

The production method of the present invention includes a step of coating the above-mentioned coating agent on a (preferably dried) core agent.
Known means can be used as means for applying the coating agent to the core. For example, there are a method in which a coating agent is dissolved in a solvent and then sprayed onto the molded core, and a method in which a solid coating agent is applied to or attached to the molded core.

<Algae control method>
The method for inhibiting algae according to the present invention is a method for inhibiting algae using the algae inhibitor described above, wherein 1 g or more and 100 g or less of the algae inhibitor are introduced per 1 m ^{2 of} water, and the gradual release of the medicinal component by the coating agent is performed. The rate is controlled, and the medicinal component is continuously eluted from the algal inhibitor on the water surface for 30 minutes or more after spraying.

If the algae inhibitor is sprayed within 30 hours of sunshine and the medicinal components continue to elute for more than 30 minutes, algae such as sea cucumbers will rise from the water and float on the water surface. The medicinal component from the algal inhibitor of the present invention is preferable because it directly affects the algae.
If the medicinal components are completely eluted in less than 30 minutes, the percentage of medicinal components that diffuse into the water below the surface of the water is large, as in the case of “spraying (using) an aqueous solution of medicinal components” as described above. There is a case. On the other hand, if the medicinal components continue to elute outside the sunshine hours, the algae such as blue sea urchins are submerged in the water outside the sunshine hours, so the medicinal components from the algal inhibitor of the present invention floating on the algae There may be cases where the medicinal effect cannot be exerted directly, and the release of medicinal components outside the sunshine hours may be wasted.
It is preferably 30 minutes or more and 9 hours or less in the sunshine hours, more preferably 1 hour or more and 8 hours or less in the sunshine hours, and particularly preferably 2 hours or more and 7 hours or less in the sunshine hours.

  However, a mode in which the release is continued until night (outside the sunshine hours) or in the sunshine hours for 2 days or more is also possible as the method for suppressing algae of the present invention, and is excluded from the method for suppressing algae of the present invention. Is not to be done.

  The algal inhibitor after the medicinal component is released may or may not maintain its shape, but normally maintains its shape. The binder or the coating agent after the medicinal component is released is usually decomposed by microorganisms in water or the like or does not affect the environment.

  The method for suppressing algae according to the present invention can be used in an aqueous environment where it is desired to suppress algae and / or suppress the generation of algae. Examples of water environments include ponds, swamps, lakes, rivers, dams, seas, and the like.

Application rate of algae inhibitor, lysine or malonic acid terms contained in algal inhibitor, preferably 0.1 to 50 g / ^{m 2,} more preferably ^{1~40g / m 2, 10~30g / m} 2 is Particularly preferred.
If the amount applied is too large, the algal inhibitor may be wasted, while if the amount applied is too small, the algae may not be suppressed well.

In addition, 1 g to 100 g of the algae inhibitor is preferably added per 1 m ^{2 of} water, more preferably 5 g to 90 g, and particularly preferably 10 g to 80 g. If the amount applied is too large, the algal inhibitor may be wasted, while if the amount applied is too small, the algae may not be suppressed well.

  From the viewpoint of exerting the effect of the algae inhibitor, the spraying time is preferably performed at the time when the aquatic breeds, and it is preferably sprayed at the time when the water temperature is 15 ° C. or higher.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples unless it exceeds the gist.

Example 1
[Examination of core agent]
The following various binders were added to a medicinal component consisting of lysine hydrochloride and malonic acid to prepare an algal inhibitor. Carboxymethylcellulose sodium (CMCNa) which is a salt of carboxymethylcellulose as “non-environmental pollutant”, calcium chloride (CaCl ₂ ) as “gelling agent”, “polymer derived from natural products” and pectin which is a polysaccharide The core agent was examined using polyvinyl alcohol (PVA), which is neither a “natural product-derived polymer” nor a “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 with respect to the entire 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 then formed into flakes to obtain a core.
Pectin and polyvinyl alcohol (PVA) were also obtained in the same manner as above.

  Ethyl cellulose (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.

The prepared algal inhibitor 0.5 g was added to 500 g of water, and the malonic acid elution rate per hour was measured.
The malonic acid concentration was determined using capillary electrophoresis (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 algal inhibitor used.
Although malonic acid was measured as a representative of the medicinal component, the solubility of the medicinal component as a whole was gradually increased because malonic acid, malonate, lysine, and lysine salt differed only in water solubility. The tendency of release was almost the same in the experiment conducted separately.

The results are shown in FIG. The sustained release of medicinal ingredients was confirmed with all binders. Pectin had a slow release rate and a high ability to gradually release medicinal ingredients. On the other hand, PVA had the highest release rate in the first 30 minutes although it had sustained release properties. 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 the addition of water was compared, when “CMCNa + CaCl ₂ ” was used as the binder, the elution rate had not yet reached 100%. It was suggested that it was excellent in sustained release.

As for the floatability in water, when “CMCNa + CaCl ₂ ” is used as a binder, all the algae inhibitor flakes float in water, but when PVA or pectin is used, there are those that float and sink in water. did.

From the above results, when considering the floating property in water, the control of the elution rate, the environmental load, etc., from the point of control of the elution rate, “CMCNa + CaCl ₂ ” that becomes a gel rather than a PVA that does not become a gel. And pectin must be used, and among them, it was found that it is more preferable to use “CMCNa + CaCl ₂ ” from the viewpoint of floating properties. In addition, PVA has a disadvantage that it has a larger environmental load than others.

  As described above, it was confirmed that polysaccharides, carboxymethylcellulose, silicic acid, or salts thereof were excellent in controlling water floatability and elution rate, but collagen or salts thereof were also suspended in water. Excellent in control of dissolution rate and dissolution rate.

Example 2
[Examination of particle size of algae inhibitor]
Next, the change in the dissolution rate of medicinal ingredients when the algal inhibitor was granulated and the particle size was changed was examined.
An algae inhibitor was prepared by coating EC as a coating agent on a flaky drug granulated by adding CMCNa and calcium chloride to lysine hydrochloride and malonic acid. 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 entire algal inhibitor.
Moreover, the particle size of the algal inhibitor was about 7 mm, 5 mm, and 3 mm, respectively.
And the malonic acid elution rate for every time was measured by the same procedure and method as in Example 1.

  The results are shown in FIG. The larger the particle size, the slower the dissolution rate of medicinal ingredients. Therefore, it was found that the elution time can be controlled by changing the particle size of the inhibitor.

Example 3
[Examination of coating amount of coating agent]
The effect of the coating amount of ethyl cellulose (EC) on the dissolution rate of medicinal ingredients 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 form a slurry, and dry the slurry to form a flake. A core agent was obtained.
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 with respect to the entire algal inhibitor.

The dried core material was coated with EC as a coating agent so as to be 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. . As a comparison, an algae inhibitor not coated with EC (coating agent 0 mass%) was also produced.
And the malonic acid elution rate for every time was measured in the same procedure as Example 1.

The results are shown in FIG. Compared with the algal inhibitor not coated with EC (0%), the elution rate of malonic acid was saturated in about 0.5 hours, and the elution rate reached 80% in about 1 hour. The algal inhibitor coated with EC (1%, 3%, 5%, 10%) took a long time until the elution rate of malonic acid was saturated, and took 3 hours or more until the elution rate reached 80%.
From this result, it was found that the elution rate of the medicinal component can be suppressed by coating the coating agent (EC). It was also shown that the elution rate becomes slower as the coating amount of EC increases.
From the above results, it was found that the elution rate of the medicinal component can be controlled 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 performed, and when fumed silica (hydrophobic silica RX300-5, 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 component was examined. .
The same amount of lysine hydrochloride and malonic acid was dissolved in pure water, and No. 3 sodium silicate was added thereto for gelation. By adding so that the converted mass of the composition formula Na ₂ O contained in the sodium silicate is the same as the mass of malonic acid, gelation can be suitably caused.

The gelled material was granulated and dried to prepare a core agent. The 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% by mass, 3% by mass, 5% by mass, 7% by mass, and 9% by mass with respect to the total mass of the algal inhibitor.
And the malonic acid elution rate for every time was measured by the same procedure and method as in Example 1.

The results are shown in FIG. It was found that the elution rate of malonic acid became slower as the coating amount of FS increased. From this result, it was found that the elution rate can be controlled by the coating amount of FS.
Further, from the results of Example 3 and Example 4, it was found that the elution rate can be slowed and the elution time can be controlled by coating the surface of the algal inhibitor with a coating agent.
It is possible to extend the elution time of the medicinal component as the coating amount is increased. On the other hand, when the coating amount is excessive, the concentration of the medicinal component per hour is small and the elution rate is lowered. The suppression effect 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. It turned out that about 1 mass%-about 7 mass% is the especially preferable range with respect to mass.

  As described above, by using ethyl cellulose (EC) and fumed silica as the coating agent, it was confirmed that the elution rate of the medicinal component can be controlled, but carboxymethyl cellulose calcium, calcium alginate, hydroxy Propylmethylcellulose, cellulose, beeswax and shellac can also be used as a coating agent to control the dissolution rate of medicinal ingredients.

  Since the algae inhibitor of the present invention can be used to suppress algae and algae growth under various water environments, the water environment is managed and adjusted by countries, public organizations, management organizations, companies, etc. It is widely used in the field.

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

Claims (8)

An algae inhibitor that suppresses algae floating on the water surface by floating on the water surface,
A core agent containing at least a medicinal component composed of lysine or lysine salt and malonic acid or malonate, and a binder holding the medicinal component;
A coating agent that is present on the surface of the core agent and controls the sustained release of the medicinal component;
An algae inhibitor characterized by comprising algae.   The algal inhibitor according to claim 1, wherein the binder is a component selected from the group consisting of a “natural product-derived polymer” and a “non-environmental pollutant”.   The algae inhibitor according to claim 1 or 2, wherein the coating agent controls the sustained release rate of the medicinal component and continues to elute the medicinal component for 30 minutes or more after spraying.   The alga according to any one of claims 1 to 3, wherein in the medicinal component, 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. Inhibitor.   The algal inhibitor according to any one of claims 1 to 4, wherein the coating agent is contained in an amount of 1 part by mass or more and 10 parts by mass or less when the total amount of the algal inhibitor is 100 parts by mass. . A method for producing an algal inhibitor according to any one of claims 1 to 5,
A step of adding a polymer and water derived from the above natural product to a powder mixture of medicinal ingredients composed of lysine or lysine salt and malonic acid or malonate to form a slurry, a step of drying the slurry, and granulation The manufacturing method of the algae inhibitor characterized by including the process to do. A method for producing an algal inhibitor according to any one of claims 1 to 5,
Add the above non-environmental pollutant and water to a powder mixture of medicinal ingredients composed of lysine or lysine salt and malonic acid or malonate to form a solution, and then add a gelling agent to the solution to form a gel. The manufacturing method of the algae inhibitor characterized by including the process, the process of drying this gel, and the process of granulating. A method for suppressing algae using the algal inhibitor according to any one of claims 1 to 5,
1 g to 100 g of the algal inhibitor per 1 m ^{2 of} water,
A method for inhibiting algae, comprising controlling a sustained release rate of a medicinal component with a coating agent and allowing the medicinal component to continue to be eluted from the algae inhibitor on the water surface for 30 minutes or more after spraying.

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